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HomeMy WebLinkAboutAGENDA REPORT 2007 1107 CC REG ITEM 10J rr 10. S. City Council Meevn og ACTION: MOORPARK CITY COUNCIL aov? AGENDA REPORT BY: TO: The Honorable City Council FROM: Yugal K. Lail, City Engineer/Public Works Director Prepared by: Shaun Kroes, Management Analys DATE: October 18, 2007 (CC meeting of 11-07-07) SUBJECT: Consider Cost Sharing Memorandum of Agreement for the Calleguas Creek Total Maximum Daily Load Monitoring and Implementation Program and Resolution Amending the Fiscal Year 2007/08 Budget to Fund the Monitoring and Implementation Program SUMMARY The City Council is being asked to approve a Memorandum of Agreement (MOA)with the Cities of Camarillo, Oxnard, Simi Valley and Thousand Oaks, the Camarillo Sanitary District, the County of Ventura, the Ventura County Waterworks District No. 1, Camrosa Water District, the U.S. Department of Navy, the California Department of Transportation (collectively, the Public Agencies), and the Ventura County Agricultural Irrigated Lands Group (Ag Group) for management, funding and cost sharing required for the implementation of the Calleguas Creek Watershed Total Maximum Daily Load (TMDL) Program. DISCUSSION To date, four TMDLs for Calleguas Creek have been adopted by the Los Angeles Regional Water Quality Control Board (RWQCB) and the Environmental Protection Agency (EPA), which include impairments for Nitrogen; Toxicity; Organochlorine Pesticides, PCBs, and Siltation; and Metals. These TMDLs require specific water quality monitoring and implementation actions that must be completed within a specified time frame. The public agencies listed above along with the Ag Group worked collaboratively on these TMDLs and have determined that it would be more cost effective to share in the costs of the required monitoring and implementation program. A MOA has been drafted to allocate the costs among the public agencies and Ag Group based on allocations adopted in the TMDLs and average discharge volume or flow from the dischargers. The MOA attachments are provided under separate cover and have been previously placed in Council Chambers for review. The first year costs for the overall \\MOR_PRI_SERV\City Share\Public Works\Everyone\Staff Reports\2007\November\11-7-2007(TMDL Cost Sharing).doc ()()I-)L() / Honorable City Council November 7, 2007 Page 2 monitoring program is a little more than $1.5 million, of which, Moorpark's contribution is $27,959. The first year costs for implementation is a little over $449,000, of which, Moorpark's contribution is $6,282. This accounts for 1.9 percent and 1.4 percent of the total contributions, respectively. Cost allocation is based on the average annual discharge volume from each responsible entity. The majority of the contributions will come from Ag Group. The Publicly Owned Treatment Works (sanitation plants) are another contributing group, and include County Waterworks, the Camarillo Sanitary District, Camrosa, and the cities of Simi Valley and Thousand Oaks. The Urban dischargers are the third group, which include the County of Ventura, Caltrans, U.S. Navy, and cities of Moorpark, Simi Valley, Thousand Oaks, Camarillo, and Oxnard. The combined cost to the City for the first year of the MOA is $34,241. The City currently has $25,000 budgeted for the TMDL program. Expense Account 1000.8320.0000.9103 includes $8,500 for the Ventura County Environmental Health Department Automotive Business Inspections and $25,000 forthe TMDL program. Staff proposes amending the FY 2007/08 budget by appropriating $15,000 from the General Fund (1000) to cover the cost increase of the TMDL MOA. STAFF RECOMMENDATIONS (Roll Call Vote) 1. Authorize the Mayor to sign the MOA. 2. Adopt Resolution No. 2007 - Attachments: 1. Memorandum of Agreement 2. Resolution No. 2007 - \\MOR_PRI_SERV\City Share\Public Works\Everyone\Staff Reports\2007\November\11-7-2007(TMDL Cost Sharing).doc Attachment 1 MEMORANDUM OF AGREEMENT Management, Funding and Cost Sharing for the Implementation of the Calleguas Creek Watershed Total Maximum Daily Load Program This Memorandum of Agreement("MOA") is entered into effective 2007, by the Camrosa Water District, the Camarillo Sanitary District, the City of Camarillo, the City of Moorpark, the City of Oxnard, the City of Simi Valley, the City of Thousand Oaks, the County of Ventura, the Ventura County Waterworks District No. 1, the U.S. Department of Navy, the California Department of Transportation (collectively, the"Public Agencies") and the Ventura County Agricultural Irrigated Lands Group within the Calleguas Creek Watershed ("Ag Group"), a subdivision of the Farm Bureau of Ventura County ("Farm Bureau"), which together with the Public Agencies are collectively the "PARTIES". The PARTIES agree as follows: RECITALS A. On October 24, 2002, the California Regional Water Quality Control Board, Los Angeles Region ("RWQCB") adopted Resolution No. 2002-017 adopting an Amendment to the Water Quality Control Plan for the Los Angeles Region to include a Total Maximum Daily Load ("TMDL") for Nitrogen Compounds and Related Effects in Calleguas Creek, a copy of which is attached and incorporated as Exhibit A. B. On July 7, 2005, the RWQCB adopted Resolution No. 2005-009 adopting an Amendment to the Water Quality Control Plan for the Los Angeles Region to incorporate a TMDL for Toxicity, Chlorpyrifos, and Diazinon in Calleguas Creek, its tributaries and Mugu Lagoon a copy of which is attached and incorporated as Exhibit B. C. On July 7, 2005, the RWQCB adopted Resolution No. 2005-010 adopting an Amendment to the Water Quality Control Plan for the Los Angeles Region to incorporate a TMDL for Organochlorine Pesticides, Polychorinated Biphenyls, and Siltation in Calleguas Creek, its tributaries and Mugu Lagoon, a copy of which is attached and incorporated as Exhibit C. D. On June 8, 2006, the RWQCB adopted Resolution No. 2006-012 adopting an Amendment to the Water Quality Control Plan for the Los Angeles Region to incorporate a TMDL for Metals for Calleguas Creek, its tributaries, and Mugu Lagoon, a copy of which is attached and incorporated as Exhibit D. E. RWQCB Resolutions 2002-017, 2005-009, 2005-010 and 2006-012 are jointly referred to herein as the "TMDLs". F. The TMDLs are not self-executing and have not been incorporated into existing National Pollutant Discharge Elimination System Permits regarding Waste Discharger Requirements for Municipal Stormwater and Urban Runoff Discharges or Publicly Owned Treatment Works ("POTWs") or the Irrigated Lands Waiver (RWQCB Order No. R4-2005-0080) (jointly referred to herein as the "NPDES Permit") within the Calleguas Creek Watershed ("CCW") in the manner required for the TMDL limits to be legally enforceable. Page 1 of 12 , G. The TMDLs require a monitoring and reporting program plan to be submitted to RWQCB for approval. H. On September 24, 2006 the PARTIES submitted to the RWQCB, in accordance with the requirements of the TMDLs, the Calleguas Creek Watershed Management Plan TMDL Monitoring and Reporting Program's Quality Assurance Program Plan ("QAPP") hereinafter referred to as "Monitoring Plan," which is attached and incorporated as Exhibit E. I. On October 15, 2007, RWQCB approved the Monitoring Plan. J. The PARTIES intend to enter into this MOA to cooperatively establish a joint monitoring and implementation program ("Program") that is consistent with the approved Monitoring Plan and consistent with the TMDLs as they presently exist or are hereafter amended. K. The U.S. Department of the Navy ("Navy") is an agency of the federal government, and therefore may be subject to limitations on its ability or requirement to comply with every provision of this MOA to the same extent that the Public Agencies are able to comply. These limitations are based upon, but not limited to, those identified in the federal Clean Water Act, the federal Antideficiency Act, the principle of sovereign immunity and the holdings of the United States Supreme Court, and other binding federal court decisions, as they interpret those sources of federal law. The limitations so mentioned include, but are not limited to, the availability of federal funding to pay for participation in this program, the ability of the Navy to participate directly in sampling, research or data gathering activities that are not located on Navy or federal lands or a point source of water discharge arising on Navy or federal lands, or other activities not specifically authorized by the federal Clean Water Act. To the extent the limitations described in this paragraph prevent the Navy from fully participating in the Program, it reserves the right, in its sole discretion, to participate in the Program and this MOA as a matter of comity. By entering into this MOA, the Navy does not authorize any of the Public Agencies to exercise regulatory authority over it except to the extent expressly permitted by state or federal law. L. The PARTIES also acknowledge that the obligation of the California Department of Transportation ("Caltrans") to contribute funds under this MOA is subject to the appropriation of funds by the California Legislature and the allocation of funds by the California Transportation Commission. AGREEMENT ARTICLE I — PURPOSE OF AGREEMENT 1.1. The purpose of this MOA is to cooperatively and voluntarily devise and jointly fund a coordinated Program that is consistent with the TMDLs, that implements the Monitoring Plan, and establishes a mechanism for the sharing of the costs associated with the Program. The PARTIES acknowledge that this MOA and the work to be accomplished hereunder is undertaken on a voluntary basis since the TMDL allocations have not been incorporated into the NPDES permits or Irrigated Lands Waiver in the manner required by law to be enforceable. 1.2. "Maximum Extent Practicable" Standard. Nothing in this MOA, nor any activity approved or carried out by the PARTIES hereunder, may be interpreted as a waiver of the position Page 2 of 12 z r„. 1 t x�i 1. . that the efforts undertaken by the PARTIES are not subject to the "Maximum Extent Practicable" standard set forth in the Clean Water Act (33 U.S.C. Section 1251 et seq.). ARTICLE II — RESPONSIBILITIES 2.1. PARTIES. A. The PARTIES agree to designate four discharger groups as follows: 1) POTWs, consisting of Camrosa Water District, Camarillo Sanitary District, Ventura County Waterworks District No. 1, and the Cities of Simi Valley and Thousand Oaks; 2) "Urban Dischargers," consisting of the Cities of Simi Valley, Thousand Oaks, Camarillo, Moorpark and Oxnard and the County of Ventura; 3) "Agricultural Dischargers," consisting of the Ag Group; and 4) "Other Dischargers," consisting of the U.S. Department of Navy and Caltrans. B. The PARTIES agree to form a "Management Committee" consisting of one representative each from the POTWs, Urban Dischargers and Other Dischargers groups and two representatives from the Agricultural Dischargers group. Each discharger group will select its applicable representatives and will also select an alternate representative to serve in the absence of each primary representative in whatever manner each group deems appropriate. The representatives of the discharger groups that consist of Public Agencies will be agency employees with appropriate technical backgrounds or responsibilities relevant to the purposes of the Program. The PARTIES authorize the Management Committee to oversee the Program and make decisions to assure the Program is carried out in a timely, accountable fashion. The PARTIES reserve the authority to adopt the annual budget, and task the Management Committee to diligently concur on a recommended budget annually in order to present a recommended budget to the PARTIES for adoption. The PARTIES further reserve the authority to make substantial changes to each budget and to review and adopt any budget increase during the fiscal year as may be required to implement the Program. C. Annually, the PARTIES must each contribute the funding allocated to their respective agency in accordance with Exhibit F and reflected in Exhibits G and H. Each PARTY's voting power and cost allocations will be based on such PARTY'S actual annual allocated costs. 2.2. MANAGEMENT COMMITTEE. A. The Management Committee will attempt to reach consensus on all issues. If a vote is necessary, each Management Committee member will have one vote. A motion requires four affirmative votes of the Management Committee for passage. The Management Committee representatives will serve a minimum term of one fiscal year starting July 1 through June 30. Each discharger group has the right to choose its representatives, including reappointing incumbent representatives, each fiscal year. B. The Management Committee will implement the Program following the principles and methods provided in this MOA. C. The Management Committee will recommend a budget for the PARTIES approval and funding as provided in this MOA. Page 3 of 12 D. The Management Committee will manage Program task timelines and budgets as provided in the approved budget. The Management Committee will review and recommend budget variances and increases in funding to the PARTIES. E. The Management Committee will select the primary contractors ("Prime Contractors") to implement each element of the Program. The Prime Contractors will be responsible for technical program management in accordance with the requirements of the Monitoring Plans and TMDLs 2.3. FISCAL AGENT. A. The PARTIES will designate a "Fiscal Agent" for the PARTIES by a separate "Fiscal Agent Contract" which will be submitted for approval by the PARTIES. The Fiscal Agent will develop a recommended annual budget for review by the Management Committee, and ultimate approval by the PARTIES. The Fiscal Agent will contract with the selected Prime Contractors to implement the Program consisting of monitoring, laboratory services, data management, reporting, and implementation actions. The PARTIES agree to reimburse the Fiscal Agent for such management services as provided in the budget and the Fiscal Agent Contract. B. The Fiscal Agent must be a public agency and must serve a term of not less than one fiscal year. C. The then current Fiscal Agent may withdraw upon providing written notice to the Management Committee before March 1 St prior to the next fiscal year. D. In the event that the Fiscal Agent withdraws from this MOA, another public agency may serve as successor Fiscal Agent. Any public agency willing to serve as successor Fiscal Agent may be nominated by another PARTY. Selection of a Fiscal Agent must be approved by the Management Committee. E. The Fiscal Agent must act in a timely manner to execute contracts with the Prime Contractor and all other contractors necessary to implement the Program. The Management Committee will select all contractors, and the Fiscal Agent will contract with those selected contractors. Upon the selection of a new Fiscal Agent, if necessary, the new Fiscal Agent will renegotiate all existing contracts to ensure that they are properly assigned to the new Fiscal Agent. F. The Fiscal Agent will be the treasurer of Program funds. The Fiscal Agent, in accordance with generally accepted accounting procedures, must keep the Program funds segregated from any other funds administered by the Fiscal Agent; must credit the Program with appropriate interest income earned on-Program funds in each fiscal year; and may not expend any funds except in accordance with the annual budget approved by the Management Committee or as otherwise directed by the Management Committee. G. By February 1St of each year, the Fiscal Agent must cause to be prepared a projected detailed annual budget for review and recommended approval by the Management Committee, and ultimate approval by the PARTIES, for the following fiscal year, as described under Section 3.1.B. The Fiscal Agent will retain all fiscal records for five years and make those records available for review by any PARTY upon request. Page 4 of 12 H. The Fiscal Agent must provide a copy of any contract executed on behalf of the PARTIES to the Management Committee upon request. I. The Fiscal Agent may request under its agreement with the PARTIES, and as part of the annual Program budget, reimbursement for reasonable and customary costs incurred in providing the services under this MOA. Reimbursement to the Fiscal Agent will be subject to Management Committee review and approval as part of the Program budget. J. The Fiscal Agent will cause to be prepared an annual audit of expenditures and a report regarding the-Program and submit such audit and report to the Management Committee within 90 days of the close of each fiscal year. 2.4. DOCUMENTATION. The PARTIES agree to provide all readily available information and documentation that is deemed necessary to perform the Program. 2.5. GRANT OF ACCESS RIGHTS. During the term of this MOA, the PARTIES (including all members of the Ag Group) will grant the right of access and entry to all monitoring locations to the Prime Contractors or any other contractor retained by the Fiscal Agent at all reasonable times for the purposes of collecting monitoring data consistent with the Monitoring Plan subject to all applicable laws of such PARTY. Any Public Agency or Prime Contractor intending to enter onto another PARTY's right-of-way, property or easement must first make a written request to the affected PARTY, identifying the site location, extent of access by persons (and equipment if any), dates and times of entry, as well as an explanation of the purpose of that entry. The affected PARTY will then determine, within 10 working days, if that entry will require a formal encroachment permit or other approval. If a formal permit or approval is required, the Public Agency or Prime Contractors must obtain such permit or approval. If a formal permit or approval is not required based on that PARTY's applicable law, the affected PARTY may still condition the right of entry on the accompaniment of a representative of the affected PARTY, who may restrict or limit the access to those persons deemed necessary at the sole discretion of the affected PARTY. ARTICLE III — FUNDING, COST& DATA SHARING 3.1. FUNDING. A. The PARTIES agree to provide funding for the costs of the Program including the services performed by the Prime Contractor and any other contractor retained by the Fiscal Agent consistent with each PARTY's percentage allocation as set forth in Exhibit F and reflected in Exhibits G and H. B. The monitoring cost estimate for the initial Program year is attached as Exhibit G. The implementation cost estimate for the initial Program year is attached as Exhibit H. If the initial year actual budget exceeds the projected costs in Exhibits G and H, the Management Committee will develop a recommendation and call for a vote of the PARTIES to approve a revised budget. After the initial year, the applicable Prime Contractor and the Fiscal Agent will prepare a draft annual budget. The Fiscal Agent will facilitate budget review by the Management Committee and, upon the Management Committee reaching agreement, presentation of the recommended annual budget to the PARTIES. Once the PARTIES reach a two-thirds majority agreement on the recommended annual budget based on the PARTIES' percentage allocations, the budget will be considered an approved annual budget for the following fiscal year. The applicable Prime Contractor and Fiscal Agent will be provided a draft budget deadline by Page 5 of 12 the Management Committee to provide sufficient time for review of the recommended Annual Budget to allow for its timely passage prior to June 30 annually. C. The Fiscal Agent will provide timely notice of fund transfers necessary to meet budgeted activities. D. The PARTIES understand and agree that the Farm Bureau of Ventura County has no specific or direct liability for the funds to be paid by the Ag Group within the Calleguas Creek Watershed pursuant to this MOA. The Farm Bureau is a facilitator with the Regional Water Quality Control Board in an Irrigated Agricultural Lands Waiver Program for properties within Ventura County, including properties within the CCW. The Farm Bureau cannot ensure that all irrigated agricultural property within the CCW is participating in, or will participate in the Ag Group. The Ag Group is the entity from which the Farm Bureau will collect funds due under this MOA. In such capacity as a facilitator, the Farm Bureau cannot ensure or guarantee that all funds due from agriculture pursuant to this MOA will be collected. The Farm Bureau will use its best efforts to secure the greatest amount of participation by agricultural property within the CCW and the collection of funds due and owing under this MOA. E. To the extent a PARTY fails to timely pay all or a portion of such PARTY's cost allocation, the Management Committee must direct the applicable Prime Contractors to reduce to the extent feasible the Program monitoring and implementation activities that directly apply to such PARTY in proportion to the reduction in contributions from such PARTY. Under no circumstances will any PARTY be required to increase its contribution based on the failure of another PARTY to pay all or a portion of its cost allocation. 3.2. CONTRACT FOR SERVICES. A. The Management Committee will assist the Fiscal Agent in issuing requests for proposals, negotiating contracts, and selecting the Prime Contractors and any other contractors. If bids for the initial year of any subsequent fiscal year costs exceed the estimates in Exhibits G and H by more than ten percent (10%), the Management Committee must notify the PARTIES and request the PARTIES' direction on approval of additional funds. Payment for contract activities may only be made upon review and approval by the Management Committee of invoices submitted by the Prime Contractors and all other contractors. B. All Prime Contractors and all other contractors will be retained by contract with the Fiscal Agent. The Fiscal Agent will disburse funds to contractors within 30 days after approval of the invoice by the Management Committee. The Fiscal Agent will perform this role for the administrative convenience of the PARTIES. C. Invoice and Payment. All costs for the Program are to be shared based upon each PARTY's percentage allocation as set forth in Exhibit F. Fifty percent (50%) of each PARTY's share of first year costs as set forth in Exhibits G and H will be invoiced by, and is due and payable to the Fiscal Agent from each PARTY upon the effective date of this MOA, and the remaining fifty percent (50%) is due after six months from the effective date of the MOA. Subsequent annual budget costs will be due and payable to the Fiscal Agent within 45 days of receipt of the invoice, or upon such other terms as the Management Committee may approve. Page 6 of 12 3.3 DATA SHARING. It is the intent of the PARTIES that the monitoring data collected will remain in draft form until released to the RWQCB under the PARTIES' NPDES permits and the Irrigated Lands Waiver. Prior to such disclosure, no PARTY may share the monitoring data generated from the Program with members of the public without first obtaining permission from the Management Committee. ARTICLE IV— GENERAL PROVISIONS 4.1. TERM. The effective date of this MOA is the date first above written. The initial term of the MOA will continue for a period of five years from the effective date. Thereafter, the MOA will automatically renew upon the anniversary of the effective date upon consensus of the PARTIES until terminated in the manner provided for in this MOA 4.2. WITHDRAWAL. A. Any PARTY may withdraw from this MOA by providing written notice to the Management Committee on or before: (i) March 1 in any year; (ii) 30 days from notice of the Management Committee's recommended annual budget; or (iii) 15 days from any other PARTY's notice of withdrawal . If notice is timely given, the withdrawal will become effective at the beginning of the next fiscal year. B. Any PARTY that withdraws from this MOA will remain liable for that PARTY's share of the costs under this MOA through the end of the then current fiscal year. C. The withdrawing PARTY will be responsible for all lawfully assessed penalties on such PARTY as a consequence of and subsequent to the withdrawal. The withdrawing PARTY will also be responsible for fulfilling all requirements of the Program applicable to such withdrawing PARTY. D. Upon withdrawal or delay in adoption of the MOU by any PARTY, the Management Committee will revise the cost sharing formula set forth in Exhibit F to equitably reduce or reapportion the withdrawing PARTY's contribution among the remaining PARTIES. 4.3. AMENDMENTS. During the term of this MOA, any PARTY may request that the other PARTIES negotiate, in good faith, modifications to the MOA that may be reasonably necessary because of changed circumstances. Any amendment to this MOA must be in writing and must be consented to by all PARTIES. Upon such consent, the amendment must be executed by each Party within three months of notice by the Management Committee. 4.4. NOTICES. Any notices, bills, invoices, or reports relating to this MOA, and any request, demand, statement or other communication required or permitted hereunder must be in writing and must be delivered to the representatives of the PARTIES at the addresses set forth in Exhibit I attached hereto. A notice will be deemed to have been received on (a) the day of delivery, if delivered by hand during regular business hours or by confirmed facsimile; or(b) on the third business day following deposit in the United States mail, postage prepaid. Page 7 of 12 P- !, 04 ' 4.5. RELATIONSHIP OF THE PARTIES. The PARTIES are, and will at all times remain as to each other, wholly independent entities. No PARTY has the power to incur any debt, obligation, or liability on behalf of any other PARTY unless expressly provided to the contrary by this MOA. No employee, agent, or officer of a PARTY will be deemed for any purposes whatsoever to be an agent, employee or officer of another PARTY. 4.6. COOPERATION, FURTHER ACTS. The PARTIES agree to cooperate fully with one another to attain the purposes and objectives of this MOA. 4.7. INDEMNIFICATION. Each PARTY will be solely responsible and liable for its individual obligations under this MOA. Each PARTY agrees to indemnify, defend, and hold the other PARTIES harmless for all losses, claims, and liability including attorney fees and costs, arising to the extent of the negligence or willful misconduct of the indemnifying PARTY. 4.8. EXECUTION OF COUNTERPARTS. This MOA may be executed in counterparts, each of which will be deemed an original, but together will constitute one and the same instrument. 4.9. GOVERNING LAW. This MOA is governed by the laws of the State of California. 4.10. SEVERABILITY. If any provision of this MOA is determined by any court to be invalid, illegal, or unenforceable to any extent, the remainder of this MOA will not be affected will be construed as if the invalid, illegal or unenforceable provision had never been contained in this MOA. (Signatures on following pages) Page 8 of 12 IN WITNESS WHEREOF, the PARTIES have caused this MOA to be executed on their behalf as of the date specified below, respectively, as follows: CAMROSA WATER DISTRICT Date: APPROVED AS TO FORM: By: By: Chair, Board of Directors General Counsel CAMARILLO SANITARY DISTRICT Date: APPROVED AS TO FORM: By: By: Chair, Board of Directors General Counsel CITY OF CAMARILLO Date: APPROVED AS TO FORM: By: By: Mayor, City Council City Attorney CITY OF MOORPARK Date: APPROVED AS TO FORM: By: By: Mayor, City Council City Attorney CITY OF OXNARD Date: APPROVED AS TO FORM: By: By: Mayor, City Council City Attorney CITY OF SIMI VALLEY Page 9 of 12 CIO Date: APPROVED AS TO FORM: By: By: Mayor, City Council City Attorney CITY OF THOUSAND OAKS Date: APPROVED AS TO FORM: By: By: Mayor, City Council City Attorney COUNTY OF VENTURA Date: APPROVED AS TO FORM: By: By: Chair, Board of Supervisors County Counsel VENTURA COUNTY WATERWORKS DISTRICT NO. 1 Date: APPROVED AS TO FORM: By: By: Chair, Board of Directors General Counsel UNITED STATES DEPARTMENT OF NAVY Date: APPROVED AS TO FORM: By: By: General Counsel VENTURA COUNTY AGRICULTURAL IRRIGATED LANDS GROUP, a subdivision of the Farm Bureau of Ventura County Date: APPROVED AS TO FORM: By: By: General Counsel STATE OF CALIFORNIA Department of Transportation Page 10 of 12 Will Kempton Director of Transportation By Douglas R. Failing District Director Approved as to Form & Procedure: By: William B. Bassett Attorney Certified as to Funds: By: District Budget Manager Certified as to Financial Terms and Conditions: By: Accounting Administrator Page 11 of 12 LIST OF EXHIBITS Exhibit A: RWQCB Resolution 02-017 — Nutrient TMDL Exhibit B: RWQCB Resolution R4-2005-009 —Toxicity TMDL Exhibit C: RWQCB Resolution R4- 2005-010 — Pesticides TMDL Exhibit D: RWQCB Resolution R4 - 2006-012 — Metals TMDL Exhibit E: CCWMP TMDL Monitoring QAPP Exhibit F: Program Cost Percentage Allocation to each PARTY Exhibit G: Estimate of First Year Program Monitoring Costs Exhibit H: Estimate of First Year Program Implementation Costs Exhibit I: PARTY Representatives Page 12 of12 Attachment 2 RESOLUTION NO. 2007- A RESOLUTION OF THE CITY COUNCIL OF THE CITY OF MOORPARK, CALIFORNIA, AMENDING THE FISCAL YEAR 2007108 BUDGET BY APPROPRIATING $15,000 FROM GENERAL FUND (1000) FOR TMDL MONITORING & IMPLEMENTATION PROGRAM WHEREAS, on June 20, 2007, the City Council adopted the budget for Fiscal Year 2007/2008; and WHEREAS, on November 7, 2007, the City Council approved the Cost Sharing Memorandum of Agreement for the Calleguas Creek TMDL Monitoring & Implementation Program; and WHEREAS, Exhibit "A" attached hereto and made a part hereof, describes said budget amendment and its resultant impacts to the budget line items. NOW, THEREFORE, THE CITY COUNCIL OF THE CITY OF MOORPARK DOES HEREBY RESOLVE AS FOLLOWS: SECTION 1. That a budget amendment in the aggregate increase of $15,000., as described in Exhibit "A" attached hereto, is hereby approved. SECTION 2. The City Clerk shall certify to the adoption of this resolution and shall cause a certified resolution to be filed in the book of original Resolutions. PASSED AND ADOPTED this 7th day of November, 2007. Patrick Hunter, Mayor ATTEST: Deborah S. Traffenstedt, City Clerk Resolution No. 2007- Page 2 EXHIBIT A BUDGET AMENDMENT FOR COST SHARING MEMORANDUM OF AGREEMENT FOR THE CALLEGUAS CREEK TMDL MONITORING & IMPLEMENTATION PROGRAM FY 2007/08 FUND ALLOCATION FROM: Fund Account Number Amount General Fund 1000-5500 $15,000.00 Total $15,000.00 DISTRIBUTION OF APPROPRIATION TO EXPENSE ACCOUNTS: Account Number Current Budget Revision Amended Budget 1000.8320.0000.9103 $33,500.00 $15,000.00 $48,500.00 Total $33,500.00 $15,000.00 $48,500.00 Approved.-�� �-, f Exhibit A State of California California Regional Water Quality Control Board,Los Angeles Region RESOLUTION NO. 02-017 October 24,2002 Amendment to the Water Quality Control Plan for the Los Angeles Region to include a TMDL for Nitrogen Compounds and Related Effects in Calleguas Creek WFIEREAS,the California Regional Water Quality Control Board,Los Angeles Region,finds that: 1. The federal Clean Water Act(CWA)requires the California Regional Water Quality Control Board(Regional Board)to develop water quality standards which include beneficial use designations and criteria to protect beneficial uses for each water body found within its region. 2. The Regional Board carries out its CWA responsibilities through California's Porter- Cologne Water Quality Control Act and establishes water quality objectives designed to protect beneficial uses contained in the Water Quality Control Plan for the Los Angeles Region(Basin Plan). 3. Section 303(d) of the CWA requires states to identify and to prepare a list of water bodies that do not meet water quality standards and then to establish load and waste load allocations,or a total maximum daily load(TMDL),for each water body that will ensure attainment of water quality standards and then to incorporate those allocations into their water quality control plans. 4. Calleguas Creek was listed on California's 1998 section 303(d)list,due to impairment for nitrogen compounds and their effects that do not protect the most sensitive beneficial uses of the water body. 5. A consent decree between the U.S. Environmental Protection Agency(USEPA),Heal the Bay,Inc., and BayKeeper,Inc.was approved on March 22, 1999. The court order directs the USEPA to complete TMDLs for all the Los Angeles Region's impaired waters within 13 years. 6. The elements of a TMDL are described in 40 CFR 130.2 and 130.7 and section 303(d)of the CWA,as well as in USEPA guidance documents(e.g.,USEPA, 1991). A TMDL is defined as"the sum of the individual waste load allocations for point sources and load allocations for nonpoint sources and natural background"(40 CFR 130.2). Regulations further stipulate that TNIDLs must be set at"levels necessary to attain and maintain the applicable narrative and numeric water quality standards with seasonal variations and a margin of safety that takes into account any lack of knowledge concerning the relationship between effluent limitations and water quality"(40 CFR 130.7(c)(1)). The regulations in 40 CFR 130.7 also state that August 30,2002 Revised: October 24,2002 Resolution No. 02-017 Page 2 TMDLs shall take into account critical conditions for stream flow,loading and water quality parameters. 7_ Upon establishment of TMDLs by the State or USEPA,the State is required to incorporate the TMDLs along with appropriate implementation measures into the State Water Quality Management Plan(40 CFR 130.6(c)(1), 130.7). The Basin Plan, and applicable statewide plans serve as the State Water Quality Management Plans governing the watersheds under the jurisdiction of the Regional Board. 8. Calleguas Creek is located in Ventura County,California. It reaches from the Simi Hills east of the City of Simi Valley to Mugu Lagoon south of the City of Oxnard. 9. The Regional Board's goal in establishing the above-mentioned TMDL is to maintain the warm water fish and wildlife habitat(WARM,WILD)and groundwater recharge (GWR)beneficial uses of Calleguas Creek as established in the Basin Plan. Additionally,ammonia is known to cause toxicity to aquatic organisms. 10.Interested persons and the public have had reasonable opportunity to participate in review of the amendment to the Basin Plan. Efforts to solicit public review and comment include ten public workshops held between January 1999 and February 2002;public notification 45 days preceding the Board hearing; and responses from the Regional Board staff to oral and written comments received from the public. 11. The amendment is consistent with the State Antidegradation Policy(State Board Resolution No. 68-16),in that the changes to water quality objectives(i)consider maximum benefits to the people of the state,(ii)will not unreasonably affect present and anticipated beneficial use of waters, and(iii)will not result in water quality less than that prescribed in policies. Likewise,the amendment is consistent with the federal Antidegradation Policy(40 CFR 131.12), 12.The basin planning process has been certified as functionally equivalent to the California Environmental Quality Act requirements for preparing environmental documents and is,therefore, exempt from those requirements(Public Resources Code section 21000 et seq.),and the required environinemtal documentation and environmental checklist have been prepared. 13.The proposed amendment results in no potential for adverse effect(de minimis finding), either individually or cumulatively,on wildlife. 14. The regulatory action meets the"Necessity"standard of the Administrative Procedures Act, Government Code section 11353,subdivision(b). 15.The Basin Plan amendment incorporating a TMDL for nitrogen compounds and related effects for the Calleguas Creek watershed must be submitted for review and approval by the State Water Resources Control Board(State Board),the State Office of Administrative Law(OAL), and the US Environmental Protection Agency August 30,2002 Revised: October 24,2002 Resolution No. 02-017 Page 3 (USEPA). The Basin Plan amendment will become effective upon approval by ORAL and USEPA.A Notice of Decision will be filed. THEREFORE,be it resolved that pursuant to Section 13240 and 13241 of the Water Code,the Regional Board hereby amends the Basin Plan as follows: 1. Pursuant to sections 13240 and 13241 of the California Water Code,the Regional Board, after considering the entire record,including oral testimony at the hearing, hereby adopts the amendment to Chapter 7 the Water Quality Control Plan for the Los Angeles Region to incorporate the elements of the Calleguas Creek Nitrogen Compounds and Related Effects TMDL as set forth in Attachment A hereto. 2. The Executive Officer is directed to forward copies of the Basin Plan amendment to the SWRCB in accordance with the requirements of section 13245 of the California Water Code. 3. The Regional Board requests that the SWRCB approve the Basin Plan amendment in accordance with the requirements of sections 13245 and 13246 of the California Water Code and forward it to OAL and the USEPA. 4. if during its approval process the SWRCB or OAL determines that minor,non- substantive corrections to the language of the amendment are needed for clarity or consistency,the Executive Officer may make such changes, and shall inform the Board of any such changes. 5. The Executive Officer is authorized to sign a Certificate of Pee Exemption. 6. Amend the text in the Basin Plan,Plans and Policies(Chapter 5)to add: "Resolution No.02-017. Adopted October 24,2002. 'Amendment to include a TMDL for Nitrogen Compounds and Related Effects for Calleguas Creek' The resolution proposes a TMDL for nitrogen compounds and related effects in Calleguas Creek." 7. The Basin Plan amendment set forth in Attachment A shall only become effective if the water quality objectives revised by Regional Board Resolution 2002-011,or equivalent water quality objectives,have been approved by the OAL and USEPA, and are consistent with the TMDL. August 30,2002 Revised: October 24,2002 Resolution No. 02-017 Page 4 I,Dennis A.Dickerson,Executive Officer,do hereby certify that the foregoing is a frill, true, and correct copy of a resolution adopted by the California Regional Water Quality Control Board,Los Angeles Region,on October 24,2002. Dennis A.Dickerson Executive Officer August 30,2002 Revised: October 24,2002 Attachment A to Resolution No. 02-017 Proposed Amendment to the Water Quality Control Plan—Los Angeles Region to Incorporate the Calleguas Creek Nitrogen Compounds and Related Effects TMDL Adopted by the California Regional Water Quality Control Board, Los Angeles Region on October 24, 2002, Amendments Table of Contents Add: Chapter 7. Total Maximum Daily Loads (TMDLs) 7-7 Calleguas Creek Nitrogen Compounds and Related Effects TMDL List of Figures,Tables,and Inserts Add: Chapter 7. Total Maximum Daily Loads (TMDLs) Tables 7-7 Calleguas Creek Nitrogen Compounds and Related Effects TMDL 7-7.1. Calleguas Creek Nitrogen Compounds and Related Effects TMDL: Elements 7-7.2. Calleguas Creek Nitrogen Compounds and Related Effects TMDL: Implementation Schedule Chapter 7. Total Maximum Daily Loads (TMDLs) Calleguas Creek Nitrogen Compounds and Related Effects TMDL This TMDL was adopted by: The Regional Water Quality Control Board on October 24, 2002. This TMDL was approved by: The State Water Resources Control Board on March 19, 2003. The Office of Administrative Law on June 5, 2003. The U.S. Environmental Protection Agency on June 20, 2003. August 30, 2002 Revised: October 24, 2002 Resolution No. 02-017 Page 2 Table 7-7.1. Calleguas Creek Nitrogen Compounds and Related Effects TMDL: Elements Element Calleguas Creek Nitrogen Compound and Related Effects Problem Elevated nitrogen concentrations (ammonia, nitrite and nitrate) are Statement causing impairments of the warm water fish and wildlife habitat, and groundwater recharge beneficial uses of Calleguas Creek. Nitrite and nitrate contribute to eutrophic effects such as low dissolved oxygen and algae growth. Ammonia contributes to toxicity. Numeric Target Numeric targets for this TMDL are listed as follows: (Interpretation of the numeric 1. Total Ammonia as Nitrogen (NH3-N) water quality NH3-N concentration(mg/L) objective, used One-hour Thirty-day to calculate the Reach average average load * Mugu Lagoon 8.1 2.9 allocations) * Calleguas Creek,South 5.5 2.4 * Calleguas Creek,North 8.4 3.0 * Revlon Slough 5.7 2.9 * Beardsley Channel 5.7 2.9 * Arroyo Las Posas 8.1 2.6 * Arroyo Simi 4.7 2.4 * Tapo Canyon 3.9 1.9 * Conejo Creek(Confluence with Calleguas 9.5 3.5 Creek to Santa Rosa Rd.) * Conejo Creek(Santa Rosa Road 8.4 3.4 to Thousand Oaks City Limit) * Conejo Creek,Hill Canyon Reach 8.4 3.1 * Conejo Creek,North Fork 3.2 1.7 * Arroyo Conejo(South Fork Conejo Creek) 5.1 3.4 * Arroyo Santa Rosa 5.7 2.4 2. Nitrate and nitrite as nitrogen (NO3-N and NO2-N) Constituent Concentration(mg/L) • NO3-N 10 • NO2-N 1 • NO3-N+NO2-N 10 Numeric targets to address narrative objectives required to protect warm freshwater and wildlife habitat are intended to implement the narrative objectives and may be revised based on the results of monitoring and special studies conducted pursuant to the implementation plan. August 30, 2002 Revised: October 24, 2002 Resolution No. 02-017 Page 3 Source Analysis The principal sources of nitrogen into Calleguas Creek are discharges from the POTWs in the watershed and runoff from agricultural activities in the watershed. Linkage Linkage between nitrogen sources and the in-stream water quality was Analysis established through a mass continuity model based on an evaluation of recent hydrodynamic and water quality data. Waste Load The waste load allocations (WLAs) are as follows: Allocations (for Concentration(mg/L) point sources) 1 NH3-N NO3-N NO2-N NO3-N+NO2-N MDEL AMEL` Daily WLA POTWS (mg/L) (lb/day) (mg/L) • Hill Canyon WTP3 5.6 3.1 254 9.0 0.9 9.0 • Simi Valley WQCF4 3.3 2.4 220 9.0 0.9 9.0 • Moorpark WTP 6.4 2.6 59 9.0 0.9 9.0 • Camarillo WRP5 7.8 3.5 177 9.0 0.9 9.0 • Camrosa WRF 6 7.2 3.0 33 9.0 0.9 9.0 Load Allocation The source analysis indicates that agricultural discharge is the major non- (for non point point source of oxidized nitrogen to Calleguas Creek and its tributaries. sources) This source is particularly significant in Revolon Slough and other agricultural drains in the lower Calleguas watershed where there are no point sources of ammonia and oxidized nitrogen. Load allocations for non-point sources are: NO3-N+NO2-N Nonpoint Source (mg/L) Agriculture 9.0 Other Nonpoint Source 9.0 Implementation 1. Refer to Table 7-7.2 2. Several of the POTWs in the Calleguas Creek watershed will require additional time to meet the nitrogen (NO3-N, NO2-N, and NO3-N + NO2-N) waste load allocations. To allow time to meet the nitrogen waste load allocations,interim limits will be allowed for a period of four years from the effective date of the TMDL during which the POTWs will be required to meet the effluent limit for NO3-N+NO2- N only. Effluent limits for the individual compounds NO3-N and 1 MDEL:Maximum daily effluent limitation 2 AMEL:Average monthly effluent limitation 3 WTP:Wastewater Treatment Plant 4 WQCF:Water Quality Control Facility 5 WRP:Water Reclamation Plant 6 WRF:Water Reclamation Facility August 30, 2002 Revised: October 24, 2002 Resolution No. 02-017 Page 4 NO2-N are not required during the interim period. Interim Limits'for NO3-N+NO2-N Monthly Average Daily Maximum POTWs (mg/L) (mg/L) • Hill Canyon WTP 36.03 38.32 • Simi Valley WQCF 31.60 32.17 • Moorpark WTP 31.5 32.01 • Camarillo WRP 36.23 37.75 *The monthly average and daily maximum interim limits are based on the 95`x'and 99`h percentiles of effluent performance data reported in the Calleguas Creek Characterization Study 3. The waste load allocations for ammonia will be applicable on the effective date of the TMDL. Interim limits for ammonia will be applicable for no more than 2 years starting from October 24, 2002 for POTWs that are not able to achieve immediate compliance with the assigned waste load allocations. The interim limits for ammonia may be established at the discretion of the Regional Board when a POTW's NPDES permit is reissued. Margin of An implicit margin of safety is incorporated through conservative model Safety assumptions and statistical analysis. In addition, an explicit margin of safety is incorporated by reserving 10% of the load, calculated on a concentration basis, from allocation to POTW effluent sources. Seasonal A low flow critical condition is identified for this TMDL based on a Variations and review of flow data for the past twenty years. This flow condition was Critical identified because less assimilative capacity is available to dilute effluent Conditions discharge. August 30, 2002 Revised: October 24, 2002 Resolution No. 02-017 Page 5 Table 7-7.2. Implementation Schedule IMPLEMENTATION TASKS,MILESTONES AND COMPLETION DATE; PROVISIONS 1. WLA for ammonia apply to POTWs. Effective Date of TMDL 2. Interim Limits for NO3-N+NO2-N apply to POTWs. 3. Formation of Nonpoint Source BMP Evaluation Committee. 4. Submittal of Non point Source Monitoring 1 year after Effective Date Workplan by Calleguas Creek Watershed of TMDL Management Plan — Water Resources/Water Quality (CCWMP) Subcommittee. This monitoring is to evaluate nutrient loadings associated with agricultural drainage and other nonpoint sources. The monitoring program will include both dry and wet weather discharges from agricultural, urban and open space sources. In addition, groundwater discharge to Calleguas Creek will also be analyzed for nutrients to determine the magnitude of these loading and the need for load allocations. A key objective of these special studies will be to determine the effectiveness of agricultural BMPs in reducing nutrient loadings. Consequently, flow and analytical data for nutrients will be required to estimate loadings from nonpoint sources. 5. Submittal of Watershed Monitoring Workplan by CCWMP Subcommittee. In addition to the analytical parameters and flow data requirements, the watershed monitoring program will establish sampling locations from which representative samples can be obtained, including all listed tributaries. Monitoring results will be compared to the numeric instream targets identified in this TMDL to determine the effectiveness of the TMDL. Data on the extent and distribution of algal mats, scum and odors will be included in the watershed monitoring program. The data will be The CCWMP Subcommittee has offered to complete tasks 4 through 9 and 11. In the event the CCWMP Subcommittee fails to timely complete these tasks,the Regional Board will consider whether to amend this Implementation Plan to assign tasks to responsible dischargers in the regulatory approach. The Regional Board also reserves its right to take any other appropriate actions including,but not limited to,exercising its authorities under Water Code section 13267. August 30, 2002 Revised: October 24, 2002 Resolution No. 02-017 Page 6 IMPLEMENTATION'TASKS,MILESTONES AND COMPLETION DATE' PROVISIONS ` used to provide further verification of the model and refine the TMDL to address nutrient effects as appropriate. 6. Submittal of Special Studies Workplan by CCWMP Subcommittee. These special studies include: Monitoring of minor point sources for nutrients to confirm assumptions that the loadings from these sources are minor; Monitoring of greenhouse discharges and runoff to assess loadings from these sources; Monitoring of groundwater extraction and discharges in the Arroyo Santa Rosa subwatershed and other areas that may add significant nutrient loadings to Calleguas Creek; and Additional studies of the type and extent of algae impairment in Calleguas Creek and Mugu Lagoon. 7. Complete Special Studies for minor sources, 3 years after Effective Date greenhouses, and groundwater loadings. of TMDL 8. Completion of ammonia Water Effect Ratio (WER) studies. 9. Complete planning and preparation for construction of TMDL remedies to reduce non- point source nitrogen loads. 10. Interim Limits for NO3-N+NO2-N expire and 4 years after Effective Date WI-As for NO3-N, NO2-N, NO3-N+NO2-N apply of TMDL to POTWs. 11. Complete Special Studies for algae impairments of 5 years after Effective Date Calleguas Creek, its tributaries and Mugu Lagoon. of TMDL 12. Regional Board consideration of revised water 6 years after Effective Date quality objectives for nitrogen compounds based of TMDL on monitoring data, special studies, and ammonia WER, if appropriate. 13. Final achievement of ammonia and oxidized 7 years after Effective Date nitrogen standards. of TMDL August 30, 2002 Revised: October 24, 2002 Exhibit B State of California California Regional Water Quality Control Board, Los Angeles Region RESOLUTION NO. R4-2005-009 July 7, 2005 . Amendment to the Water Quality Control Plat:for the Los Angeles Region to Incorporate a Total Maximum Daily Load for Toxicity,Chlorpyrifos,and Diazinon in Calleguas Creek its Tributaries and Mugu Lagoon WHEREAS, the California Regional Water Quality Control Board, Los Angeles Region, finds that: 1. The Federal Clean Water Act(CWA)requires the California Regional Water Quality Control Board, Los Angles Region (Regional Board) to develop water quality objectives, which are sufficient to protect beneficial uses for each water body found within its region. 2. A consent decree between the U.S. Environmental Protection Agency (USEPA), Heal the Bay, Inc. and BayKeeper, Inc. was approved on March 22, 1999. This court order directs the USEPA to complete Total Maximum Daily Loads(TMDLs) for all impaired waters within 13 years. A schedule was established in the consent decree for the completion of the first 29 TMDLs within 7 years, including completion of a TMDL to reduce toxicity, chlorpyrifos, and diazinon in the Calleguas Creek Watershed by March 22, 2006. The remaining TMDLs will be scheduled by Regional Board staff within the 13-year period. 3. The elements of a TMDL are described in 40 CFR 130.2 and 130.7 and section 303(d) of the CWA, as well as in USEPA guidance documents (Report No. EPA/440/4-91/001). A TMDL is defined as the sum of the individual waste load allocations for point sources, load allocations for nonpoint sources and natural background(40 CFR 130.2). Regulations further stipulate that TMDLs must be set at levels necessary to attain and maintain the applicable narrative and numeric water quality standards with seasonal variations and a margin of safety that takes into account any lack of knowledge concerning the relationship between effluent limitations and water quality (40 CFR 130.7(c)(1)). The regulations in 40 CFR 130.7 also state that TMDLs shall take into account critical conditions for stream flow, loading and water quality parameters. 4. The numeric targets in this TMDL are not water quality objectives and do not create new bases for enforcement against dischargers apart from the water quality objectives they translate. The targets merely establish the bases through which load allocations (LAs) and waste load allocations (WLAs) are calculated. WLAs are only enforced for a discharger's own discharges, and then only in the context of its National Pollutant Discharge Elimination System(NPDES)permit, which must be consistent with the assumptions and requirements of the WLA. The Regional Board will develop permit requirements through a subsequent permit action that will allow all interested persons, including but not limited to municipal storm water dischargers,to provide comments on how the WLA will be translated into permit requirements. 5. Upon establishment of TMDLs by the State or USEPA, the State is required to incorporate the TMDLs along with appropriate implementation measures into the State Water Quality Resolution No.R4-2005-009 Page 2 Management Plan (40 CFR 130.6(c)(1), 130.7). This Water Quality Control Plan for the Los Angeles Region (Basin Plan), and applicable statewide plans, serves as the State Water Quality Management Plans governing the watersheds under the jurisdiction of the Regional Board. 6. The SWRCB adopted Policy for Implementation of Toxics Standards for Inland Surface Waters, Enclosed Bays, and Estuaries of California (also known as the State Implementation Plan or SIP) on March 2, 2000. The SIP was amended by Resolution No. 2000-30, on April 26,2000, and the Office of Administrative Law approved the SIP on April 28,2000. The SIP applies to discharges of toxic pollutants in the inland surface waters, enclosed bays and estuaries of California which are subject to regulation under the State's Porter-Cologne Water Quality Control Act (Division 7 of the Water Code) and the Federal Clean Water Act. This policy also establishes the following: implementation provisions for priority pollutant criteria promulgated by USEPA through the CTR and for priority pollutant objectives established by Regional Water Quality Control Boards in their water quality control plans (Basin Plans) and chronic toxicity control provisions. 7. On May 18, 2000, the U.S. EPA promulgated the numeric criteria for priority pollutants for the State of California, known as the California Toxics Rule (CTR) and as codified as 40 CFR section 131.38. 8. The Calleguas Creek Watershed is located in southeast Ventura County, California, and in a small portion of western Los Angeles County, and drains an area of approximately 343 square miles from the Santa Susana Pass in the east, to Mugu Lagoon in the southwest. Current land use is approximately 26 percent agriculture, 24 percent urban, and 50 percent open space. The tributaries and the streams of the Calleguas Creek Watershed are divided into fourteen segments, or reaches. The 2002 Clean Water Act 303(d) list identified six reaches as impaired for water column toxicity,two for sediment toxicity, two for chlorpyrifos in fish tissue, and one for organophosphate pesticides in water. These listings were approved by the State Water Resources Control Board on February 4,2003. 9. The Regional Board's goal in establishing the Calleguas Creek Toxicity TMDL is to determine and set forth measures needed to prevent impairment of water quality due to water column toxicity in all impaired reaches by requiring reductions in diazinon and chlorpyrifos from both point and non-point sources, and by developing a numeric target for unknown causes of toxicity. 10. Calleguas Creek stakeholders have been actively engaged with US EPA and the Regional Board on a variety of watershed planning initiatives in the Calleguas Creek Watershed. Key stakeholders have formed the Calleguas Creek Watershed Management Plan (CCWMP), an established, stakeholder-led watershed management group that has been continually operating since 1996. The Calleguas Creek Watershed Management Plan has broad participation from Federal, State and County agencies, municipalities, POTWs, water purveyors, groundwater management agencies, and agricultural and environmental groups. As part of its mission to address issues of long-range comprehensive water resources; land use; economic development; open space preservation, enhancement and management, the CCWMP proposed to US EPA and Regional Board to take the lead on development of the TMDLs. 11. Regional Board staff have participated in the development of a detailed technical document that analyzes and describes the specific necessity and rationale for the development of this TMDL. The technical document entitled "Calleguas Creek Watershed Toxicity TMDL" Resolution No.R4-2005-009 Page 3 prepared by Larry Walker Associates and is an integral part of this Regional Board action and was reviewed, considered, and accepted by the Regional Board as a supporting background report before acting. Further, the technical document provides the detailed factual basis and analysis supporting the problem statement,numeric targets (interpretation of the narrative and numeric water quality objectives used to calculate the pollutant allocations), source analysis, linkage analysis, waste load allocations (for point sources), load allocation (for nonpoint sources),margin of safety, and seasonal variations and critical conditions of this TMDL. 12. On May 5, 2005, prior to the Board's action on this resolution, public hearings were conducted on the Calleguas Creek Watershed Toxicity, Chlorpyrifos and Diazinon TMDL. Notice of the hearing for the Calleguas Creek Watershed Toxicity, Chlorpyrifos and Diazinon TMDL was published in accordance with the requirements of Water Code Section 13244. This notice was published in the Ventura County Star on April 26, the Daily News Los Angeles on April 26, and the Signal Newspaper on April 27, 2005 13. The public has had reasonable opportunity to participate in the review of the amendment to the Basin Plan. A draft of the Calleguas Creek Watershed Toxicity TMDL was released for public comment on April 26, 2005; a Notice of Hearing was published and circulated 45 days preceding Board action; Regional Board staff responded to oral and written comments received from the public; and the Regional Board held a public hearing on July 7, 2005 to consider adoption of the TMDL. 14. In amending the Basin Plan, the Regional Board considered the factors set forth in Sections 13240 and 13242 of the California Water Code. 15. The amendment is consistent with the State Antidegradation Policy (State Board Resolution No. 68-16), in that it does not authorize any lowering of water quality and is designed to implement existing water quality objectives. Likewise, the amendment is consistent with the federal Antidegradation Policy (40 CFR 131.12). 16. The basin planning process has been certified as functionally equivalent to the California Environmental Quality Act requirements for preparing environmental documents (Public Resources Code, Section 21000 et seq.) and as such, the required environmental documentation and CEQA environmental checklist have been prepared. A CEQA Scoping hearing was conducted on May 31, 2005 in the City of Thousand Oaks, 2100 E. Thousand Oaks Blvd., Thousand Oaks, California. A notice of the CEQA Scoping hearing was sent to interested parties including cities and/or counties with jurisdiction in or bordering the Calleguas Creek watershed. 17. The proposed amendment could have a significant adverse effect on the environment. However, there are feasible alternatives and/or feasible mitigation measures that would substantially lessen any significant adverse impact. 18. The regulatory action meets the "Necessity" standard of the Administrative Procedures Act, Government Code, Section 11353, Subdivision(b). 19. The Basin Plan amendment incorporating a TMDL for Toxic Pollutants in Calleguas Creek watershed must be submitted for review and approval by the State Water Resources Control Board (State Board), the State Office of Administrative Law (OAL), and the USEPA. The Basin Plan amendment will become effective upon approval by USEPA. A Notice of Decision will be filed State of California Secretary of Resources. Y Resolution No.R4-2005-009 Page 4 THEREFORE,be it resolved that pursuant to sections 13240 and 13242 of the Water Code, the Regional Board hereby amends the Basin Plan as follows: 1. Pursuant to Sections 13240 and 13242 of the California Water Code, the Regional Board, after considering the entire record, including oral testimony at the hearing, hereby adopts the amendments to Chapter 7 of the Water Quality Control Plan for the Los Angeles Region, as set forth in Attachment A hereto, to incorporate the elements of the Calleguas Creek Watershed Toxicity TMDL. 2. The Executive Officer is directed to forward copies of the Basin Plan amendment to the State Board in accordance with the requirements of section 13245 of the California Water Code. 3. The Regional Board requests that the State Board approve the Basin Plan amendment in accordance with the requirements of sections I3245 and 13246 of the California Water Code and forward it to OAL and the USEPA. 4. If during its approval process Regional Board staff, the State Board or OAL determines that minor,non-substantive corrections to the language of the amendment are needed for clarity or consistency, the Executive Officer may make such changes, and shall inform the Board of any such changes. 5. The Executive Officer is authorized to sign a Certificate of Fee Exemption. I, Jonathan S. Bishop, Executive Officer, do hereby certify that the foregoing is a full, true, and correct copy of a resolution adopted by the California Regional Water Quality Control Board, Los Angeles Region,on July 7, 2005. 7 it of onathan S. Bishop Date Executive Officer Attachment A to Resolution No. R4-2005-009 Amendment to the Water Quality Control Plan—Los Angeles Region to Incorporate the Total Maximum Daily Load for Toxicity, Chlorpyrifos, and Diazinon in the Calleguas Creek,its Tributaries and Mugu Lagoon Adopted by the California Regional Water Quality Control Board, Los Angeles Region on 7 July, 2005. Amendments Table of Contents Add: Chapter 7. Total Maximum Daily Loads (TMDLs) 7- Calleguas Creek Watershed Toxicity TMDL List of Figures,Tables,and Inserts Add: Chapter 7. Total Maximum Daily Loads (TMDLs) Tables 7-16 Calleguas Creek Watershed Toxicity TMDL 7-16.1. Calleguas Creek Watershed Toxicity TMDL: Elements 7-16.2. Calleguas Creek Watershed Toxicity TMDL: Implementation Schedule Chapter 7. Total Maximum Daily Loads (TMDLs) Calleguas Creek Watershed Toxicity TMDL This TMDL was adopted by: The Regional Water Quality Control Board on July 7, 2005. This TMDL was approved by: The State Water Resources Control Board on September 22, 2005. The Office of Administrative Law on December 22, 2005. The U.S. Environmental Protection Agency on March 14, 2006. July 7, 2005 Resolution No. R4-2005-009 Page 2 Table 7-16.1. Calleguas Creek Watershed Toxicity TMDL: Elements TMDL Element Calleguas Creek Watershed Toxicity TMDL Problem Discharge of wastes containing chlorpyrifos, diazinon, other Statement pesticides and/or other toxicants to Calleguas Creek,its tributaries and Mugu Lagoon cause exceedances of water quality objectives for toxicity established in the Basin Plan. Elevated levels of chlorpyrifos have been found in fish tissue samples collected from a segment of Calleguas Creek. Chlorpyrifos and diazinon are organophosphate pesticides used in both agricultural and urban settings. Excessive chlorpyrifos and diazinon can cause aquatic life toxicity in inland surface and estuarine waters such as Calleguas Creek and Mugu Lagoon. The California 2002 303(d)list of impaired waterbodies includes listings for"water column toxicity," "sediment toxicity," chlorpyrifos in fish tissue," and "organophosphate pesticides in water" for various reaches of Calle uas Creek, its tributaries and Mugu Lagoon. Numeric Targets This TMDL establishes a numeric toxicity target of 1.0 toxicity unit —chronic (1.0 TUc) to address toxicity in reaches where the toxicant has not been identified through a Toxicity Identification Evaluation (TIE) (unknown toxicity). TUC =Toxicity Unit Chronic = 100/NOEC (no observable effects concentration) A sediment toxicity target was defined in the technical report for reaches where the sediment toxicant has not been identified through a TIE. The target is based on the definition of a toxic sediment sample as defined by the September 2004 Water Quality Control Policy For Developing California's Clean Water Act Section 303(d) List (SWRCB). Chlorpyrifos Numeric Targets (ug/L) Chronic Acute (4 day average) (1 hour average) Freshwater 0.014 0.025 Saltwater(Mugu Lagoon) 0.009 0.02 Diazinon Numeric Targets (ug/L) Chronic Acute (4 day average) (1 hour average) Freshwater 0.10 0.10 Saltwater(Mugu Lagoon) 0.40 0.82 July 7, 2005 Resolution No. R4-2005-009 Page 3 TMDL Element Calle uas'Creek Watershed Toxicity TMDL Additionally, the diazinon criteria selected as numeric targets are currently under review by the USEPA. If water quality objectives become available, the Regional Board may reconsider this TMDL and revise the water toxicity numeric target. Source Analysis Source analysis determined that agricultural and urban uses are the largest sources of chlorpyrifos and diazinon in the watershed. Urban use of diazinon and chlorpyrifos is unlikely to be a long-term source to the Calleguas Creek Watershed (CCW) as both of these pesticides have been banned for sale for non-agricultural uses on December 31, 2005 by federal regulation. As a result, the proportion of the loading from urban sources will likely decrease after December 2005. Chlorpyrifos—Sources by Use Dry Weather Wet Weather Agriculture 66% 80% Urban 23% 20% POTW 11% <1% Other <1% <1% Diazinon—Sources by Use Dry Weather Wet Weather Agriculture 30% 1% Urban 13% 62% POTW 57% 37% Other <1% <1% Linkage Analysis Water quality modeling established the linkage of sources of chlorpyrifos and diazinon in the CCW to observed water quality data. The linkage analysis qualitatively describes the connection between water column concentrations and sediment and fish tissue concentrations. The qualitative analysis demonstrates that the water column analysis conducted by laboratories implicitly includes sediment associated diazinon and chlorpyrifos loads transported to receiving waters as almost all water quality data do not differentiate between dissolved and particulate fractions. The linkage analysis assumes a reduction in water column concentrations will result in a reduction in fish tissue as chlorpyrifos in freshwater fish tissue rapidly depurate within several days of removal from exposure. Additionally, as chlorpyrifos preferentially binds to sediment the linkage analysis suggests that sediment concentrations of July 7, 2005 Resolution No. R4-2005-009 Page 4 TMDL Element Calleguas Creek Watershed Toxicity chlorpyrifos will need to decrease to achieve water quality numeric targets. The modeling approach reflects the uncertainty in current conditions and the potential impacts of watershed planning actions that may affect those conditions. A detailed description of the model is provided in an Attachment to the TMDL Technical Report. Wasteload Major point sources: Allocations (WLA) A wasteload of 1.0 TUB is allocated to the major point sources (POTWs) discharging to the Calleguas Creek Watershed. Additionally, the following wasteloads for chlorpyrifos and diazinon are established for POTWs. A margin of safety of 5% was included in the targets for chlorpyrifos for discharges to the Calleguas and Revolon subwatersheds. Chlorpyrifos WLAs, ug/L POTW Interim WLA Final WLA (4 day) (4 day) Hill Canyon WWTP 0.030 0.014 Simi Valley WQCP 0.030 0.014 Ventura County (Moorpark) WTP 0.030 0.014 Camarillo WRP 0.030 0.0133 Camrosa WRP 0.030 0.0133 Diazinon WLAs,uWL Interim Interim Final WLA Acute Chronic (Acute or Chronic) (1 hour) (4 day) POTW Hill Canyon WWTP 0.567 0.312 0.10 Simi Valley WQCP 0.567 0.312 0.10 Ventura County (Morepark)WTP 0.567 0.312 0.10 Camarillo WRP 0.567 0.312 0.10 Camrosa WRP 0.567 0.312 0.10 A wasteload of 1.0 TU,is allocated to Urban Stormwater Co- Permittees (MS4) discharges to the Calleguas Creek Watershed. July 7, 2005 Resolution No. R4-2005-009 Page 5 TMDL Element: Calleguas Creek Watershed Toxicity TMDL Additionally, the following wasteloads for chlorpyrifos and diazinon are established for MS4 discharges. Chlorpyrifos WLAs, ug/L Interim WLA Final WLA (4 day) (4 day) 0.45 0.014 Diazinon WLAs,ug/L Interim WLA Interim WLA Final WLA Acute(1 hour) Chronic(4 day) Acute and Chronic 1.73 0.556 0.10 Minor point sources: Minor sources include NPDES permittees other than POTWs and MS4s, discharging to the Calleguas Creek Watershed. A wasteload of 1.0 TUB is allocated to the minor point sources discharging to the Calleguas Creek Watershed. Additionally, the following wasteloads for chlorpyrifos and diazinon are established. Chlorpyrifos WLAs, ug/L Interim WLA Final WLA (4 day) (4 day) 0.45 0.014 Diazinon WLAs,uWL Interim WLA Interim WLA Final WLA Acute(1 hour) Chronic(4 day) Acute and Chronic 1.73 0.556 0.10 Load Allocations Non Point Source Dischargers: A load of 1.0 TU,is allocated to nonpoint sources discharging to the Calleguas Creek Watershed. July 7, 2005 Resolution No. R4-2005-009 Page 6 TMDL'Element Calleguas Creek Watershed Toxicity TMDL Additionally, the following loads for chlorpyrifos and diazinon are established. These loads apply to dischargers in accordance with the subwatershed into which the dischargers discharge. A margin of safety of 5% was included for chlorpyrifos for discharges to the Calleguas and Revolon subwatersheds. Chlorpyrifos Load Allocations, ug/L Interim Interim Final Subwatershed Acute(1hour) Chronic(4 day) Acute and Chronic Arroyo Simi 2.57 0.810 0.014 Las Posas 2.57 0.810 0.014 Conejo 2.57 0.810 0.014 Calleguas 2.57 0.810 0.0133 Revolon 2.57 0.810 0.0133 Mugu Lagoon 2.57 0.810 0.014 Diazinon Load Allocations,ug/L Interim LA Interim LA Final LA Acute Chronic Acute and Chronic 0.278 0.138 0.10 Margin of Safety In addition to the implicit margin of safety achieved by conservative assumptions and by using a concentration based TMDL, an explicit margin of safety of 5% has been added to the targets for chlorpyrifos in the Calleguas and Revolon subwatersheds to address uncertainty in the linkages between the water column criteria and fish tissue and sediment concentrations. The Calleguas and Revolon subwatersheds include those reaches listed for sediment toxicity and chlorpyrifos in fish tissue. Future Growth Ventura County accounts for slightly more than 2% of the state's residents with a population of 753,197 (US Census Bureau, 2000). GIS analysis of the 2000 census data yields a population estimate of 334,000 for the CCW, which equals about 44% of the county population. According to the Southern California Association of Governments (SCAG), growth in Ventura County averaged about 51% per decade from 1900-2000; with growth exceeding 70% in the 1920s, 1950s, and 1960s. The phase-out of chlorpyrifos and diazinon is expected to reduce loads from urban and POTWs significantly by 2007. Use of diazinon in agriculture has declined considerably between 1998 and 2003. Conversely, chlorpyrifos use July 7, 2005 Resolution No. R4-2005-009 Page 7 TMDL Element` Calleguas Creek Watershed Toxicity TMDL in agriculture has remained relatively stable over the same period. The phase out of chlorpyrifos and diazinon as well as population growth will cause an increase in the use of replacement pesticides (e.g. pyrethroids) in the urban environment and may have an impact on water and/or sediment toxicity. Additionally,population growth may affect an increase in the levels of chlorpyrifos and diazinon loading in the CCW from imported products which contain residues of these pesticides. Critical The critical condition in this TMDL is defined as the flowrate at Conditions which the model calculated the greatest in-stream diazinon or chlorpyrifos concentration in comparison to the appropriate criterion. The critical condition for chlorpyrifos was in dry weather based on a chronic numeric target; the critical condition for diazinon was in wet weather based on an acute numeric target except in Mugu Lagoon where it was in dry weather based on the chronic numeric target. Implementation WLAs established for the major points sources, including POTWs Plan in the CCW will be implemented through NPDES permit effluent limits. The final WLAs will be included in NPDES permits in accordance with the compliance schedules provided. The Regional Board may revise these WLAs based on additional information as described in the Special Studies and Monitoring Section of the Technical Report. The toxicity WLAs will be implemented in accordance with US EPA, State Board and Regional Board resolutions, guidance and policy at the time of permit issuance or renewal. Currently, these WLAs would be implemented as a trigger for initiation of the TRE/TIE process as outlined in USEPA's `Understanding and Accounting for Method Variability in Whole Effluent Toxicity Applications Under the National Pollutant Discharge Elimination System Program"(2000) and current NPDES permits held by dischargers to the CCW. Stormwater WLAs will be incorporated into the NPDES permit as receiving water limits measured in-stream at the base of each subwatershed and will be achieved through the implementation of BMPs as outlined below. Evaluation of progress of the TMDL will be determined through the measurement of in-stream water quality and sediment at the base of each of the CCW subwatersheds. The Regional Board may revise these WLAs based on additional information developed through special studies and/or monitoring conducted as part of the TMDL. July 7, 2005 Resolution No. R4-2005-009 Page 8 TMDL Element Calleguas Creek'Watershed Toxicity`TMDL As shown in the attached table the following implementation actions will be taken by the MS4s discharging to the CCW and POTWs located in the CCW: • Plan, develop, and implement an urban pesticides public education program; • Plan, develop, and implement urban pesticide education and chlorpyrifos and diazinon collection program; • Study diazinon and chlorpyrifos replacement pesticides for use in the urban environment; and, • Conduct environmental monitoring as outlined in the Monitoring Plan and NPDES Permits. LAs for chlorpyrifos and diazinon will be implemented through the State's Nonpoint Source Pollution Control Program (NPSPCP), nonpoint source pollution (i.e. Load Allocations). The LARWQCB is currently developing a Conditional Waiver for Irrigated Lands. Once adopted, the Conditional Waiver Program will implement allocations and attain numeric targets of this TMDL. Compliance with LAs will be measured at the monitoring sites approved by the Executive Officer of the Regional Board through the monitoring program developed as part of the Conditional Waiver, or through a monitoring program that is required by this TMDL. The toxicity LAs will be implemented in accordance with US EPA, State Board and Regional Board resolutions, guidance and policy at the time of permit or waiver issuance or renewal. The following implementation actions will be taken by agriculture dischargers located in the CCW: • Enroll for coverage under a waiver of waste discharge requirements for irrigated lands; • Implement monitoring required by this TMDL and the Conditional Waiver program; 4. Complete studies to determine the most appropriate BMPs given crop type,pesticide, site specific conditions, as well as the critical condition defined in the development of the LAs; and, .� Implement appropriate BMPs and monitor to evaluate effectiveness on in-stream water and sediment quality. The Regional Board may revise this TMDL based on monitoring data and special studies of this TMDL. If the Regional Board revises NPDES permits or the Basin Plan to use other methods of July 7, 2005 Resolution No. R4-2005-009 Page 9 TMDL Element CalIe uas Creek Watershed Toxicity TMDL evaluating toxicity or if other information supporting other methods becomes available, the Regional Board may reconsider this TMDL and revise the water toxicity numeric target. Additionally, the development of sediment quality guidelines or criteria and other water quality criteria revisions may call for the reevaluation of the TMDL. The Implementation Plan includes this provision for reevaluating the TMDL to consider sediment quality guidelines or criteria and revised water quality objectives and the results of im lementation studies, if appropriate. July 7, 2005 Resolution No. R4-2005-009 Page 10 Table 7-16.2. Overall Implementation Schedule for Calleguas Creek Watershed Toxicity TMDL Implementation Action 'Responsible part Date Interim chlorpyrifos and diazinon waste-load allocations POTW permittees 2 1 ' and MS4 Effective date apply. Copermittees 2 Interim chlorpyrifos and diazinon load allocations apply.' Agricultural Effective date Dischargers Finalize and submit workplan for integrated Calleguas POTW permittees, 6 months after 3 Creek Watershed Monitoring Program for approval by MS4 Copermittees, z effective date the Regional Board Executive Officer.3 and Agricultural of amendment Dischargers POTW permittees, 6 months after E.O. Initiate Calleguas Creek Watershed Toxicity TMDL MS4 Copermittees, 4 approval of Monitoring Monitoring Program developed under Task 3 workplan. and Agricultural Program(task 3)workplan. Dischargers Special Study 41 - Investigate the pesticides that will POTW permittees replace diazinon and chlorpyrifos in the urban 2 5 and MS4 2 years after effective date environment,their potential impact on receiving waters, Copermittees and potential control measures. Special Study#2—Consider results of monitoring of 6 months after completion sediment concentrations by source/land use type through Agricultural of CCW OC Pesticides, special study required in the OC Pesticide,PCB and 3 6 Dischargers and PCBs and Siltation TMDL siltation TMDL Implementation Plan. If the special study MS4 Copermittees sediment concentrations is not completed through the OC Pesticides,PCBs and special study. Siltation TMDL no consideration is necessary Develop and implement collection program for diazinon POTW permittees 7 and chlorpyrifos and an educational program. Collection and MS4 3 years after effective date'` and education could occur through existing programs Copermittees such as household hazardous waste collection events Develop an Agricultural Water Quality Management Plan in conjunction with the Conditional Waiver for Irrigated Agricultural 2 8 Lands,or(if the Conditional Waiver is not adopted in a Dischargers3 3 years after effective date timely manner)develop an Agricultural Water Quality Management Plan as part of the Calleguas Creek WMP. Identify the most appropriate BMPs given crop type, Agricultural 2 9 pesticide,site specific conditions,as well as the critical Dischargers3 3 years after effective date condition defined in the development of the LAs. 10 Implement educational program on BMPs identified in Agricultural 1 year after E.O. approval of the Agricultural Water Quality Management Plan. Dischargers Plan(Task 7) Special Study#3 Calculation of sediment transport rates Agricultural 6 months after completion 11 in CCW. Consider findings of transport rates developed Dischargers3 and of CCW OC Pesticides, through the OC Pesticide,PCB and siltation TMDL MS4 Copermittees PCBa and Siltation TMDL 'Interim WLAs and LAs are effective immediately upon TMDL adoption. WLAs will be placed in POTW NPDES permits as effluent limits. WLAs will be placed in stormwater NPDES permits as in-stream limits. LAs will be implemented using applicable regulatory mechanisms. 2 Effective date of this TMDL. 3 The Regional Board regulatory programs addressing all discharges in effect at the time an implementation task is due may contain requirements substantially similar to the requirements of an implementation task. If such a requirement is in place in another regulatory program including other TMDLs,the Executive Officer may determine that such other requirements satisfy the requirements of an implementation task of the TMDL and thereby coordinate this TMDL implementation plan with other regulatory programs. July 7, 2005 Resolution No. R4-2005-009 Page 11 Responsible Implementation Action Party Date Implementation Plan. If the special study is not sediment transport special completed through the OCsTMDL,no consideration is study.Z necessary.3 12 Begin implementation of BMPs. Agricultural 1 year after E.O. approval of Dischargers Plan(Task 8) Agricultural 3 years after E.O. approval 13 Evaluate effectiveness of BMPs. Dischargers 3 of Plan(Task 8)2 Based on monitoring data and on the results of Stakeholders and Implementation Actions 1-13 and if sediment guidelines Regional Board are promulgated,or water quality criteria are revised, 2 years after the submittal of 14 and/or if targets are achieved without attainment of information necessary to WLAs or LAs reevaluate the TMDLs,interim or final reevaluate the TMDL WLAs and LAs and implementation schedule,if necessary. POTW permittees 2 years after the effective 15 Achievement of Final WLAs and MS4 2 Co ermittees date of the TMDL 16 Achievement of Final LAs Agricultural 10 years after the effective Dischar ers date of the TMDL July 7, 2005 Exhibit C State of California California Regional Water Quality Control Board,Los Angeles Region RESOLUTION NO. R4-2005-010 July 7,2005 Amendment to the Water Quality Control Plan for the Los Angeles Region to Incorporate a Total Maximum Daily Load for Organochlorine Pesticides, Polychorinated Biphenyls,and Siltation in Calieguas Creek,its Tributaries,and Mugu Lagoon WHEREAS, the California Regional Water Quality Control Board, Los Angeles Region, finds that: 1. The Federal Clean Water Act(CWA) requires the California Regional Water Quality Control Board, Los Angles Region (Regional Board) to develop water quality objectives, which are sufficient to protect beneficial uses for each water body found within its region. 2. A consent decree between the U.S. Environmental Protection Agency (USEPA), Heal the Bay, Inc. and BayKeeper, Inc. was approved on March 22, 1999. This court order directs the USEPA to complete Total Maximum Daily Loads(TMDLs) for all impaired waters within 13 years. A schedule was established in the consent decree for the completion of the first 29 TMDLs within 7 years, including completion of a TMDL to reduce Organochlorine (OC) pesticides and Polychlorinated Biphenyls (PCBs) at Calleguas Creek Watershed by March 22, 2006. The remaining TMDLs will be scheduled by Regional Board staff within the l3- year period. 3. The elements of a TMDL are described in 40 CFR 130.2 and 130.7 and section 303(d)of the CWA, as well as in USEPA guidance documents(Report No. EPA/440/4-91/001). A TMDL is defined as the sum of the individual waste load allocations for point sources, load allocations for nonpoint sources and natural background (40 CFR 130.2). Regulations further stipulate that TMDLs must be set at levels necessary to attain and maintain the applicable narrative and numeric water quality standards with seasonal variations and a margin of safety that takes into account any lack of knowledge concerning the relationship between effluent limitations and water quality (40 CFR 130.7(c)(1)). The regulations in 40 CFR 130.7 also state that TMDLs shall take into account critical conditions for stream flow, loading and water quality parameters. 4. The numeric targets in this TMDL are not water quality objectives and do not create new bases for enforcement against dischargers apart from the water quality objectives they translate. The targets merely establish the bases through which load allocations (LAs) and waste load allocations (WLAs) are calculated. WI-As are only enforced for a discharger's own discharges, and then only in the context of its National Pollutant Discharge Elimination System(NPDES) permit, which must be consistent with the assumptions and requirements of the WLA. The Regional Board will develop permit requirements through a subsequent permit action that will allow all interested persons, including but not limited to municipal storm water dischargers,to provide comments on how the WLA will be translated into permit requirements. Resolution No.R4-2005-010 Page 2 5. Upon establishment of TMDLs by the State or USEPA, the State is required to incorporate the TMDLs along with appropriate implementation measures into the State Water Quality Management Plan(40 CFR 130.6(c)(1), 130.7). This Water Quality Control Plan for the Los Angeles Region (Basin Plan), and applicable statewide plans, serves as the State Water Quality Management Plans governing the watersheds under the jurisdiction of the Regional Board. 6. The SWRCB adopted Policy for Implementation of Toxics Standards for Inland Surface Waters, Enclosed Bays, and Estuaries of California (also known as the State Implementation Plan or SIP) on March 2, 2000. The SIP was amended by Resolution No. 2000-30, on April 26,2000,and the Office of Administrative Law approved the SIP on April 28, 2000. The SIP applies to discharges of toxic pollutants in the inland surface waters, enclosed bays and estuaries of California which are subject to regulation under the State's Porter-Cologne Water Quality Control Act (Division 7 of the Water Code) and the Federal Clean Water Act. This policy also establishes the following: implementation provisions for priority pollutant criteria promulgated by USEPA through the CTR and for priority pollutant objectives established by Regional Water Quality Control Boards.in their water quality control plans (Basin Plans) and chronic toxicity control provisions. 7. On May 18, 2000, the U.S. EPA promulgated the numeric criteria for priority pollutants for the State of California, known as the California Toxics Rule (CTR) and as codified as 40 CFR section 131.38. 8. The Calleguas Creek Watershed is located in southeast Ventura County, California, and in a small portion of western Los Angeles County, and drains an area of approximately 343 square miles from the Santa Susana Pass in the east, to Mugu Lagoon in the southwest. Current land use is approximately 26 percent agriculture, 24 percent urban, and 50 percent open space. The tributaries and the streams of the Calleguas Creek Watershed are divided into fourteen segments, or reaches. The 2002 Clean Water Act 303(d) list identified eleven reaches out of thirteen reaches of the Calleguas Creek watershed as impaired for OC pesticides and PCBs. These listings were approved by the State Water Resources Control Board on February 4,2003. 9. The Regional Board's goal in establishing the Calleguas Creek OC Pesticides, PCBs and Siltation TMDL is to determine and set forth measures needed to prevent impairment of water quality due to OC pesticides and PCBs in Calleguas Creek. 10. Calleguas Creek stakeholders have been actively engaged with US EPA and the Regional Board on a variety of watershed planning initiatives in the Calleguas Creek Watershed. Key stakeholders have formed the Calleguas Creek Watershed Management Plan (CCWMP), an established, stakeholder-led watershed management group that has been continually operating since 1996. The Calleguas Creek Watershed Management Plan has broad participation from Federal, State and County agencies, municipalities, POTWs, water purveyors, groundwater management agencies, and agricultural and environmental groups. As part of its mission to address issues of long-range comprehensive water resources; land use; economic development; open space preservation, enhancement and management, the CCWMP proposed to US EPA and Regional Board to take the lead on development of the TMDLs. 11. Regional Board staff have worked with the CCWMP and US EPA in the development of a detailed technical document that analyzes and describes the specific necessity and rationale for the development of this TMDL. The technical document entitled "Calleguas Creek Resolution No.R4-2005-010 Page 3 Watershed OC Pesticides and PCBs TMDL" prepared by Larry Walker Associates is an integral part of this Regional Board action and was reviewed, and accepted by the Regional Board as a supporting technical analysis before acting. Regional Board staff led the development of the TMDL analysis for siltation with participation from CCWMP and Stakeholders. The technical document provides the detailed factual basis and analysis supporting the problem statement, numeric targets (interpretation of the narrative and numeric water quality objectives, used to calculate the pollutant allocations), source analysis, linkage analysis, waste load allocations (for point sources), load allocation (for nonpoint sources), margin of safety, and seasonal variations and critical conditions of this TMDL. 12. Regional Board staff used all available information in its analysis of the siltation listing for Mugu Lagoon. Based on available information, Regional Board staff find that excessive siltation into estuaries can impair aquatic life habitat through excess deposition. Furthermore, historic pesticides and PCBs adhere to sediment particles and are transported with sediment to Calleguas Creek and Mugu Lagoon. Staff find sufficient existing data to establish the annual excess sediment and silt loading to Mugu Lagoon, but insufficient existing data to establish the annual loading of sediment and silt to Mugu Lagoon under the highly variable meteorological and hydrological conditions within the Calleguas Creek watershed. Consequently, this TMDL establishes interim wasteload and interim load allocations as a sediment mass reduction, and provides for special studies to develop a refined TMDL as discussed below in order to protect aquatic life and wetland habitat beneficial uses. The interim wasteload and load reductions represent staff s best professional judgement of the sediment mass reductions needed to achieve compliance with the TMDL targets based on achieving the regional narrative water quality objectives for wetlands hydrology and habitat, and solid, suspended, or settleable materials that can cause siltation that degrades aquatic life habitat. 13. During the implementation period, stakeholders will conduct a special study to assess the amount of sediment, silt and pollutants that are conveyed to and deposited within the Mugu Lagoon over time. After the special study has been completed and reviewed by a Science Advisory Panel in accordance with the TMDL Implementation Plan, the Regional Board will re-consider the TMDL and the final wasteload and load allocations. The revised final TMDL and allocations may be expressed in terms of total mass loading of sediment, silt and/or pollutants to Mugu Lagoon. 14. On May 5, 2005, prior to the Board's action on this resolution, public hearings were conducted on the Calleguas Creek Watershed OC Pesticides, PCBs and Siltation TMDL. Notice of the hearing for the Calleguas Creek Watershed OC Pesticides and PCBs TMDL was published in accordance with the requirements of Water Code Section 13244. This notice was published in the Ventura County Star on April 26, the Daily News Los Angeles on April 26,and the Signal Newspaper on April 27,2005. 15. The public has had reasonable opportunity to participate in the review of the amendment to the Basin Plan. A draft of the Calleguas Creek Watershed OC Pesticides and PCBs TMDL was released for public comment on April 26, 2005; a Notice of Hearing and Notice of Filing were published and circulated 45 days preceding Board action; Regional Board staff responded to oral and written comments received from the public; and the Regional Board held a public hearing on July 7,2005 to consider adoption of the TMDL. 16. In amending the Basin Plan, the Regional Board considered the factors set forth in Sections 13240 and 13242 of the California Water Code. Resolution No. R4-2005-010 Page 4 17. The amendment is consistent with the State Antidegradation Policy (State Board Resolution No. 68-16), in that it does not authorize any lowering of water quality and is designed to implement existing water quality objectives. Likewise,the amendment is consistent with the federal Antidegradation Policy(40 CFR 131.12). 18. The basin planning process has been certified as functionally equivalent to the California Environmental Quality Act requirements for preparing environmental documents (Public Resources Code, Section 21000 et seq.) and as such, the required environmental documentation and CEQA environmental checklist have been prepared. A CEQA Scoping hearing was conducted on May 31, 2005 in the City of Thousand Oaks, 2100 E. Thousand Oaks Blvd., Thousand Oaks, California. A notice of the CEQA Scoping hearing was sent to interested parties including cities and/or counties with jurisdiction in or bordering the Calleguas Creek watershed. 19. The proposed amendment could have a significant adverse effect on the environment. However, there are feasible alternatives and/or feasible mitigation measures that would substantially lessen any significant adverse impact. 20. The regulatory action meets the "Necessity" standard of the Administrative Procedures Act, Government Code, Section 11353, Subdivision(b). 21. The Basin Plan amendment incorporating a TMDL for OC Pesticides and PCBs in Calleguas Creek watershed must be submitted for review and approval by the State Water Resources Control Board(State Board),the State Office of Administrative Law(OAL), and the USEPA. The Basin Plan amendment will become effective upon approval by USEPA. A Notice of Decision will be filed with the State of California Secretary of Resources. THEREFORE, be it resolved that pursuant to sections 13240 and 13242 of the Water Code, the Regional Board hereby amends the Basin Plan as follows: 1. Pursuant to Sections 13240 and 13242 of the California Water Code, the Regional Board, after considering the entire record, including oral testimony at the hearing, hereby adopts the amendments to Chapter 7 of the Water Quality Control Plan for the Los Angeles Region, as set forth in Attachment A hereto, to incorporate the elements of the Calleguas Creek Watershed OC Pesticides and PCBs TMDL. 2. The Executive Officer is directed to forward copies of the Basin Plan amendment to the State Board in accordance with the requirements of section 13245 of the California Water Code. 3. The Regional Board requests that the State Board approve the Basin Plan amendment in accordance with the requirements of sections 13245 and 13246 of the California Water Code and forward it to OAL and the USEPA. 4. If during its approval process Regional Board staff, the State Board or OAL determines that minor,non-substantive corrections to the language of the amendment are needed for clarity or consistency, the Executive.Officer may make such changes, and shall inform the Board of any such changes. Resolution No.R4-2005-010 Page 5 5. The Executive Officer is authorized to sign a Certificate of Fee Exemption. I, Jonathan S. Bishop, Executive Officer, do hereby certify that the foregoing is a full, true, and correct copy of a resolution adopted by the California Regional Water Quality Control Board,Los Angeles Region,on July 7,2005. /3 f/.r1ot onathan S. Bisho Date Executive Officer Attachment A to Resolution No. R4-2005-010 Amendment to the Water Quality Control Plan—Los Angeles Region to Incorporate a Total Maximum Daily Loads (TMDLs) for Organochlorine (OC) Pesticides, Polychlorinated Biphenyls (PCBs) and Siltation in Calleguas Creek, Its Tributaries,and Mugu Lagoon Adopted by the California Regional Water Quality Control Board, Los Angeles Region on July 7, 2005. Amendments Table of Contents Add: Chapter 7. Total Maximum Daily Loads (TMDLs) 7- 17 Calleguas Creek Organochlorine Pesticides, Polychlorinated Biphenyls, and Siltation TMDL List of Figures,Tables, and Inserts Add: Chapter 7. Total Maximum Daily Loads (TMDLs) Tables 7-17 Calleguas Creek Organochlorine Pesticides, Polychlorinated Biphenyls, and Siltation TMDL 7-17.1 Calleguas Creek Organochlorine Pesticides, Polychlorinated Biphenyls, and Siltation TMDL: Elements 7-17.2 Calleguas Creek Organochlorine Pesticides,Polychlorinated Biphenyls, and Siltation TMDL: Implementation Schedule Chapter 7. Total Maximum Daily Loads (TMDLs) Calleguas Creek Organochlorine Pesticides, Polychlorinated Biphenyls, and Siltation TMDL Add: This TMDL was adopted by the Regional Water Quality Control Board on July 7, 2005. This TMDL was approved by: The State Water Resources Control Board on September 22, 2005. The Office of Administrative Law on January 20, 2006. The U.S. Environmental Protection Agency on March 14, 2006. The following table includes the elements of the TMDL: July 7, 2005 Attachment A to Resolution No. R4-2005-010 Table 7-17.1. Calleguas Creek Watershed OC Pesticides, PCBs, and Siltation TMDL: Elements TMDL Element ! Calleguas Creek Watershed OC Pesticide,PCBs,and Siltation TMDL' Problem Eleven of fourteen reaches in the Calleguas Creek Watershed Statement (CCW) were identified on the 2002 303(d) list of water-quality limited segments as impaired due to elevated levels of organochlorine (OC)pesticides and/or polychlorinated biphenyls (PCBs) in water, sediment, and/or fish tissue. Additionally, Mugu Lagoon was listed as impaired for sedimentation/siltation. OC pesticides and PCBs can bioaccumulate in fish tissue and cause toxicity to aquatic life in estuarine and inland waters. Siltation may transport OC Pesticides and PCBs to surface waters and impair a uatic life and wildlife habitats. Numeric The following tables provide the targets for water,fish tissue, and Targets sediment for this TMDL. Water column targets were derived from the California Toxic Rule (CTR) water quality criteria for protection of aquatic life. Chronic criteria(Criteria Continuous Concentration, or CCC) were applied unless otherwise noted in the table below: Water Quality Targets(ng/L)l Constituent Freshwater Marine Aldrin 300.0 130.0 Chlordane 4.3 4.0 Dacthal 3,500,000.0 (a)3 4,4'-DDD4 (a)3 (a)3 4,4'-DDE5 (a)3 (a)3 4,4'-DDT 6 1.0 1.0 Dieldrin 56.0 1.9 Endosulfan I 56.0 8.7 Endosulfan Il 56.0 8.7 Endrin 36.0 2.3 HCH(alpha-BHC') (a)3 (a)3 HCH(beta-BHC) (a)3 (a)3 HCH(delta-BHC) (a)3 (a)3 1 ng/L:nanogram per litter 'Marine numeric targets applied to Mugu Lagoon 3 Numeric targets have not been established for these constituents °DDD:Dichlorodiphenyldchloroethane 5 DDE:Dichlorodiphenyldichloroethylene 6 DDT:Dichlorodiphenyltrichloroethane BHC:Hexachlorocyclohexane Page 2 July 7, 2005 Attachment A to Resolution No. R4-2005-010 TMDL Element Calleguas Creek Watershed OC Pesticide,PCBs,and Siltation TMDL HCH(gamma BHC) 950.0 160.0 Heptachlor 3.8 3.6 Heptachlor Epoxide 3.8 3.6 PCBs 140.0' 30.0' Toxaphene 0.2 0.2 Fish tissue targets are derived from CTR human health criteria for consumption of organisms. Fish Tissue Targets(ng/Kg) Constituent Aldrin 50.0 Chlordane 830.0 Dacthal (a)2 4,4'-DDD 45,000.0 4,4'-DDE 32,000.0 4,4'-DDT 32,000.0 Dieldrin 650.0 Endosulfan I 65,000,000.0 Endosulfan II 65,000,000.0 Endrin 3,200,000.0 HCH(alpha-BHC) 1,700.00 HCH(beta-BHC) 6,000.0 HCH(delta-BHC) (a)' HCH(gamma BHC) 8,200. Heptachlor 2,400.0 Heptachlor Epoxide 1,200.0 PCBs 5,300.03 Toxaphene 9,800.0 Sediment targets were derived from sediment quality guidelines contained in National Oceanographic and Atmospheric Administration (NOAA) Screening Quick Reference Tables (SQuiRT, Buchman, 1999). Sediment Quality Targets(ng/dry Kg) Constituent Freshwater,TEL Marine',ERL' Aldrin (a)' (a)' Chlordane 4,500.0 500.0 Dacthal (a)' (a)' 4,4'-DDD 3,500.0 2,000.0 'Applies to sum of all congener or isomer or homolog or Aroclor analyses 2 Numeric targets have not been established for these constituents 3 Applies to sum of all congener or isomer or homolog or Aroclor analyses 4 TEL=Threshold Effects Level s Marine numeric targets applied to Mugu Lagoon 'ERL=Effects Range-Low. Page 3 July 7, 2005 Attachment A to Resolution No. R4-2005-010 TMDL Element Calleguas Creek Watershed_QC Pesticide,PCBs,and Siltation TMDL 4,4'-DDE 1,400.0 2,200.0 4,4'-DDT (a)' 1,000.0 Dieldrin 2,900.0 20.0 Endosulfan I (a)' (a)' Endosulfan lI (a)' (a)' Endrin 2,700.0 (a)' HCH(alpha-BHC) (a)' (a)' HCH(beta-BHC) (a)' (a)' HCH(delta-BHC) (a)' (a)' HCH(gamma BHC) 940.0 (a)' Heptachlor (a)' (a)' Heptachlor Epoxide 600.0 (a)' PCBs 34,000.02 23,000.0 Toxaphene (a)' (a)' Siltation Targets This TMDL includes two numeric targets for siltation reduction and maintenance of existing habitat in Mugu Lagoon which are listed below: • Siltation reduction Annual average reduction in the import of silt of 5,200 tons/year, which will be measured at the US Naval Base total suspended sediment gauge at the entrance to Mugu Lagoon. • Maintenance of existing habitat in Mugu Lagoon Preservation of the existing 1400 acres of aquatic habitat in Mugu Lagoon. Source Analysis Monitoring data from major NPDES discharges and land use runoff were analyzed to estimate the magnitude of OC pesticides and PCBs loads to Calleguas Creek, its tributaries and Mugu Lagoon. The largest source of OC pesticides in the listed waters is agricultural runoff. Most PCB residues are due to past use of PCBs as coolants and lubricants in transformers, capacitors, and other electrical equipment. Atmospheric deposition is also a potential source of PCBs. Urban runoff and POTWs are minor sources of OC pesticides and PCBs. Data analysis suggests that groundwater, atmospheric deposition, and imported water are not significant sources of OC pesticides, PCBs, or sediment. Further evaluation of these sources is set forth in the Implementation Plan. Linkage The linkage analysis is based on a conceptual model for the fate, Analysis transformation, and uptake of OC pesticides and PCBs and a mass- balance model that connects the sources of OC pesticides and PCBs to their fate and transport in Calleguas Creek, its tributaries, and Mu a La oon. The linkage analysis indicates: 1) OC pesticides Page 4 July 7, 2005 Attachment A to Resolution No. R4-2005-010 TMDL Element Calleguas Creek Watershed OC Pesticide,PCBs,and Siltation TMDL and PCBs concentrations in tissue are proportional to OC pesticides and PCBs concentrations in sediments; 2) OC pesticides and PCBs concentrations in water are a function of OC pesticides and PCBs concentrations in sediment; and 3) OC pesticides and PCBs concentrations in sediment are a function of OC pesticides and PCBs loading and sediment transport. Because sediments store, convey and serve as a source of OC pesticides and PCBs, a reduction of OC pesticides and PCBs concentrations in sediment will result in a reduction of OC pesticides and PCBs concentration in the water column and fish tissue. In this linkage analysis, DDE is used as a representative constituent, because DDE is consistently detected in monitoring and exceeds numeric targets in water, sediment, and tissue samples. Also, other OC Pesticides and PCBs possess similar physical and chemical properties to DDE. Wasteload Allocations 1. Interim and Final WLAs* for Pollutants in Effluent for POTWs. The interim wasteload allocations for POTWs will be re- considered by the Regional Board on a 5-year basis. This re- consideration will be based on sufficient data to calculate Interim Wasteload Allocations in accordance with SIP procedures. a) Interim WLAs (ng/L) Constituent POTW Hill Canyon Simi Valley Moorpark Camarillo Camrosa Daily Daily Daily Daily Daily Chlordane 1.2 100.0 100.0 100.0 100.0 4,4-DDD 20.0 50.0 50.0 6.0 50.0 4,4-DDE 260.0 1.2 1.2 188.0 50.0 4,4-DDT 10.0 10.0 10.0 10.0 10.0 Dieldrin 10.0 10.0 10.0 10.0 10.0 PCBs 500.0 500.0 500.0 31.0 500.0 Toxaphene 500.0 500.0 500.0 500.0 500.0 *WLAs shall be applied to POTWs'effluent b) Final WLAs (ng/L) Constituent POTW Hill Canyon Simi Valley Moorpark Camarillo Camrosa Daily Monthly Daily Monthly Daily Monthly Daily Monthly Daily Monthly Chlordane 1.2 0.59 1.2 0.59 1.2 0.59 1.2 0.59 1.2 0.59 4,4-DDD 1.7 0.84 1.7 0.84 1.7 0.84 1.7 0.84 1.7 0.84 4,4-DDE 1.2 0.59 1.2 0.59 1.2 0.59 1.2 0.59 1.2 0.59 4,4-DDT 1.2 0.59 1.2 0.59 1.2 0.59 1.2 0.59 1.2 0.59 Dieldrin 0.28 0.14 0.28 0.14 0.28 0.14 0.28 0.14 0.28 0.14 Page 5 July 7, 2005 Attachment A to Resolution No. R4-2005-010 TMDL Element Calleguas Creek Watershed OC Pesticide,PCBs,and Siltation TMDL" PCBs 0.34 0.17 0.34 0.17 0.34 0.17 0.34 0.17 0.34 0.17 Toxaphene 0.33 0.16 0.33 0.16 0.33 0.16 0.33 0.16 0.33 0.16 The final WLAs will be included in NPDES permits in accordance with schedule in the implementation plan. The Regional Board may revise final WLAs prior to the dates they are placed into permits and/or prior to the dates of final WLA achievement based on special studies and monitoring of this TMDL. 2. Interim and Final WLAs for Pollutants in Sediment for Stormwater Permittees a) Interim WLAs (ng/g) Constituent Subwatershed Mugu Calleguas Revolon Arroyo Arroyo Conejo Lagoon' Creek Slough Las Posas Simi Creek Chlordane 25.0 17.0 48.0 3.3 3.3 3.4 4,4-DDD 69.0 66.0 400.0 290.0 14.0 5.3 4,4-DDE 300.0 470.0 1,600.0 950.0 170.0 20.0 4,4-DDT 39.0 110.0 690.0 670.0 25.0 2.0 Dieldrin 19.0 3.0 5.7 1.1 1.1 3.0 PCBs 180.0 3,800.0 7,600.0 25,700.0 25,700.0 3,800.0 Toxaphene 22,900.0 260.0 790.0 230.0 230.0 260.0 Compliance with sediment based WLAs is measured as an in- stream annual average at the base of each subwatershed where the discharges are located. b) Final WLAs (ng/g) Constituent Subwatershed Mugu Calleguas Revolon Arroyo Arroyo Conejo Lagoon' Creek Slough Las Posas Simi Creek Chlordane 3.3 3.3 0.9 3.3 3.3 3.3 4,4-DDD 2.0 2.0 2.0 2.0 2.0 2.0 4,4-DDE 2.2 1.4 1.4 1.4 1.4 1.4 4,4-DDT 0.3 0.3 0.3 0.3 0.3 0.3 Dieldrin 4.3 0.2 0.1 0.2 0.2 0.2 PCBs 180.0 120.0 130.0 120.0 120.0 120.0 Toxaphene 360.0 0.6 1.0 0.6 0.6 0.6 1 The Mugu Lagoon subwatershed includes Duck Pond/Agricultural Drain/Mugu/Oxnard Drain#2. Compliance with sediment based WLAs is measured as an in- stream annual average at the base of each subwatershed where the discharges are located. 3. Final WLAs for Pollutants in Water Column for Minor Point Sources WLAs for pollutants in water column are allocated below to Page 6 July 7, 2005 Attachment A to Resolution No. R4-2005-010 TMDL Element Calleguas Creek Watershed OC Pesticide,PCBs,and Siltation TMDL'' minor point sources enrolled under NPDES permits or WDRs, which discharge to Calleguas Creek. Constituent Daily Maximum(ng/L) Monthly Average(ng/L) Chlordane 1.2 0.59 4,4-DDD 1.7 0.84 4,4-DDE 1.2 0.59 4,4-DDT 1.2 0.59 Dieldrin 0.28 0.14 PCBs 0.34 0.17 Toxaphene 0.33 0.16 4. Siltation WLA for MS4 MS4 dischargers will receive an allocation of 2,496-tons/yr. reduction in sediment yield to Mugu Lagoon. The baseline from which the load reduction will be evaluated will be determined by a special study of this TMDL. The load allocation will apply after the baseline is established, as described in the Implementation Plan. Load Compliance with sediment based LAs listed below is measured as Allocations an in-stream annual average at the base of each subwatershed. 1. Interim and Final Load Allocations a) Interim Sediment LAs (ng/g) Constituent Subwatershed Mugu Calleguas Revolon Arroyo Arroyo Conejo Lagoons Creek Slough Las Posas Simi Creek Chlordane 25.0 17.0 48.0 3.3 3.3 3.4 4,4-DDD 69.0 66.0 400.0 290.0 14.0 5.3 4,4-DDE 300.0 470.0 1,600.0 950.0 170.0 20.0 4,4-DDT 39.0 110.0 690.0 670.0 25.0 2.0 Dieldrin 19.0 3.0 5.7 1.1 1.1 3.0 PCBs 180.0 3,800.0 7,600.0 25,700.0 25,700.0 3,800.0 Toxaphene 22900.0 260.0 790.0 230.0 230.0 260.0 s The Mugu Lagoon subwatershed includes Duck Pond/Agricultural Drain/Mugu/Oxnard Drain#2. b) Final Sediment LAs (ng/g) Constituent Subwatershed Mugu Calleguas Revolon Arroyo Arroyo Conejo Lagoon' Creek Slough Las Posas Simi Creek Page 7 July 7, 2005 Attachment A to Resolution No. R4-2005-010 TMDL Element Calleguas Creek Watershed OC Pesticide,PCBs,and Siltation TMDL" Chlordane 3.3 3.3 0.9 3.3 3.3 3.3 4,4-DDD 2.0 2.0 2.0 2.0 2.0 2.0 4,4-DDE 2.2 1.4 1.4 1.4 1.4 1.4 4,4-DDT 0.3 0.3 0.3 0.3 0.3 0.3 Dieldrin 4.3 0.2 0.1 0.2 0.2 0.2 PCBs 180.0 120.0 130.0 120.0 120.0 120.0 Toxaphene 360.0 0.6 1.0 0.6 0.6 0.6 1 The Mugu Lagoon subwatershed includes Duck Pond/Agricultural Drain/Mugu/Oxnard Drain#2. 2. Siltation LAs Agricultural dischargers will receive an allocation of 2,704 tons/yr. Reduction in sediment yield to Mugu Lagoon. The baseline from which the load reduction will be evaluated will be determined by a special study of this TMDL. The load allocation will apply after the baseline is established, as described in the Implementation Plan. Margin of This TMDL relies on an implicit margin of safety,by incorporating Safety conservative assumptions throughout its development, including: • Basing percent reductions on the historical data set of water and fish tissue concentrations, which does not reflect the effects of attenuation the over the past ten years. • Determining the percent reduction in sediment,by basing it on the greater percent reduction of either water or fish tissue concentrations based on available data. • Reducing the allowable concentration for upstream subwatersheds, to ensure protection of those subwatersheds downstream from upstream inputs. • Choosing Threshold Effects Levels (TELs) and Effects Range Lows (ERLs) as numeric targets for sediment, which are the most protective applicable sediment guidelines. • Selecting the more stringent of the allowable concentration (as calculated by percent reduction methodology) or the numeric target for sediment (TEL or ERL), when available, as the WLA and LA for all reaches with 303(d) listings for sediment. Future Growth Ventura County accounts for slightly more than 2% of the state's residents with a population of 753,197 (US Census Bureau, 2000). GIS analysis of the 2000 census data yields a population estimate of 334,000 for the CCW, which equals about 44% of the county population. According to the Southern California Association of Governments (SLAG), growth in Ventura County averaged about 51% per decade from 1900-2000; with growth exceeding 70% in the 1920s, 1950s, and 1960s. Significant population growth is ex ected to occur within and near present city limits until at least Page 8 July 7, 2005 Attachment A to Resolution No.114-2005-010 TMDL Element Calleguas Creek Watershed OC Pesticide,PCBs,and Siltation TMDL 2020. Since most of the listed OCs and PCBs in the CCW are banned, this growth is not expected to increase current loads. Urban application of those OC pesticides which are still legal (dacthal and endosulfan) may increase, but overall use may decrease because urban expansion tends to reduce total acreage of agricultural land. Population growth may result in greater OC loading to POTW influent from washing food products containing OC residues. This loading may be proportional to the increase in population, if per capita domestic water use and pesticide load per household remain constant. Increased flow from POTWs should not result in impairment of the CCW as long as effluent concentration standards are met for each POTW. As urban development occurs, construction activities may have a range of effects on OC loading to the CCW. Exposure of previously vegetated or deeply buried soil might lead to increased rates of transportation and volatilization. Conversely, urbanization of open space and/or agriculture areas may cover OC pesticides bound to sediments. Future growth in the CCW may result in increased groundwater concentrations of currently used OC pesticides. This is a potential concern for dacthal, which is still used and has been found in groundwater(although current levels of dacthal are significantly lower than all available targets). The effects of future growth upon PCB loads are unknown,but not likely to prove significant, since atmospheric deposition and accidental spills are the primary loading pathways. Any increase in OCs due to population growth may be offset by decreased inputs from banned OCs, as their presence attenuates due to fate and transport processes. Critical The linkage analysis found correlation between concentrations of Conditions OC pesticides and PCBs in water and total suspended solids (TSS), and a potential correlation between OC pesticides and PCBs concentrations in water and seasonality (wet vs. dry season). A similar correlation between sediment loading and wet weather is also noted. OC pesticides and PCB pollutants are of potential concern in the Calleguas Creek Watershed due to possible long-term loading and food chain bioaccumulation effects. There is no evidence of short- term effects. However, pollutant loads and transport within the Page 9 July 7, 2005 Attachment A to Resolution No. R4-2005-010 TMDL Element Calleguas Creek Watershed OC Pesticide,PCBs,and Siltation TMDL' watershed may vary under different flow and runoff conditions. Therefore the TMDLs consider seasonal variations in loads and flows but are established in a manner which accounts for the longer time horizon in which ecological effects may occur. Wet weather events, which may occur at any time of the year, produce extensive sediment redistribution and transport downstream. This would be considered the critical condition for loading. However, the effects of organochlorine compounds are manifested over long time periods in response to bioaccumulation in the food chain. Therefore, short-term loading variations (within the time scale of wet and dry seasons each year) are not likely to cause significant variations in beneficial use effects. Therefore, although seasonal variations in loads and flows were considered, the TMDL was established in a manner which accounts for the longer time horizon in which ecological effects may occur Implementation The final WLAs will be included in NPDES permits in accordance Plan with the compliance schedules provided in Table 7-17.2. The Regional Board may revise these WLAs based on additional information developed through Special Studies and/or Monitoring of this TMDL. WLAs established for the five major POTWs in this TMDL will be implemented through NPDES permit limits. The proposed permit limits will be applied as end-of-pipe concentration-based effluent limits for POTWs. Compliance will be determined through monitoring of final effluent discharge as defined in the NPDES permit. The implementation plan for POTWs focuses on implementation of source control activities. Consideration of annual averaging of compliance data will be evaluated at the time of permit renewal based on available information, Regional Board policies, and US EPA approval. In accordance with current practice, a group concentration-based WLA has been developed for MS4s, including the Caltrans MS4. The grouped allocation will apply to all NPDES-regulated municipal stormwater discharges in the CCW. Other NPDES- regulated stormwater permittees will be assigned a concentration- based WLA consistent with the interim and final WLAs set forth above. Stormwater WLAs will be incorporated into the NPDES permit as receiving water limits measured at the downstream points of each subwatershed and are expected to be achieved through the implementation of BMPs as outlined in the implementation plan. Page 10 July 7, 2005 Attachment A to Resolution No. R4-2005-010 TMDL Element Calleguas Creek Watershed OC Pesticide,PCBs,and Siltation TMDL The Regional Board will need to ensure that permit conditions are consistent with the assumptions of the WLAs. If BMPs are to be used, the Regional Board will need to detail its findings and conclusions supporting the use of BMPs in the NPDES permit fact sheets. Should federal, state, or regional guidance or practice for implementing WLAs into permits be revised, the Regional Board may reevaluated the TMDL to incorporate such guidance. LAs will be implemented through the State's Nonpoint Source Pollution Control Program (NPSPCP). The LARWQCB is developing a Conditional Waiver for Irrigated Lands, which includes monitoring at sites subject to approval by the Executive Officer of the Regional Board. Should adoption of the Conditional Waiver be delayed, monitoring will be required as part of this TMDL. Studies are currently being conducted to assess the effectiveness of BMPs for reduction of pollutants from agricultural operations. Results will be used to develop Agricultural Water Quality Management Plans, including the implementation of agricultural BMPs. Additionally, an agricultural education program will be developed to inform growers of the recommended BMPs and the Management Plan. As shown in Table 7-17.2, implementation actions will be taken by agricultural dischargers located in the CCW. The implementation of agricultural BMPs will be based on a comprehensive approach to address pollutant loads discharged from agricultural operations. The Regional Board may revise these LAs based on the collection of additional information developed through special studies and/or monitoring conducted as part of this TMDL. A number of provisions in this TMDL might provide information that could result in revisions to the TMDL. Additionally, the development of sediment quality criteria and other water quality criteria revisions may require the reevaluation of this TMDL. Finally, the use of OC pesticides in other countries which may be present in imported food products, compounded with the persistence of OC pesticides and PCBs in the environment, indicate that efforts-to control sources and transport of OCs to receiving waters may not result in attainment of targets and allocations due to activities that are outside the control of local agencies and agriculture. For these reasons, the Implementation Plan includes this rovision for reevaluating the TMDL to consider revised water Page 11 July 7, 2005 Attachment A to Resolution No. 114-2005-010 TMDL Element Calleguas Creek Watershed 4C Pesticide,PCBs,and Siltation TMDL quality objectives and the results of implementation studies, if appropriate. The siltation portion of the TMDL includes wasteload and load allocations set as an annual mass reduction from a baseline value of sediment and silt deposited in Mugu Lagoon. The baseline value of sediment and silt conveyed to Mugu Lagoon is to be determined by a TMDL Special Study and established by the Regional Board through an amendment to the TMDL. The Special Study is eight years in duration to ensure that the full range of current conditions that affect loading of sediment and siltation to Mugu Lagoon are considered. If appropriate, the Special Study may also result in a revision to the mass load reduction. The Special Study will be overseen by a Science Advisory Panel consisting of local,regional, and/or national experts in estuarine habitat biology, hydrology, and engineering. At the conclusion of the special study, the Regional Board will reconsider the TMDL to establish sustainable wasteload and load allocations recommended by the Special Study to support aquatic life and wetland habitat beneficial uses. In implementing this TMDL, staff recognize that dischargers may be implementing management measures and management practices to reduce sediment and Siltation loads through permit and waiver programs during the special studies. Further, since the effective date of the Consent Decree,reaches of Calleguas Creek have been listed due to sediment, and another TMDL may be initiated during the Special Study of this TMDL. Staff's intent is to coordinate the requirements of this TMDL with other programs that reduce sedimentation and siltation. The Special Study can consider sediment and silt load reductions through existing permits and the forthcoming conditional waiver for irrigated lands. Load and wasteload allocations become effective after the Regional Board actions based on the Special Study, nine years after the effective date of the TMDL. Page 12 July 7, 2005 Attachment A to Resolution No. 114-2005-010 Table 7-17.2 Implementation Schedule Itcm { Lnp1[eeii�ation°Action - Responsilble Party q p � d, , n y r "C m letioa'Date- Interim organochlorine pesticide and polychlorinated Effective date of the 1 biphenyls wasteload allocations apply. NPDES Permittees amendment 2 Interim organochlorine pesticide and polychlorinated Agricultural Dischargers Effective date of the biphenyls load allocations apply. amendment Finalize and submit workplan for organochlorine pesticide and polychlorinated biphenyls TMDL monitoring,or finalize and submit a workplan for an Integrated Calleguas Creek Watershed organochlorine pesticide and POTW Permittees,MS4 6 months after effective 3 polychlorinated biphenyls Monitoring Program for approval Permittees,Agricultural date of the amendment by the Executive Officer. The monitoring workplan will Dischargers,US Navy include,but not be limited to,appropriate water,biota,and sediment loading and monitoring to verify attainment of targets and protection of beneficial uses. Initiate Calleguas Creek Watershed organochlorine POTW Permittees,MS4 6 months after Executive pesticide,polychlorinated biphenyls,and siltation Officer approval of 4 Monitoring Program developed under the Task 3 workplan Permittees,Agricultural Dih US N Monitoring Program(Task approved b the Executive Officer. scargers, avy 3)workplan Submit a workplan for approval by the Executive Officer to identify urban,industrial and domestic sources of 5 organochlorine pesticides and polychlorinated biphenyls POTW Permittees,MS4 1 year after effective date and control methods and to implement a collection and Permittees,US Navy of the amendment disposal program for organochlorine pesticides and polychlorinated biphenyls . Submit a workplan for approval by the Executive Officer to 6 identify agricultural sources and methods to implement a Agricultural Dischargers 1 year after effective date collection and disposal program for organochlorine of the amendment pesticides and polychlorinated biphenyls. Special Study#1 —Submit a workplan and convene a Science Advisory Panel to quantify sedimentation in Mugu Lagoon and sediment transport throughout the Calleguas Creek Watershed. Evaluate management methods to control siltation and contaminated sediment transport to Calleguas Creek,identify appropriate BMPs to reduce sediment loadings,evaluate numeric targets and wasteload and load allocations for siltation/sedimentation to support POTW Permittees,MS4 1 year after effective date 7 habitat related beneficial uses in Mugu Lagoon, evaluate Permittees,Agricultural of the amendment the effect of sediment on habitat preservation in Mugu Dischargers,and US Navy Lagoon,and evaluate appropriate habitat baseline, effectiveness of sediment and siltation load allocations on a subwatershed basis,and methods to restore habitat for approval by the Executive Officer. Additionally,this special study will evaluate the concentration of organochlorine pesticides and polychlorinated biphenyls in sediments from various sources/land use t es.2 Page 13 July 7, 2005 Attachment A to Resolution No. R4-2005-010 ks }P w p �we���$t10I1 AC40I Develop an Agricultural Water Quality Management Plan in consideration of the forthcoming Conditional Waiver for Irrigated Lands,or,if the Conditional Waiver for Irrigated 9 Lands is not adopted in a timely manner,develop an Agricultural Dischargers 3 years after effective date Agricultural Water Quality Management Plan as part of the of the amendment Calleguas Creek WMP. Implement an educational program on BMPs identified in the Agricultural Water Quality Management Plan. Based on results of the Task 5 workplan approved by 10 Executive Officer,implement a collection and disposal POTW Permittees,MS4 5 years after effective of program for organochlorine pesticides and polychlorinated Permittees,US Navy the amendment bi hen ls. Based on results of the Task 6 workplan approved by 11 Executive Officer implement a collection and disposal Agricultural Dischargers 5 years after effective of program for organochlorine pesticides and polychlorinated the amendment bi hen ls. Re-evaluation of POTW Interim wasteload allocations for 5 years, 10 years and 15 12 organochlorine pesticides and polychlorinated biphenyls Regional Board years after the effective based on State Implementation Plan procedures. date of the amendment Special Study#1 —Submit results of Special Study#1, POTW Permittees,MS4 8 years after effective date 13 including recommendations for refining the siltation load Permittees,Agricultural of the amendment and wasteload allocations. Dischargers,and US Navy 14 Re-evaluation of siltation and sediment load and wasteload Regional Board 9 years after effective date allocations based on Special Stud #1. of the amendment 15 Effective date of siltation load allocation and wasteload Agricultural dischargers, 9 years after effective date allocation. US Navy,MS4 permittees of the amendment Special Study#3—Evaluate natural attenuation rates and POTW Permittees, evaluate methods to accelerate organochlorine pesticide Agricultural Dischargers, 10 years after effective date 16 and polychlorinated biphenyl attenuation and examine the MS4 Permittees, and US of the amendment attainability of wasteload and load allocations in the Navy Calle uas Creek Watershed. Special Study#4(optional)—Examine of the food web and bioconcentration relationships throughout the watershed to 12 years after effective date 17 evaluate assumptions contained in the Linkage Analysis and Interested Parties of the amendment ensure that protection of beneficial uses is achieved.z Based on the results of Implementation Items 1-17,if sediment guidelines are promulgated or water quality criteria are revised,and/or if fish tissue and water column 10 years after effective date 18 targets are achieved without attainment of WLAs or LAs, Regional Board of the amendment the Regional Board will consider revisions to the TMDL targets,allocations,and schedule for expiration of Interim Wasteload and Interim Load Allocations.3 Agricultural Dischargers, 20 years after effective date 19 Achieve Final WLAs and LAs POTW Permittees,and of the amendment MS4 Permittees Page 14 July 7, 2005 Attachment A to Resolution No. 114-2005-010 'Be Regional Board regulatory programs addressing all discharges in effect at the time an implementation task is due may contain requirements substantially similar to the requirements of an implementation task. If such a requirement is in place in another regulatory program including other TMDLs,the Executive Officer may determine that such other requirements satisfy the requirements of an implementation task of this TMDL and thereby coordinate this TMDL implementation plan with other regulatory programs. Special studies included in the Implementation Plan are based on the TMDL Technical Documents. 3 After completion of this special study,the TMDL will be reopened in order to enable the Regional Board to evaluate whether a shorter time period is appropriate for the achievement of the final WI-As and LAs. Page 15 July 7, 2005 Exhibit D State of California California Regional Water Quality Control Board,Los Angeles Region RESOLUTION NO. R4-2006-012 June 8, 2006 Amendment to the Water Quality Control Plan for the Los Angeles Region to Incorporate a Total Maximum Daily Load for Metals for the Calleguas Creek,its Tributaries,and Mugu Lagoon WHEREAS, the California Regional Water Quality Control Board, Los Angeles Region, finds that: 1. The Federal Clean Water Act(CWA)requires the California Regional Water Quality Control Board, Los Angles Region (Regional Board) to develop water quality objectives, which are sufficient to protect beneficial uses for each water body found within its region. Water bodies that do not meet water quality objectives or support beneficial uses are considered impaired. 2. A consent decree between the U.S. Environmental Protection Agency (U.S. EPA), Heal the Bay, Inc_ and BayKeeper, Inc. was approved on March 22, 1999. This court order directs the U.S. EPA to complete'rotal Maximum Daily Loads (TMDLs) for all impaired waters within 13 years. A schedule was established in the consent decree for the completion of the first 29 TMDLs within 7 years, including completion of a TMDL to reduce metals in the Calleguas Creek, its tributaries, and Mugu Lagoon by U.S. EPA by March 22, 2007. The remaining TMDLs will be scheduled by Regional Board staff within the 13-year period. 3. The elements of a TMDL are described in 40 CFR 130.2 and 130.7 and section 303(d) of the CWA, as well as in U.S. EPA guidance documents (Report No. EPA/440/4-91/001). A TMDL is defined as the sum of the individual waste load allocations for point sources, load allocations for nonpoint sources and natural background(40 CFR 130.2). Regulations further stipulate that TMDLs must be set at levels necessary to attain and maintain the applicable narrative and numeric water quality standards with seasonal variations and a margin of safety that takes into account any lack of knowledge concerning the relationship between effluent limitations and water quality (40 CFR 130.7(c)(1)). The regulations in 40 CFR 130.7 also state that TMDLs shall take into account critical conditions for stream flow, loading and water quality parameters. 4. The numeric targets in this TMDL are not water quality objectives and do not create new bases for enforcement against dischargers apart from the existing, numeric water quality standards they translate.The targets merely establish the bases through which load allocations {J-As) and waste load allocations (WLAs) are calculated. WLAs are only enforced for a discharger's own discharges, and then only in the context of its National Pollutant Discharge Elimination System (NPDES) permit, which must contain effluent limits consistent with the assumptions and requirements of the WLA (40 C.F.R. 122.44(d)(vii)(B)). The Regional Board will develop permit requirements through subsequent permit actions that will allow all interested persons, including but not limited to municipal storm water dischargers,to provide comments on how the WLA will be translated into permit requirements. Resolution No.R4-2006-012 Page 2 5. As envisioned by Water Code section 13242, the TMDL contains a "description of surveillance to be undertaken to determine compliance with objectives." The Compliance Monitoring and Special Studies elements of the TMDL recognize that monitoring will be necessary to assess the on-going condition of the Calleguas Creek, its tributaries, and Mugu Lagoon and to assess the on-going effectiveness of efforts by dischargers to reduce metals loading to the Calleguas Creek. Special studies may also be appropriate to provide further information about new data, new or alternative sources, and revised scientific assumptions. The TMDL does not establish the requirements for these monitoring programs or reports, although it does recognize the type of information that will be necessary to secure. The Regional Board's Executive Officer will issue orders to appropriate entities to develop and to submit monitoring programs and technical reports. The Executive Officer will determine the scope of these programs and reports, taking into account any legal requirements, and issue the orders to the appropriate entities. 6. Upon establishment of TMDLs by the State or U.S. EPA, the State is required to incorporate the TMDLs along with appropriate implementation measures into the State Water Quality Management Plan (40 CFR 130.6(c)(1), 130.7). This Water Quality Control Plan for the Los Angeles Region (Basin Plan), and applicable statewide plans, serves as the State Water Quality Management Plans governing the watersheds under the jurisdiction of the Regional Board. Attachment A to this resolution contains the Basin Planning language for this TMDL. 7. The Calleguas Creek Watershed is located in southeast Ventura County, California, and in a small portion of western Los Angeles County, and drains an area of approximately 343 square miles from the Santa Susana Pass in the east, to Mugu Lagoon in the southwest. Current land use is approximately 26 percent agriculture, 24 percent urban, and 50 percent open space. The tributaries and the streams of the Calleguas Creek Watershed are divided into fourteen segments, or reaches. The 2002 Clean Water Act 303(d) list identified lower reaches of the Calleguas Creek watershed(reach 1,2,and 3)as impaired for copper, mercury, nickel, selenium, and zinc. These listings were approved by the State Water Resources Control Board on February 4, 2003. The proposed TMDL addresses impairments of water quality caused by these metals in lower reaches of the Calleguas Creek Watershed. 8. On May 18, 2000, the USEPA promulgated numeric criteria for priority pollutants for the State of California, known as the California Toxics Rule (CTR), codified as 40 CFR section 131.38. Federal water quality standards under section 303 of the Clean Water Act consist of designated uses and criteria to protect those uses_ (40 C.F.R. 131.3(i)). Designated uses are beneficial uses under state law, and criteria are water quality objectives under state law. The CTR establishes the numeric water quality objectives for various toxic pollutants. These objectives apply "without exeception" to all inland surface waters within the State of California, including the Los Angeles region. (40 C.F.R. 131.38(d)(1)-(2)). 9. "[I]t is the national policy that the discharge of toxic pollutants in toxic amounts be prohibited." (33 U.S.C. 1251(a)(3).) Water quality standards, including the CTR, reflect this express national policy of Congress. When a pollutant is present at levels in excess of the CTR numbers, then the pollutant is present in toxic amounts. In this sense, the numeric objectives in the CTR are USEPA's determination of when priority pollutants are present at toxic amounts in contravention of Congress's national policy. W. The Regional Board's goal in establishing the Calleguas Creek Metals TMDL is to protect the aquatic life and wildlife beneficial uses of Calleguas Creek, its tributaries, and Mugu Resolution No,R4-2006-012 Page 3 Lagoon, and to achieve the numeric water quality objectives set to protect these uses as contained in the CTR. 11. The water quality targets for copper in the TMDL are expressed as the copper water quality objective multiplied by a water-effect ratio (WER) consistent with the federal California Toxics Rule (CTR). A WER is a means to account for a difference between the toxicity of copper in laboratory dilution water and its toxicity in local waterbodies. A WER of 1.0 indicates equivalence between local waters and laboratory dilution water, while a WER of greater (less) than 1.0 indicates lower (higher) toxicity in local waters than in laboratory dilution waters. The water-effect ratio (WER) has a default value of 1.0 unless a site-specific WER is approved. To use a WER other than the default of 1.0, a study must be conducted consistent with USEPA's WER guidance and adopted by the Regional Board through the state's basin plan amendment process. 12. A WER study for Mugu Lagoon (Reach 1) lower Calleguas Creek (Reach 2), Revolon Slough (Reach 4) and Beardsley Wash (Reach 5) was conducted by Larry Walker Associates for the Calleguas Creek Management Group with involvement by Regional Board staff. A draft technical report dated September 21, 2005 contains recommended WERs of 2.13 for Mugu Lagoon and Revolon Slough and 4.06 for lower Calleguas Creek. 13, Regional Board staff commented on the draft report in a letter to Larry Walker Associates dated March 15, 2006. Regional Board staff identified several concerns and data limitations of the study that constrained the scientifically defensible alternatives available to the Board. Given these data limitations and unresolved technical issues, Regional Board staff proposed a single WER for the lagoon and lower creek that would be protective. Regional Board staff agreed to reconsider this single WER value if additional wet weather data were collected in the creek and technical issues were resolved. In response to Regional Board comments, Larry Walker Associates sampled an additional wet weather event on April 14, 2006 and Regional Board staff is actively engaged in discussions with Larry Walker Associates and independent technical experts to resolve other technical issues. 14. Upon resolution of these issues,Regional Board staff will recommend site-specific WERs for Mugu Lagoon (Reach 1), lower Calleguas Creek (Reach 2), Revolon Slough (Reach 4) and Beardsley Wash (Reach 5) to the Regional Board. Prior to Regional Board consideration, the proposed basin plan amendment to incorporate site-specific WERs must be submitted for peer review as required by Health and Safety Code section 57004 and be subject to public review and comment. 15. If site-specific WERs are approved by the Regional Board, the TMDL targets and allocations shall be implemented in accordance with the approved WERs using the equations set forth in Table 7-19.1 under "Numeric Targets", "Waste Load Allocations" and "Load Allocations", of the TMDL. 16_ Calleguas Creek stakeholders have been actively engaged with USEPA and the Regional Board on a variety of watershed planning initiatives in the Calleguas Creek Watershed. Key stakeholders have formed the Calleguas Creek Watershed Management Plan (CCWMP), an established, stakeholder-led watershed management group that has been continually operating since 1995. The CCWMP has broad participation from federal, State and county agencies, municipalities, POTWs, water purveyors, groundwater management agencies, and agricultural and environmental groups. As part of its mission to address issues of long-range comprehensive water resources; land use; economic development; open space preservation, Resolution No,R4-2006-012 Page 4 enhancement and management,the CCWMP proposed to USEPA and Regional Board to take the lead on development of the TMDLs. 17. Regional Board staff have worked with the CCWMP and USEPA in the development of a detailed technical document that analyzes and describes the specific necessity and rationale for the development of this TMDL_ The technical document entitled "Calleguas Creek Watershed Metals and Selenium TMDL" prepared by Larry Walker Associates is an integral part of this Regional Board action and was reviewed, and accepted by the Regional Board as a supporting technical analysis before acting. The technical document provides the detailed factual basis and analysis supporting the problem statement,numeric targets(interpretation of the narrative and numeric water quality objectives, used to calculate the pollutant allocations), source analysis, linkage analysis,waste load allocations (for point sources), load allocation (for nonpoint sources), margin of safety, and seasonal variations and critical conditions of this TMDL. 18. On June 8, 2006, prior to the Board's action on this resolution, public hearings were conducted on the Calleguas Creek Watershed Metals TMDL. Notice of the hearing for the Calleguas Creek Watershed Metals TMDL was published in accordance with the requirements of Water Code Section 13244. This notice was published in the Ventura County Star on April 10,2006. 19. The public has had reasonable opportunity to participate in the review of the amendment to the Basin Plan. A draft of the Calleguas Creek Watershed Metals TMDL was released for public comment on March 30, 2006; a Notice of Hearing and Notice of Filing were published and circulated 45 days preceding Board action; Regional Board staff responded to oral and written comments received from the public; and the Regional Board held a public hearing on June 8, 2006 to consider adoption of the TMDL. 20. In amending the Basin Plan, the Regional Board considered the requirements set forth in Sections 13240 and 13242 of the California Water Code. 21. Because the TMDL implements existing numeric water quality objectives (i.e., the numeric water quality criteria established by U.S. EPA in the CTR), the Regional Board has consistently maintained(along with the State Water Resources Control Board)that adopting a TMDL does not require the water boards to consider the factors of Water Code section 13241. The consideration of the Water Code section 13241 factors, by section 13241's express terms, only applies "in establishing water quality objectives." Here the Regional Board is not establishing water quality objectives,but as required by section 303(d)(1)(C) of the Clean Water Act is adopting a TMDL that will implement the previously established objectives that have not been achieved. 22. While the Regional Board is not required to consider the factors of Water Code section 13241, it, nonetheless, has developed and received significant information pertaining to the Water Code section 13241 factors and considered that information in developing and adopting this TMDL_ The past, present, and probable future beneficial uses of water have been considered in that the Calleguas Creek is designated for a multitude of beneficial uses in the Basin Plan. Various living organisms (including vegetation, fish, invertebrates, and wildlife) are present in, transient through, and will be present in the Calleguas Creek. Dry weather surface water in the Calleguas Creek watershed is primarily composed of groundwater, municipal wastewater, urban non-stormwater discharges, and agricultural runoff. In the upper reaches of the watershed, upstream of any wastewater discharges, Resolution No.R4-2006-012 Page 5 groundwater discharge from shallow surface aquifers provide a constant base flow_ "Storm- peaking" refers to peak discharges limited to a wet weather season and concentrated into a few days after short-term, discrete storm events, when flow commonly is two to three orders of magnitude greater than non-storm flow. The environmental characteristics of the Calleguas Creek are spelled out at length in the Basin Plan and in the technical documents supporting this Basin Plan amendment, and have been considered in developing this TMDL. Water quality conditions that reasonably could be achieved through the coordinated control of all factors which affect water quality in the area have been considered via the discussion of likely means of compliance, and studies indicating that a mix of best management practices (BMPs), rather than advanced treatment plants, would achieve the water quality criteria established in the CTR. Authorizing certain storm water dischargers to rely on BMPs in the first instances reflects the reasonableness of the action in terms of the ability to implement the requirements, as well as a belief that the water quality conditions can reasonably be achieved in any event. Establishing a plan that will ensure the Calleguas Creek is not toxic is a reasonable water quality condition. However, to the extent that there would be any conflict between the consideration of the factor in Water Code section 13241 subdivision (c), if the consideration were required, and the Clean Water Act, the Clean Water Act would prevail. Notably, national policy established by Congress prohibits the discharge of toxic pollutants in toxic amounts. Economic considerations were considered throughout the development of the TMDL. Some of these economic considerations arise in the context of Public Resources Code section 21159 and are equatly applicable here. This implementation program recognizes the economic limitations on achieving immediate compliance—especially for municipal storm water dischargers. The TMDL also authorizes the use of BMPs, to the extent authorized by law, for various storm water dischargers. Economic considerations were considered and are reflected in an implementation program that is flexible and allows t0 years for POTWs, and 15 years for agricultural and permitted stormwater dischargers to comply with the final allocations. The need for housing within the region has been considered, but this TMDL is unlikely to affect housing needs. Whatever housing impacts could materialize are ameliorated by the flexible nature of this TMDL and the implementation schedule. 23. The amendment is consistent with the State Antidegradation Policy (State Board Resolution No. 68-16), in that it does not authorize any lowering of water quality and is designed to implement existing water quality objectives. Likewise, the amendment is consistent with the federal Antidegradation Policy(40 CFR 131.12). 24. Pursuant to Public Resources Code section 21080.5, the Resources Agency has approved the Regional Water Boards' basin planning process as a "certified regulatory program" that adequately satisfies the California Environmental Quality Act (CEQA) (Public Resources Code, Section 21000 et seq.)requirements for preparing environmental documents. (14 Cal. Code Regs. § 15251(g); 23 Cal. Code Regs. § 3782.) As such, the Regional Water Board's basin planning documents together with an Environmental Checklist, are the "substitute documents" that contain the required environmental documentation under CEQA. (23 Cal Code Regs. § 3777.) The detailed technical report entitled "Calleguas Creek Watershed Metals and Selenium TMDL", this resolution, and the Environmental Checklist serve as the substitute documents for this project. The project itself is the establishment of a TMDL for toxic metals in the Calleguas Creek, its tributaries, and Mugu Lagoon. While the Regional Board has no discretion to not establish a TMDL (the TMDL is required by federal law) or for determining the water quality standard to be applied (the CTR establishes the numeric water quality objectives that must be implemented), the Board does exercise discretion in assigning waste load allocations and load allocations, determining the program of Resolution No.R4-2006-012 Page 6 implementation, and setting various milestones in achieving the numeric water quality standards established in the CTR. 25. A CEQA Scoping hearing was conducted on January 26, 2006 in the City of Thousand Oaks, 2100 E. Thousand Oaks Blvd., Thousand Oaks, California. A notice of the CEQA Scoping hearing was sent to interested parties including cities and/or counties with jurisdiction in or bordering the Calleguas Creek watershed. 26. The lengthy implementation period allowed by the TMDL, will allow many compliance approaches to be pursued. In preparing the accompanying CEQA substitute documents, the Regional Board has considered the requirements of Public Resources Code section 21159 and California Code of Regulations, title 14, section 15187, and intends the substitute documents to serve as a tier 1 environmental review. Many compliance obligations will be undertaken directly by public agencies that will have their own obligations under CEQA. In addition, public agencies such as the Ventura County, Farm Bureau and the Resource Conservation Disctrict, are expected to facilitate compliance obligations per participated growers, and to the extent that the proposed projects including installation of BMPs, are subject to project- level CEQA analysis, the public agency may assume those responsibilities. Individual growers who propose BMPs that impact waters of the State through dredge or fill operations will be subjected to applicable State and federal permitting requirements. In this instance, the "Lead" State agency will assure compliance with project-level CEQA analysis. Project level impacts will need to be considered in any subsequent environmental analysis performed by other public agencies, pursuant to Public Resources Code section 21159.2, If not properly mitigated at the project level, there could be adverse environmental impacts. The substitute documents for this TMDL, and in particular the Environmental Checklist and staff's responses to comments, identify broad mitigation approaches that should be considered at the project level. Consistent with CEQA, the substitute documents do not engage in speculation or conjecture and only consider the reasonably foreseeable environmental impacts of the methods of compliance, the reasonably foreseeable feasible mitigation measures, and the reasonably foreseeable alternative means of compliance, which would avoid or eliminate the identified impacts. 27. The proposed amendment could have a significant adverse effect on the environment. However, there are feasible alternatives, feasible mitigation measures, or both that would substantially lessen any significant adverse impact. The public agencies responsible for those parts of the project can and should incorporate such alternatives and mitigation into any subsequent projects or project approvals. Possible alternatives and mitigation are described in the CEQA substitute documents, specifically the TMDL technical report and the Environmental Checklist. To the extent the alternatives, mitigation measures, or both are not deemed feasible by those agencies, the necessity of implementing the federally required metals TMDL and removing the metals-related toxicity impairment from the Calleguas Creek (an action required to achieve the express, national policy of the Clean Water Act) outweigh the unavoidable adverse environmental effects. 28_ Health and Safety Code section 57004 requires external scientific peer review for certain water quality control policies. Prior to public notice of the draft TMDL, the Regional Board submitted the scientific basis and scientific portions of the Calleguas Creek Watershed Metals and Selenium TMDL to Theo Dillaha, Ph.D., P.E. (Virginia Tech) and Rhea L. Williamson, Ph.D. (San Jose State University) for external scientific peer review. Written peer review reports were received by the Regional Board. Minor modifications were made to the Resolution No. R4-2006-012 Page 7 scientific portions of the TMDL to address concerns identified during the peer review process_ 29. The regulatory action meets the "Necessity" standard of the Administrative Procedures Act, Government Code, Section 11353, Subdivision (b). As specified above, federal regulations require that TMDLs be incorporated into the water quality management plan. The Regional Board's Basin Plan is the Regional Board's component of the water quality management plan, and the Basin Plan is how the Regional Board takes quasi-legislative, planning actions. Moreover, the TMDL is a program of implementation for existing water quality objectives, and is, therefore, appropriately a component of the Basin Plan under Water Code section 13242. The necessity of developing a TMDL is established in the TMDL staff report, the section 303(d) list, and the data contained in the administrative record documenting the metals impairments of the Calleguas Creek, its tributaries,and Mugu Lagoon. 30_ The Basin Plan amendment incorporating a TMDL for metals for the Callegus Creek, its Tributaries, and Mugu Lagoon must be submitted for review and approval by the State Water Resources Control Board (State Board), the State Office of Administrative Law (OAL), and the U.S. EPA. The Basin Plan amendment will become effective upon approval by U.S. EPA. A Notice of Decision will be filed with the Resources Agency. THEREFORE,be it resolved that pursuant to sections 13240 and 13242 of the Water Code, the Regional Board hereby amends the Basin Plan as follows: 1. Pursuant to Sections 13240 and 13242 of the California Water Code, the Regional Board, after considering the entire record, including oral testimony at the hearing, hereby adopts the amendments to Chapter 7 of the Water Quality Control Plan for the Los Angeles Region, as set forth in Attachment A hereto, to incorporate the elements of the Calleguas Creek, its Tributaries, and Mugu Lagoon Metals TMDL. 2, The Executive Officer is directed to forward copies of the Basin Plan amendment to the State Board in accordance with the requirements of section 13245 of the California Water Code. 3. The Regional Board requests that the State Board approve the Basin Plan amendment in accordance with the requirements of sections 13245 and 13246 of the California Water Code and forward it to OAL and the U,S. EPA. 4. If during its approval process Regional Board staff, the State Board or OAL determines that minor, non-substantive corrections to the language of the amendment are needed for clarity or consistency, the Executive Officer may make such changes, and shall inform the Board of any such changes. 5. The Executive Officer is authorized to sign a Certificate of Fee Exemption. Resolution No.R4-2006-012 Page 8 1, Jonathan Bishop, Executive Officer, do hereby certify that the foregoing is a full, true, and correct copy of a resolution adopted by the California Regional Water Quality Control Board, Los Angeles Region, on June 8, 2006. nathan S.Bishop Date Executive Officer Attachment A to Resolution No. R4-2006-012 Proposed Amendment to the Water Quality Control Plan—Los Angeles Region to Incorporate the Total Maximum Daily Load for Metals and Selenium in the Calleguas Creek, its Tributaries and Mugu Lagoon Adopted by the California Regional Water Quality Control Board, Los Angeles Region on June 8, 2006 Amendments Table of Contents Add: Chapter 7. Total Maximum Daily Loads (TMDLs) 7- 19 Calleguas Creek Watershed Metals and Selenium TMDL List of Figures, Tables, and Inserts Add: Chapter 7. Total Maximum Daily Loads(TMDLs) Tables 7-19 Calleguas Creek Watershed Metals and Selenium TMDL 7-19.1. Calleguas Creek Watershed Metals and Selenium TMDL: Elements 7-19.2. Calleguas Creek Watershed Metals and Selenium TMDL: Implementation Schedule Chapter 7. Total Maximum Daily Loads (TMDLs) Calleguas Creek Watershed Metals and Selenium TMDL This TMDL was adopted by: The Regional Water Quality Control Board on June 8, 2006. This TMDL was approved by: The State Water Resources Control Board on[Insert date]. The Office of Administrative Law on [Insert date]. The U.S. Environmental Protection Agency on [Insert date]. The elements of the TMDL are presented in Table 7-19.1 and the Implementation Plan in Table 7-19.2 June 8, 2006 - 1 - Attachment A to Resolution No. R4-2006-012 Table 7-19.1. Calleguas Creek Watershed Metals and Selenium TMDL: Elements TMDL Element Calleguas Creek Wa�ed Metals and Selenium TN1DL Problem Three of fourteen reaches in the Calleguas Creek Watershed(CCW) Statement including Revolon Slough, Lower Calleguas Creek—Reach 2, and Mugu Lagoon are identified on the 2002 Clean Water Act Section 303(d) list of water-quality limited segments as impaired due to elevated levels of metals and selenium in water. The 303(d) listings, which were approved by the State Water Resources Control Board in February 2003, require the development of TMDLs to establish the maximum amount of pollutants a water body can receive without exceeding water quality standards. TMDLs for listed metals and selenium are presented herein in one document because, as a class of compounds, they possess similar physical and chemical properties that influence their persistence, fate, and transport in the environment. Numeric Targets This TMDL establishes four types of numeric targets: (1) CTR criteria in dissolved fraction for copper,nickel, and zinc, and in total recoverable form for mercury and selenium; (2) Fish tissue targets for mercury; (3)Bird egg targets for mercury and selenium; and (4) Sediment quality guidelines for copper, nickel, and zinc for 303(d) listed reaches. Attainment of sediment quality targets will be evaluated in combination with sediment toxicity data, if available. 1. Copper Targets Water Quality Target Sediment Target Suhwatershed tug dissolved Copper/L,) (SQuiRTs,ERL) Dry Weather Wet Weather CCC CMC (PPh) Mugu Lagoon 3.1*WER' 4.8*WER' 34000 Calleguas Creek 2 11*WER' 4.8*WER' 34000 Calleguas Creek 3 25.9 26.3 NA2 Revolon/Beardsley 3.1*WER' 4.8*WER' NA' Cone'o 27.9 41.6 NA2 Arroyo Simi/Las Posas 1 29.3 29.8 1 NA2 ' The water quality targets for copper in the TMDL are expressed as the copper water quality criteria from the federal California Toxics Rule(CTR).Those criteria include a numerical threshold multiplied by a water-effect ratio(WER). The WER has a default value of 1.0 unless a site-specific WFR is approved.I'D use a WER other than the default of 1.0.a study must be conducted consistent with USEPA's WER guidance and adopted by the Regional Board through the state's basin plan amendment process.A WER study for Mugu Lagoon(Reach 1),lower Calleguas Creek(Reach 2),Revolon Slough (Reach 4)and Beardsley Wash(Reach 5)has been submitted to the Regional Board.If the Regional Board approves site-specific WERs for copper in these waterbodies,the TMDL targets will be modified in accordance with all legal and regulatory requirements and implemented in accordance with the approved WERs using the equations set forth in Table 7-19.1 above. 2 Sediment targets were not selected as alternative target for this reach as it is not on the 303(d)list. June 8,2006 - 2 - Attachment A to Resolution No. R4-2006-012 _ a uas Creek.Watershed Metals >nd`Sele�lium TMDL TMDL Element Caul 2. Mercury Targets a) Fish Tissue(Human Health): 0.3 mg methylmercury/kg wet weight b) Fish Tissue(Wildlife): Trophic Level(TL)3' <50 mm:0.03 mg methylmercury/kg wet weight TL3 50-150mm: 0.05 mg methylmercury/kg wet weight TL3 150-350mm: 0.1 mg methylmercury/kg wet weight c) Bird Egg(Wildlife): less than 0.5 mg total mercury/kg wet weight d) Water Column Target: 0.051 ug total mercury/L 'Tropic Level 3: Predators(e.g.,minnows,sunfish) on tropic level 2 organism(e g.,copepods and water fleas) 3. Nickel Targets Water Quality Target Sediment Target Subwatershed (ug dissolved Nickel/L) (SQuiRTs,ERL) Dry Weather Wet Weather (ppb) CCC CMC Mugu Lagoon 8.2 74 20900 Calle uas Creek 2 8.2 74 NA' Calle uas Creek 3 149 856 NA' RevolonBeardsle 8.2 74 NA' Cone'o 160 1292 NA' Arro o Simi/Las Posas 168 958 1 NA` 'Sediment targets were not selected as alternative target for this reach as it is not listed on the 303(d)list. A study to support a SSO for nickel has been submitted to the Regional Board and is currently under reviewed by the Regional Board and U.S.EPA staff. If a SSO for nickel is approved,the Regional Board will consider revision to the numeric targets for nickel based on the approved SSO. 4. Selenium Targets Water Quality Target Subwatershed (ug Total Selenium/L) Bird Egg Dry Weather Wet Weather (ug/g) CCC CMC Mugu Lagoon 71 290 6 Calle uas Creek 2 5 290 6 Calle uas Creek 3 5 NA' 6 Revolon/Beardsley 5 290 6 Cone'o 5 NA' 6 Arroyo Simi/Lis Posas 5 NA' 6 "NA"indicates that a target is not available for this constituent as criterion for fresh water is not defined in the CTR. June 8, 2406 - 3 - Attachment A to Resolution No.R4-2006-012 TMDL Element Calleguss�areg .k Watershed Metala=-and.selenium TMDL 5. Zinc Targets Water Quality Target Sediment Target Subwatershed (ug dissolved Zinc/L) S uiRTs,ER-L) Dry Weather Wet Weather (ppb) CCC CMC Mugu La oon 81 90 150400 Calle uas Creek 2 81 90 NA` Calle uas Creek 3 338 214 NA' Revolon/Beardsle 81 90 NA' Cone'o 365 324 NA' Arro o Simi/Las Posas 1 382 240 1 NA' Sediment targets were not selected as alternative target for this reach as it is not an the 303(d)list. Source Analysis Significant sources of metals and selenium include urban runoff, agricultural runoff, groundwater seepage, and POTW effluent. For mercury,open space was also a significant source. Sources were also analyzed as a function of wet and dry weather. Higher loads were delivered during wet weather for all constituents, due to the association between metals and particulate matter.. The source analysis indicates naturally occurring mercury in soil may be a significant source,naturally occurring nickel, copper, zinc, and selenium in soil may be a contributing source and naturally occurring selenium in groundwater may be a significant source. The TMDL Implementation Plan also includes special studies to address natural sources of metals in soil. -Linkage Analysis Linkage between sources and instream pollutant concentrations was established through a dynamic water quality Hydrologic Simulation Program—FORTRAN(HSPF). The model output generally resulted in a conservative estimate of receiving water concentrations for metals. The model was used to calculate load reductions necessary to meet Numeric Targets. The load and waste load allocations were calculated based on the load reductions required to meet the numeric targets. Waste Load In the case of copper, nickel, and selenium, waste load allocations Allocations (WLAs) are developed for both wet and dry-weather. The dry-weather WLAs apply to days when flows in the stream are less than the 86th percentile flow rate for each reach. The wet-weather WLAs apply to days when flows in the stream exceed the 86th percentile flow rate for each reach. Annual mass loads of mercury in suspended sediment were developed according to low,medium, and high annual flow categories. A margin of safety of 15% was included in the WLAs for copper and nickel. June 8,2006 -4- Attachment A to Resolution No. R4-2006-012 TMDL Element CaUeguas Creek�'4tg ers$e&MetaU and Selettlum I'LL DL POTWs Concentration-based and mass-based WLAs are established for copper, nickel, and selenium in total recoverable forms, and are applied to POTWs during both wet and dry weather. Mass-based WLAs are developed for mercury for POTWs. Zinc allocations are not set because current information indicate that numeric targets for zinc are attained. The TMDL Implementation Plan includes a task to provide State Board data to support delisting of zinc. Waste load allocations for selenium are not set for POTWs because POTWs do not discharge to reaches listed for selenium. A margin of safety of 15%was included in the WLAs for copper and nickel. Interim limits are included to allow time for dischargers to put in place implementation measures necessary to achieve final waste load allocations. The daily maximum and monthly average interim limits are set equal to the 99th and 95th percentile of available discharge data respectively. 1. Interim and Final WLAs for Total Recoverable Copper in Water Column Interim Final* POTW Daily Monthly Dally Monthly Maximum Average Maximum Average Ibfday (ug/L) (ug/L) (ug/L)** (ug/L)** Hill Canyon 20.0 16.0 (a) (a) 0.11*WER- W WTP 0.04 Simi Valley (b) (b) 31,0 30.5 (c) WacP Moorpark (b) (b) 31.(l AU (d) WTP Camarillo . 012*WER- WRP 37.0 20.0 (a) (a) 0.04 Camrosa (b) (b) Z7A Z7.0 (d) WRP " If site-specific WERs are approved by the Regional Board,TMDL waste load allocations shall be implemented in accordance with the approved WERs using the equations set forth above. Regardless of the final WERs,total copper loading shall not exceed current loading. In addition,effluent concentrations shall not exceed the performance standards of current treatment technologies. ** Concentration-based targets have been converted to total recoverable allocations using the CTR default translator of 0.96 (a) Concentration-based final limits will be included in the permits in accordance with NPDES guidance and requirements,but are not calculated as part of the TMDL. (b) Interim limits are not required because the discharger is meeting the final limits. (c) Discharges from Simi Valley WQCP do not reach lower Calleguas Creek and Mugu lagoon during dry weather. Monitoring will be conducted and mass-based WLAs will be evaluated if targets are not met in Arroyo Simi/Las Posas or downstream reaches. (d) Discharger does not contribute loading during dry weather.Concentration-based WI-As apply during wet weather when discharges occur. Monitoring will be conducted and mass-based WLAs will be evaluated if targets are not met in receiving water and/or downstream reaches. 2. Interim and Final WLAs for Total Recoverable Nickel in Water Column June 8, 2006 - 5 - Attachment A to Resolution No. 114-2006-012 TMDL Element G .lie _Creek Watershed ll t b and� f #1 TMDL .................. . Interim Final POTW Daily Monthly Dally Monthly Maximum Average Maximum Average lb/day (ug/L) (ug/L) (U91 • (ug/L)•" Hill Canyon 8.3 6.4 (a) (a) 0.3 WWTP Simi Valley (b) (b) 960,0 169.0 (c) WQCP Moorpark (b) (b) 960.0 16910 (d) WTP Camarillo 16.0 6.2 (a) (a) 0.2 WRP Camrosa (b) (b)j 858.0 149.0 ((1) WRP Concen(ration-based targets have been converted to total recoverable allocations using the CTR default translator of 0.998. **Concentration-based targets have been converted to total recoverable allocations using the CTR default translator of 0.997. (a) Concentration-based final limits will be included in the permits in accordance with NPDES guidance and requirements,but are not calculated as part of the TMDL. (b) interim limits are not required because the discharger is meeting the final limits. (c) Discharges from Simi Valley WQCP do not reach lower Calleguas Creek and Mugu lagoon during dry weather. Monitoring will be conducted and mass-based WLAs will be evaluated if targets are not met in Arroyo Simi/Las Posas or downstream reaches, (d) Discharger does not contribute loading during dry weather.Concentration-based WLAs apply during wet weather when discharges occur. Monitoring will be conducted and mass-based WLAs will be evaluated if targets are not met in receiving water and/or downstream reaches. A study to support a SSO for nickel has been submitted to the Regional Board and is currently under reviewed by the Regional Board and U.S.EPA staff. If a SSO for nickel is approved,the Regional Board will consider revision to the final WLAs.for nickel based on the approved SSO. 3. Interims and Final WLAs for Mercury in Suspended Sediment: Waste load allocations for POTWs are based on the median monthly mercury effluent concentrations which are currently more stringent than the numeric targets multiplied by the design flow where the total load in water is assumed equal to the suspended sediment load. Interim WLAs for are based on 90th percentile concentration observed in effluent discharge and design flow and apply to all flow conditions. POTW Interim Final (lb/month) (lb/month) Hill Canyon WWTP 0.23 0.022 Simi Valley WQCP 0.18 0.031 Moorpark WTP N/A NIA Camarillo WRP 0.03 0.015 Camrosa WRP I NIA NIA June 8, 2006 - 6 - Attachment A to Resolution No. R4-2046-012 TMDL Elenf nt . CaIleguas Creek Watershed,Metals aitd Selenium ' `NDL Urban Runoff Mass-based WLAs are established for copper,nickel, and selenium in total recoverable forms. Mass-based WLAs are developed for mercury in suspended sediment. Interim limits are included to allow time for dischargers to put in place implementation measures necessary to achieve final waste load allocations. The daily maximum and monthly average interim limits are set equal to the 99th and 95th percentile of available discharge data. I. Interim Limits and Final Waste Load Allocations for Total Recoverable Copper, Nickel, and Selenium Interim limits and waste load allocations are applied in receiving water. A. Interim Limits Calle uas and Cone o Creek Revolon Slough Canstltuents Dry Daily Dry Monthly Wet Daily Dry Daily Monthly wet Daily Maximum Average Maximum Maximum Maximum (ugfL) (ugtL) (ug/L) (uglL) AvAer L e (ugfL) Copper 23 19 204 23 19 204 Nickel 15 1 13 a 15 13 a Selenium I b h 14 c 13 c a (a) The current loads do not exceed the TMDL under wet conditions,interim limits are not required. (b) Selenium allocations have not been developed for this reach as it is not on the 303(d)list. Implementation actions includes consideration of watershed-wide selenium impacts. (c) Attainment of interim limits will be evaluated in consideration of background loading data,if available. B.Final WLAs 1. Dry-Weather WLAs in Water Column (lbs/day) Flow Calleguas and Conejo Creek Revolon Slough Range Average Elevated Average Elevated 9 Low Flow Flow Flow Law Flow Flow Flow Copper` 0.04'WER 0.12*WER 0.18*WER 0.03*WER 0:06"WER 0.13"WER 0.02 0.02 0.03 -001 -0.03 0.02 Nlckel 0.100 0.120 0.440 0.050 0.069 0.116 Selenium a (a) (a) 0.004 0.003 0.004 ' if site-specific WERs are approved by the Regional Board,TMDL waste load allocations shall be implemented in accordance with the approved WERs using the equations set forth above. Regardless of the final WERs,total copper loading shall not exceed current loading. (a) Selenium allocations have not been developed for this reach as it is not on the 303(d)list. Implementation actions include consideration of the watershed-wide selenium impacts. J une 8, 2006 - 7 - Attachment A to Resolution No. R4-2006-012 TMDL Element Calleguas Creek 'WatershedMetals and Selenium TMDL 2. Wet-Weather WLAs in Water Column (lbs/day) Constituent Calleguas Creek Revolon Slough Copper, (0.00054*QA2*0.032*Q-0.17)*WER-0.06 (0.0002*Q2+0.0005*Q)*WER Nlckel** 0.014*Q^2+0.82*Q 0.027*Q^2+0.47*Q Selenium`* (a) 0.027*Q"2+0.47*Q * If site-specific WERs are approved by the Regional Board,TMDL waste load allocations shall be implemented in accordance with the approved WERs using the equations set forth above. Regardless of the final W ERs,total copper loading shall not exceed current loading. **Current loads do not exceed loading capacity during wet weather. Sum of all loads cannot exceed loads presented in the table (a) selenium allocations have not been developed for this reach as it is not on the 303(d)list. Implementation actions include consideration of the watershed-wide selenium impacts. Q: Daily storm volumc. II. Interim Limits and Final WLAs for Mercury in Suspended Sediment(lbs/yr) Final WLAs are set at 80%reduction from HSPF load estimates. Interim limits for mercury in suspended sediment are set equal to the highest annual load within each flow category,based on HSPF output for the years 1993-2003. Calleguas Creek Revolon Slough Flow Range Interim Final Interim Final (lbs/yr) (lbslyr) (lbslyr) (lbslyr) 0-15,000 MGY 3.3 0.4 1.7 0.1 15,000-25,000 MGY 10.5 1.6 4 D.7 Above 25,000 MGY 64.6 9.3 10.2 1.8 MGY: million gallons per year. June 8, 2006 - g - Attachment A to Resolution No. R4-2006-012 TMDL Element Calleguai.crimkWatershed Metals and Selenium TMDL Final WLAs for Other NPDES Dischargers I. Final WLAs for Total Recoverable Copper, Nickel, and Selenium Copper* Nickel Selenium Reach Dry Monthly Wet Daily Dry Monthly Wet Daily Dry Monthly Wet Daily Everage Maximum Average Maximum Average Maximum (ug/L)— (uaL)** (ugIL)— (ug/L)—* (ug/L) (uglL) 1 3.7*WER 5.8*WER 8.2 74 b b 2 3.7*WER 5.8*WER 8.2 74 (b) (b) 3 27.0 27.4 149 859 (b) (b) 4 3.7*WER 5.8*WER 8.3 75 5 290 5 3.7*WER 5.8*WER 8.3 75 5 290 6 (a) 31.0 (a) 958 (b) (b) 7 a) 31.0 (a) 958 b) b 8 a 31,4 a 958 (b) (b) 9 291 433 160 1296 (b) (b) 10 29.1 43.3 160 1296 b b) 11 29.1 43.3 160 1296 b b 12 29.1 43.3 160 1296 (b) (b) 13 29.1 1 433 160 12% b b " If site-specific WERs are approved by the Regional Board,TMDL waste load allocations shall be implemented in accordance with the approved WERs using the equations set forth above. Regardless of the final WERs,total copper loading shall not exceed current loading. In addition,effluent concentrations shall not exceed the performance standards of current treatment technologies ** Concentration-based targets have been converted to total recoverable allocations using the CTR default translator of 4.96 for freshwater reaches and 0.83 for saltwater reaches. *** Concentration-based targets have been convened to total recoverable allocations using the CTR default translator of 0.997 for freshwater reaches and 0.99 for saltwater reaches. (a) Discharges from these reaches do not reach lower Calleguas Creek and Mugu Lagoon during dry weather. Allocations are not required for these reaches. (b) Selenium waste load allocations have not been developed for this reach as it is not on the 303(d)list. Implementation actions include consideration of the watershed-wide selenium impacts. II. Final WLAs for Mercury There is insufficient information to assign mass based WLAs to these sources. Therefore concentration-based waste loads allocations are set equal to 0.051 (ug/L) for other NPDES dischargers based on the CTR water column target for protection of human health from consumption organism only. Load Allocation Mass-based load allocations(LAS) for agriculture, and open space are developed for copper, nickel, and selenium in total recoverable forms. Open space represents background loads from ambient sources (i.e. natural soil concentrations, atmospheric deposition, and natural groundwater seepage) discharged from undeveloped open space, but not ambient sources that are discharged from developed land, such as agricultural and urban areas. LAs are developed for both wet and dry- weather. The d7-weather LAs apply to days when flows in the stream are less than 86t percentile flow rate for each reach. The wet-weather LAs appi to days when flows in the stream exceed 86th percentile flow Tune 8, 2006 - 9- Attachment A to Resolution No. R4-2006-012 ;TMDL Element Calleguas.Creek,Watt rshed- a ls.andgele m TMOL rate for each reach. Annual mass loads of mercury in suspended sediment were developed according to low,medium, and high annual flow categories. A margin of safety of 15%was included in the LAs for copper and nickel. 1. Interims and Final Load Allocations for Total Recoverable Copper,Nickel, and Selenium Interim limits are included to allow time for dischargers to put in place implementation measures necessary to achieve final load allocations. The daily maximum and monthly average interim limits are set equal to the 99th and 95th percentile of available discharge data. Interim limits and load allocations are applied in receiving water at the compliance points. A. Interim Limits Calla uas and Cone"o Creek Revolon Slou h Constituents Dry Daily Monthly wet Daily Dry Daily Monthly Wet Daily Maximum Average Maximum Maximum Average Maximum (ug/L) u (ug1L) (ugiL) L (uglL) Copper 24 19 1390 24 19 1390 Nickel 1 43 42 a 43 42 i ja) Selenium b b b 6.7 c 6 C a (a) The current loads do not exceed the TMDL under wet conditions,interim limits are not required. (b) Selenium allocations have not been developed for this reach as it is not on the 303(d)list. Implementation actions includes consideration of watershed-wide selenium impacts. (c) Attainment of interim limits will be evaluated in consideration of background loading data,if available. B.Final Load Allocation 1. Dry Weather LAs in Water Column (lbslday) Calleguas Creek Revolon Slough Constituent Average Elevated Low Average Elevated Low Flow Flow Flow Flow Flow Flow Agriculture 0.07" WER- 0.12'WER 0.31•WER O.D7"WER 0.14'WER- 0.35'WER- Copper* 0.03 0.02 0.05 0.03 0.07 0.07 Open Space 0.150 0.080 0.130 1 0,050 0.120 0.110 Nickel Agriculture 0.420 0.260 0.970 0.390 0.690 1.600 O pen S ace 0.450 0.420 0.560 0.010 0.020 0.620 Selenium Agriculture a a a 0.008 0.007 0.018 Open Space a) a a 0.180 0.310 0.490 If site-specific WERs are approved by the Regional Board,TMDL load allocations shall be implemented in accordance with the approved WERs using the equations set forth above. (a) Selenium allocations have nol been developed for this reach as it is not on the 303(d)list. Implementation actions include consideration of the watershed-wide selenium impacts. June 8, 2006 _ 10- Attachment A to Resolution No. R4-2006-012 TMDL Element Calleguas.Cii ni t Irshed Metals and Seleanium TMDL 2. Wet Weather LAs in Water Column (lbs/day) Constituent Calleguas Creek Revolon Slough (0.00017*Q^2*0-01*Q- (0.00123*Q^2+0.0034*Q)* Copper* Agriculture 0.05)"1NER-0.02 VVER Open Space 0.0000537*Q^2+0.00321*Q 0.0000432*QA 2+0.000765'0 rAckel- Agriculture 0-014*Q^2+0.82*Q 0.027*QA2+0.47*Q Open Space 0.014*W2+4.82*Q 0.027*Q^2+0.47*Q Selenium*" Agriculture (a) 0.1*Q^2+1.8*Q Open Space I(a) 0.027*Q^2+0.47*Q * If site-specific W ERs are approved by the Regional Board,TMDL load allocations shall be implemented in accordance with the approved WERs using the equations set forth above. ** Current loads do not exceed loading capacity during wet weather. Sum of all loads cannot exceed loads presented in the table (a) Selenium allocations have not been developed for this reach as it is not on the 301(d)list. Implementation actions include consideration of the watershed-wide selenium impacts- Q Daily storm volume II. Interim and Final LAs for Mercury in Suspended Sediment (lbs/yr) Final LAs are set at 80%reduction from HSPF load estimates. Interim limits for mercury in suspended sediment are set equal to the highest annual load within each flow category,based on HSPF output for the years 1993-2003 Calleguas Creek Revolon Slough Flow Range Agriculture Open Space Agriculture Open Space Interim Final Interim Final Interim Final Interim Final 0-15,000 MGY' 3.9 0.5 5,5 0.7 2 0.2 2.9 0.2 15,000-25,000 MGY 12.6 1.9 17.6 2.7 4.8 0.8 6.7 1.1 Above 25,000 MGY 77.5 11.2 108.4 17.9 12.2 1 2.2 17.1 2 MGY:million gallons per year. Margin of Safety A margin of safety(MOS) for the TMDL is designed to address any uncertainty in the analysis that could result in targets not being achieved in the water bodies, Both implicit and explicit MOS are included for this TMDL. The implicit MOS stems from the use of conservative assumptions made during development of multiple numeric targets to ensure sufficient protection under all conditions and conservative methods employed in developing the TMDL. Background loads are assigned to the TMDL and assumed to remain constant throughout implementation of the TMDL. This results in higher required reductions for the other sources. Calculation of allocations is based on never exceeding numeric target concentrations rather than the once in three years exceedance referenced in the CTR. Calculations of current loads and loading capacity for Mugu Lagoon are based on the combined discharges from Calleguas Creek and Revolon Slough(without any dilution rovided by tidal flushing),which over predicts actual June 8, 2006 - 11 - Attachment A to Resolution No. R4-2006-012 ..... .. TMDL Element Calleguas Creek W aitd'Metals and Selenium ' DL concentrations in the Lagoon. A 15% explicit MOS is also included for copper and nickel to account for the uncertainty resulting from the calculation of the allowable load based on the median flow rate and translator of each flow category. The 15% explicit MOS is determined sufficient to address the elevated flow category,but still account for the more conservative nature of low and average category. Future Growth Ventura County accounts for slightly more than 2%of the state's residents with a population of 753,197 (US Census Bureau, 2000). GIS analysis of the 2000 census data yields a population estimate of 334,000 for the CCW, which equals about 44%of the county population. According to the Southern California Association of Governments (SCAG), growth in Ventura County averaged about 51%per decade from 1900-2000; with growth exceeding 70% in the 1920s, 1950s, and 1960s. Significant population growth is expected to occur within and near present city limits until at least 2020. Future growth may initially increase loadings as construction activities expose bare soil and increase erosion-related discharges to receiving water. However, once development has been completed the presence of impermeable land surface and landscaped areas may reduce the amount of natural soils that are eroded and carried to the stream. For copper, future growth could increase loadings from urban areas and POTWs due to increased traffic (i.e., brake pad residues), architectural copper use and corrosion of copper pipes. Selenium loading may increase if increase irrigation raises the groundwater table and increases high selenium groundwater seepage to surface waters. However, if increased growth results in increased water demand and high selenium groundwater is pumped and treated to supply this demand, the selenium could decrease. Seasonal Seasonal variations are addressed for copper, nickel, and selenium by Variations and developing separate allocation for wet and dry weather. Critical Critical conditions for copper,nickel, and selenium are developed using model Conditions results to calculate the maximum observed 4-day average dry weather concentration and the associated flow condition. Wet weather, as a whole, is defined as a critical condition. For mercury,there is no indication that mercury contamination in Mugu Lagoon is consistently exacerbated at any particular time of the year. Since the potential effects of mercury are related to bioaccumulation in the food chain over long period time,any other short term variations in concentration which might occur are not likely to cause significant impacts upon beneficial uses. Therefore, seasonal variations do not affect critical conditions for Calleguas Creek watershed mercury TMDL. June S, 2006 - 12 - Attachment A to Resolution No. R4-2006-012 . .... 1€`1, DL Element Calleguas Creek Watershed Metes t d;S ttun T1VIDL ...... ........ Special Studies Special Studies and Monitoring Plan Several special studies are planned to improve understanding of key aspects related to achievement of WLAs and LAs for the Metals and Selenium TMDL L Special Study#1 (Optional)---Evaluation and Initiation of Natural Sources Exclusion The TMDL technical report has identified ambient sources as the primary significant selenium and mercury loadings in the watershed and as potentially significant sources of copper and nickel. The portion of all ambient sources associated with open space runoff and natural groundwater seepage is accounted for in this TMDL as"background load." This special study will evaluate whether or not background loads for each constituent qualify for natural source exclusion. This study will also consider whether or not any portion of the ambient source contribution for agricultural or urban runoff loads qualify for natural source exclusions and/or provide a basis for site specific objectives. The presence of natural sources makes achievement of selenium and mercury targets during all conditions unlikely. For copper, achievement of the CTR targets or the WER based targets (if approved) in Revolon Slough may not be feasible due to the magnitude of background loads. Completion of site specific objectives and/or a use attainability analysis shall be required to review any potential change to water quality objectives for these constituents. This special study will be used to develop the necessary information to revise the water quality objectives for selenium and mercury and possibly for copper and nickel. 2. Special Study#2 —Identification of selenium contaminated Groundwater Sources The purpose of this special study will be to identify groundwater with high concentrations of selenium that is either being discharged directly to the stream or used as irrigation water. The investigation will focus on areas where groundwater has a high probability of reaching the stream and identify practical actions to reduce the discharge of the groundwater to the stream. The analysis will include an assessment of the availability of alternative water supplies for irrigation water,the costs of the alternative water supplies and the costs of reducing groundwater discharges. June 8, 2006 - 13 - Attachment A to Resolution No. R4-2006-412 MDL Element Calleguas Creek Watershed Metals and Selenia TMDL 3. Special Study#3—Investigation of Soil Concentrations and Identification of"Hat Spots" The purpose of this special study will be to identify terrestrial areas with high concentrations of metals and/or selenium, either due to anthropogenic sources or resulting from high natural concentrations in soils. Use of detailed soil maps for the watershed in combination with field survey and soil sampling may lead to identification of areas important for reducing overall loads reaching the stream. Identification of any areas with elevated soil concentrations of metals and/or selenium would create an opportunity for efficient and targeted implementation actions, such as remediation or erosion control. 4. Special Study#4(Optional)—Determination of Water Effect Ratio for Copper in Revolon Slough The purpose of this optional special study would be to calculate a WER for copper that is specific to Revolon Slough. A WER was not previously developed for Revolon Slough because it was not listed for copper. Subsequent monitoring demonstrated that the saltwater copper CTR criterion was exceeded in the Revolon Slough. This Study would parallel the developed WER for Mugu Lagoon and Calleguas Creek. This is an optional special study to be conducted if desired by the stakeholders or determined necessary by the Executive Officer. 5. Special Study#5(Optional) —Determination of Site-Specific Objectives far Mercury and Selenium Special Study#1 will evaluate whether a natural source exclusion is appropriate for background loads of mercury and selenium or any portion of the ambient source contributions to non-background loads in the Calleguas Creek watershed. This special study will develop any SSOs deemed necessary to account for the background conditions and/or site-specific impacts of mercury and selenium(and possibly for copper and nickel)on wildlife and humans in the watershed. This is an optional special study to be conducted if desired by the stakeholders or determined necessary for establishing a natural source exclusion. Monitoring Plan The Calleguas Creek Watershed TMDL Monitoring Plan (CCWTMP) is designed to monitor and evaluate the implementation of this TMDL and refine the understanding of metal and selenium loads. CCWTMP is intended to parallel efforts of the Calleguas Creek Watershed Nutrients June 8, 2006. - 14 - Attachment A to Resolution No. R4-2006-012 TMDL Element Calleguas Creek'6 -ite h.W.Metals and Selenium``TMDL TMDL, Toxicity TMDL, and OC Pesticide,PCBs, and Sediment TMDL monitoring programs. The proposed CCWTMP shall be made available for public review before approval by the Executive Officer. The goals of the CCWTMP include: (1)to determine compliance with copper, mercury,nickel, and selenium numeric targets at receiving water monitoring stations and at POTWs discharges; (2)to determine compliance with waste load and load allocations for copper,mercury, nickel, and selenium at receiving water monitoring stations and at POTWs discharges; (3)to monitor the effect of implementation action by urban, POTW, and agricultural dischargers on in-stream water quality; and (4) to implement the CCWTMP in a manner consistent with other TMDL implementation plans and regulatory actions within the Calleguas Creek watershed. Monitoring conducted through the Conditional Waiver Program may meet part of the needs of the CCWTMP. To the extent monitoring required by the Metals and Selenium TMDL Implementation Plan parallels monitoring required by the Conditional Waiver Program,it shall be coordinated with the Conditional Waiver Program monitoring conducted by individuals and groups subject to the term and conditions of the Conditional Waiver. Monitoring will begin within one year of the effective date of the TMDL. In-stream water column samples will be collected monthly for analysis of general water quality constituents (GWQC), copper, mercury, nickel, selenium, and zinc for the first year. After the first year, the Executive Officer will review the monitoring report and revise the monitoring frequency as appropriate. In-stream water column samples will be generally be collected at the base of Revolon Slough and Calleguas Creek, and in Mugu Lagoon (collection of flow-based samples will occur above the tidal prism). Additionally, sediment samples will be collected semi-annually in Mugu Lagoon and analyzed for sediment toxicity resulting from copper, mercury, nickel, selenium, and zinc. At such a time as numeric targets are consistently met at these points, an additional site or sites will be considered for monitoring to ensure numeric targets are met throughout the lower watershed. Additional samples will be collected concurrently at representative agricultural and urban runoff land use stations as well as at POTWs in each of the subwatersheds and analyzed for GWQCs, copper, mercury, nickel, selenium, and zinc. The location of the land use stations will be determined before initiation of the CCWTMP. Environmentally relevant detection limits will be used for metals and selenium (Le. detection limits lower than applicable target), if available at a June 8, 2006 - Is - Attachment A to Resolution No. R4-2006-012 TMDL Element Calleguas Greek watershed Metals and Selenium TMDL . commercial laboratory. Compliance sam pling station locations: Subwatershed Station ID Station Location Contituent Water Column:Cu,Ni,Hg,Se,Zn Mugu Lagoon 01-11-BR 11th Street Bridge Bird Egg:H9,Se Fish Tisue:Hg,Se Sediment:Cu,Ni,H9,Se,Zn Revolon Slough 04-WOOD Revolon Slough East Water Column:Cu,Ni,Hg,Se,Zn Side of Wood Road Fish Tisue:Hg.Se 03-CAMAR Calleguas Creek at Uni versity Drive Water Column:Cu,Ni,Hg,Se,Zn University Calleguas Creek 03D-CAMR Camrosa Water Water Column:Cu,Ni,Hg,Se,Zn Reclamation Plant 9AD-CAMR Camarillo Water Water Column:Cu,Ni,Hg,Se,Zn Reclamation Plant Hill Canyon Conejo Creek 10D-HILL Wastewater Treatment Water Column:Cu,Ni,Hg,Se,Zr Plant Implementation The final WLAs will be included for permitted stormwater discharges, Plan POTWs, and other NPDES discharges in accordance with the compliance schedules provided in Table 7-19.2. The Regional Board may revise these WLAs based on additional information developed through special studies and/or monitoring conducted as part of this TMDL. In addition,the implementation schedule was developed with the assumption that a WER for copper and a SSO for nickel will proceed following the TMDL. Should adoption and approvals of the WER and SSO not proceed, additional implementation actions could be required. The implementation plan includes discussion of implementation actions to address these conditions. WLAs established for the three major POTWs in this TMDL will be implemented through NPDES permit limits. Compliance will be determined through monitoring of final effluent discharge as defined in the NPDES permit. The Hill Canyon and Camarillo WRPs are working towards discontinuing the discharge of effluent to Conejo Creek. If this plan is implemented,the POTW allocations for the watershed will be achieved by reduction of effluent discharges to the stream. The implementation plan includes sufficient time for this plan to be implemented. However, if this plan is altered, the POTWs will need to meet allocations through other method such as source control activities. The Regional Board will need to ensure that permit conditions are consistent with the assumptions of the WLAs. Should federal, state, or regional guidance or practice for implementing WLAs into permits be revised, the Regional Board may reevaluate the TMDL to incorporate such guidance. June 8, 2006 - 16 - Attachment A to Resolution No. R4-2006-012 TM L Element Calleguas Creek.Watershed MOtals and Sele>ulnifn TMDL........ In accordance with current practice, a group concentration-based WLA has been developed for all permitted stormwater discharges, including municipal separate storm sewer systems(MS4s), Caltrans, general industrial and construction stormwater permits, and Naval Air Weapons Station Point Mugu. MS4 WLAs will be incorporated into the NPDES permit as receiving water limits measured in-stream at the base of Revolon Slough and Calleguas Creek, and in Mugu Lagoon and will be achieved through the implementation of BMPs as outlined in the implementation plan. The Regional Board will need to ensure that permit conditions are consistent with the assumptions of the WLAs. If BMPs are to be used,the Regional Board will need to detail its findings and conclusions supporting the use of BMPs in the NPDES permit fact sheets. Should federal, state, or regional guidance or practice for implementing WLAs into permits be revised, the Regional Board may reevaluated the TMDL to incorporate such guidance. The Regional Board may revise these WLAs based on the collection of additional information developed through special studies and/or monitoring conducted as part of this TMDL. LAs will be implemented through the State's Nonpoint Source Pollution Control Program(NPSPCP) and Conditional Waiver for Discharges from Irrigated Lands adopted by the Los Angeles Regional Water Quality Control Board on November 3, 2005. Compliance with LAs will be measured in-stream at the base of Revolon Slough and Calleguas Creek and in Mugu Lagoon and will be achieved through the implementation of BMPs consistent with the NPSPCP and the Conditional Waiver Program. The Conditional Waiver Program requires the development of an agricultural water quality management plan (AWQMP)to address pollutants that are exceeding receiving water quality objectives as a result of agricultural discharges. Therefore, implementation of the load allocations will be through the development of an AWQMP for metals and selenium. Implementation of the load allocations will also include the coordination of BMPs being implemented under other required programs to ensure metal discharges are considered in the implementation. Additionally, agricultural dischargers will participate in educational seminars on the implementation of BMPs as required under the Conditional Program. Studies are currently being conducted to assess the extent of BMP implementation and provide information on the effectiveness of BMPs for agriculture. This information will be integrated into the AWQMP that will guide the implementation of agricultural BMPs in the Calleguas Creek watershed. After implementation of these actions, compliance with the allocations and TMDL will be evaluated and the allocations reconsidered if necessary June 8, 2006 - 17 - Attachment A to Resolution No. R4-2006-012 TMDL Element Calleguas Creek WateTShi Metals and SeW L based on the special studies and monitoring plan section of the implementation plan Agricultural and urban dischargers will have a required 25%, 50% and 100%reduction in the difference between the current loadings and the load allocations at 5, 10 and 15 years after the effective date, respectively. Achievement of required reductions will be evaluated based on progress towards BMP implementation as outlined in the UWQMPs, AWQMP, Conditional Waiver for Irrigated Lands, and in consideration of background loading information, if available. If the interim reductions are not met,the dischargers will submit a report to the Executive Officer detailing why the reductions were not met and the steps that will be taken to meet the required reductions. As shown in Table 7-19.2, implementation of LAs will be conducted over a period of time to allow for implementation of the BMPs, as well as coordination with special studies and implementation actions resulting from other TMDL Implementation Plans (Nutrient, Historic Pesticides and PCBs, Sediment, Metals, Bacteria, etc.). The Regional Board may revise the LAs based on the collection of additional information developed through special studies and/or monitoring conducted as part of this TMDL. June 8, 2006 - 18 - Attachment A to Resolution No. R4-2006-012 Table 7-19.2 Calleguas Creek Watershed Metals and Selenium TMDL: Implementation Schedule Item Iiii k <i rotation Action.' Rim] o ldfile Party Campletxo>v Date ..... POTWs,Permitted Effective date of interim Metals and Selenium Stormwater z Effective date of the I TMDL waste load allocation(WLAs),and final Dischargers amendment WLAs for other NPDES permittees (PSD),Other NPDES Permittees 2 Effective date of interim Metals and Selenium Agricultural Effective date of the TMDL load allocation(LAs) Dischargers amendment Submit Calleguas Creek Watershed Metals and POTWs,PSD, Within 3 months after the 3a Selenium Monitoring Program Agricultural effective date of the Dischargers amendment POTWs,PSD, Within 3 months of 3b Implement Calleguas Creek Watershed Metals and Agricultural Executive Officer Selenium Monitoring Program Dischargers approval of the monitoring program Re-calibrate HSPF water quality model based on POTWs,PSD, 1 year after submittal of 3c first year of monitoring data Agricultural first annual monitoring Dischargers report Conduct a source control study,develop and submit Within 2 years after the an Urban Water Quality Management Program 4a (UWQMP)for copper,mercury,nickel,and M54s effective date of the amendment selenium Conduct a source control study,develop and submit Within 2 years after the 4b an UWQMP for copper,mercury,nickel,and Caltrans effective date of the selenium amendment Conduct a source control study,develop and submit NAWS point Mugu Within 2 years after the 4c an UWQMP for copper,mercury,nickel,and (US Navy) effective date of the selenium amendment Within 1 year of approval 5 Implement UWQMP PSD of UWQMP by the Executive Officer Develop and submit an Agricultural Water Quality Agricultural Within 2 years after the 6 Management Program(AWQMP)as described in effective date of the the Conditional Waiver Program Dischargers amendment Agricultural Within 1 year of approval 7 Implement AWQMP of AWQMP by the Dischargers Executive Officer Develop WLAs and LAs for zinc if impairment for Regional Board or Within 1 year of the final 8 Mugu Lagoon is maintained on the final 2006 USEPA 2006 303(d)list 303(d)list Submit progress report on salinity management Within 3 years after the 9 plan,including status of reducing WRP effluent POTWs effective date of the discharges to Conejo and Calleguas Creek reaches of the watershed amendment 10 If progress report identifies the effluent discharges POTWs Within 4 years after the reduction is not progressing,develop and effective date of the The Regional Board regulatory programs addressing all discharges in effect at the time this implementation task is due may contain requirements substantially similar to the requirements of these implementation tasks.if such requirements are in place in another regulatory program including other TMDLs,the F,xecutive 011-icer may revise or eliminate this implementation task to coordinate this TMDL implementation plan with other regulatory programs. s Permitted Stormwater Dischargers(PSD)include MS4s,Caltrans,the Naval Air Weapons Station at Point Mugu,and general industrial and construction permittees. June 8, 2006 - 19 - Attachment A to Resolution No. R4-2006-012 ._...... __....... .................... _..._......._._............... ... Item Inaple�tadpn Acton Res ��Party Completion Date,-- implement source control activities for copper, amendment mercur nickel,and selenium Re-evaluation of POTW interim waste load Within 5 years after the 11 allocations for copper,mercury,and nickel POTWs effective date of the amendment Evaluate the results of the OCs TMDL,Special 12a Study—Calculation of sediment transport rates in Agricultural Within 6 months of the Calleguas Creek watershed for applicability to Dischargers,PSD completion of the study the metals and selenium TMDL Include monitoring for copper,mercury,nickel,and Within 2 years after the selenium in the OC pesticides TMDL,special Agricultural 126 Study—Monitoring of sediment by source and land Dischargers,PSD effective date of the use type amendment Expand scope of the OC Pesticide TMDL,Special If necessary,prior to end 12c Study—Examination of food webs and Interested parties of the implementation accumulation in the Calleguas Creek watershed to period ensure protection of wildlife to include mercury Evaluate the results of the OC Pesticides TMDL, 12d Special Study—Effects of BMPs on Sediment and Agricultural Within 6 months of Siltation to determine the impacts on metals and Dischargers,PSD completion of the study selenium Submit work plan for.Special Study#1 (Optional)— Agricultural Within I year after the 13a Identification of Natural Sources Exclusion Dischargers,PSD effective date of the amendment Submit results of Special Study#1 (Optional)— Agricultural Within 3 years of 14b Identification of Natural Sources Exclusion Dischargers,PSD approval of workplan by Executive Officer Submit work plan for Special Study#2 — POTWs,PSD,and Within I year after the 14a Identification of selenium Contaminated Agricultural effective date of the Groundwater Sources Dischargers amendment Submit results of Special Study#2 —Identification POTWs,PSD,and Within 1 year of approval 14b of selenium Contaminated Groundwater Sources Agricultural of workplan by Executive Dischargers Officer Submit work plan for Special Study#3 — PSD and Within 1 year after the 15a Investigation of Metals'"Hot Spot"and Natural Agricultural effective date of the Soil Discharger amendment Submit results of Special Study#3 —Investigation PSD and Within 2 years of 156 of metals'"Hot Spot"and Natural Soil Agricultural approval of workplan by Dischar er Executive Officer Special Study#4(Optional)—Determination of PSD and If necessary,prior to end 16 WER for copper in Revolon Slough Agricultural of the implementation Dischargers period Special Study#5 (Optional)—Determination of Site PSD and If necessary,prior to end 17 Specific Objective for Mercury and Selenium Agricultural of the implementation Dischargers period Evaluate effectiveness of BMPs implemented under PSD and 6 years after the effective IS the AWQMP and L WQMP in controlling metals Agricultural date of the amendment and selenium discharges Dischargers Evaluate the results of implementation actions 14 POTWs,PSD,and Within I year after the 19 and 15(Special Study#2&#3)and implement Agricultural completion of the studies actions identified by the studies Dischar ers 20 If needed,implement additional BMPs or revise Agricultural 7 years after the effective existing BMPs to address any issues not covered by Dischargers I date of the amendment June 8, 2006 -20 - Attachment A to Resolution No. R4-2006-012 Item Im lamentation Actionr _ Respgnsible.Party Inmtion Date implementation efforts of related Calleguas Creek watershed TMDLs(Nutrients,Toxicity,OC Pesticides,PCBs,and Siltation)and the Conditional Waiver Program 21 Consider nickel SSO proposed by stakeholders Regional Board 1 years after the effective date of the amendment Publicly notice tentative copper water effects ratio Within 2 months of 22 for Regional Board consideration,if deemed Regional Board receipt of peer review appropriate based on peer review Staff comments Based on the result from items 1-23,Regional 2 years from submittal of 23 Board will consider re-evaluation of the TMDLs, Regional Board information necessary for WLAs,and LAs if necessary re-evaluation POTWs will be required to reduce loadings by 50% and 100%of the difference between the and 10 years after the 24 current loading and the WLAs at 8,and 10 years POTWs effective date of the amendment after the effective date,respectively. Re-evaluation of Agricultural and Urban load and waste load allocations for copper,mercury,nickel, and selenium based on the evaluation of BMP 5, 10,and 15 years after effectiveness. Agricultural and urban dischargers Agricultural and 25 will have a required 25%,50%,and 100% Urban Dischargers the effective date of the reduction in the difference between the current amendment loadings and the load allocations at 5, 10,and 15 ears after the effective date,respectively. Stakeholders and Regional Board staff will provide information items to the Regional Board,including: 2 years after the effective 26 progress toward meeting TMDL load reductions, Regional Board date,and every 2 years water quality data,and a summary of following im lementation activities completed to date Achievement of Final WLAs and attainment of Within 10 years after the 27 water quality standards for copper,mercury,nickel, POTWs effective date of the and selenium amendment' Achievement of Final WLAs and LAs and Agricultural Within 15 years after the 28 attainment of water quality standards for copper, Dischar PSD effective date of the nickel,mercury and selenium gers, amendment' 'Date of achievement of WLAs and LAs based on the estimated timeframe for educational programs,special studies,and implementation of apprupriate BMPs and associated monitoring. The Conditional Waiver Program will set timeframes for the BMP management plans. June 8,2006 - 21 - Exhibit E August 15, 2007 Revision 1 DRAFT Calleguas Creek Watershed Management Plan Quality Assurance Project Plan (QAPP) Monitoring and Reporting Program Plan for the Nitrogen , OC and PCBs, and Toxicity Total Maximum Daily Loads submitted to Los Angeles Regional Water Quality Control Board prepared by LARRY WALKER ASSOCIATES on behalf of the CALLEGUAS CREEK WATERSHED MANAGEMENT PLAN WATER QUALITY/WATER RESOURCES SUBCOMMITTEE A. PROJECT MANAGEMENT 1. Title and Approval Sheets Calleguas Creek Watershed Management Plan Quality Assurance Project Plan (QAPP) Total Maximum Daily Load Monitoring and Reporting Program Plan for the Nitrogen, OC and PCBs, and Toxicity TMDLs Regional Board Point of Contact Don Kendall, Chair Calleguas Creek Watershed Water Date Resources/Quality Subcommittee Fiscal Agent/ Program To be determined Date Manager Project Manager To be determined Date Project QA Manager To be determined Date Lab QA Officer Jeff Cotsifas, Pacific EcoRisk(Toxicity Lab) Date Lab QA Officer Rich Gossett, CRG Marine Laboratories Date LARWQCB Project Manager Thanhloan Nguyen Date LARWQCB QA Officer Yanjie Chu Date 2. Table of Contents A. PROJECT MANAGEMENT 2 1. Title and Approval Sheets.......................................................................2 2. Table of Contents ...................................................................................1 3. Distribution List.......................................................................................3 4. Project Organization ...............................................................................4 5. Problem Definition/Background ..............................................................7 6. Project Description ...............................................................................10 7. Quality Objectives and Criteria for Measurement Data.........................15 8. Training and Certification......................................................................17 9. Documents and Records......................................................................17 B. DATA GENERATION AND ACQUISITION 18 10. Sampling Process Design.....................................................................19 11. Sampling Methods................................................................................36 12. Sample Handling and Custody .............................................................43 13. Analytical Methods ...............................................................................47 14. Quality Control......................................................................................58 15. Instrument/Equipment Testing, Inspection and Maintenance...............63 16. Instrument/Equipment Calibration and Frequency................................64 17. Inspection/Acceptance of Supplies and Consumables.........................67 18. Non-Direct Measurements....................................................................67 19. Data Management................................................................................67 C. ASSESSMENT AND OVERSIGHT 68 20. Assessments and Response Actions ...................................................68 21. Reports to Management.......................................................................69 D. DATA VALIDATION AND USABILITY 71 22. Data Review, Verification and Validation Requirements.......................71 23. Data Verification ...................................................................................71 24. Data Validation .....................................................................................71 E. AMENDMENTS TO QAPP 72 F. REFERENCES 73 CCWTMP QAPP 1 August 15,2007 Revision 1 TABLES Table 1. Description of CCW Reaches Based on 2002 303(d) List.................................................. 9 Table 2. Constituents and Monitoring Frequency for CCWTMP (varies by site) .............................12 Table 3. Optional Constituents and Monitoring Frequency for CCWTMP (varies by site)...............13 Table 4.Year 1 Project Deliverable Schedule for CCWTMP...........................................................15 Table 5. Data Quality Objectives.....................................................................................................16 Table 6. CCWTMP Compliance Monitoring and Nutrient Investigation Sites and Annual Sampling Frequency...............................................................................................................24 Table 7. Toxicity Investigation Monitoring Sites and Sampling Frequency......................................25 Table 8. CCWTMP Land Use Monitoring Sites and Sample Frequency.........................................26 Table 9. Compliance, Toxicity, and Nutrient Investigation Monitoring Schedules' ..........................35 Table 10. Sample Collection Requirements of Monitoring Programs in the CCW...........................38 Table 11. Sample Container, Volume, Initial Preservation, and Holding Time Requirements.........45 Table 12. Analytical Methods and Project Reporting Limits for Field Measurements......................48 Table 13.Analytical Methods and Project Method Detection and Reporting Limits for Laboratory Analysis..................................................................................................................49 Table 14. Quality Control Requirements.........................................................................................59 Table 15. Required Data Completeness.........................................................................................60 Table 16. Calibration of Field Measurement Equipment.................................................................65 Table 17. Reports to Management Schedule..................................................................................69 FIGURES Figure 1. Calleguas Creek Watershed TMDL Monitoring Program Management Structure............. 6 Figure 2. Calleguas Creek Watershed............................................................................................. 8 Figure 3. CCWTMP Compliance Monitoring Sampling Sites—Receiving Water............................27 Figure 4. Compliance Monitoring Receiving Water Sampling Sites—Freshwater Sediment...........28 Figure 5. Compliance Monitoring Receiving Water Sampling Sites—Freshwater Fish Tissue .......29 Figure 6. Compliance Monitoring Sampling Sites—POTW Effluent................................................30 Figure 7. Compliance Monitoring Sampling Zones—Mugu Lagoon Sediment................................31 Figure 8. Compliance Monitoring Sampling Zones—Mugu Lagoon Tissue ....................................32 Figure 9. Toxicity Investigation Receiving Water Sampling Sites—Water and Sediment...............33 Figure10. Land Use Sampling Sites...............................................................................................34 Figure 11. Example Field Measurement Equipment Calibration Log Sheet....................................66 Figure 12. Example Field Measurement Equipment Calibration Verification Log Sheet..................66 APPENDICES Appendix A: Sampling Site Descriptions Appendix B: Basin Plan Amendments Appendix C: Supporting Documents for Field Procedures Appendix D: Supporting Documents for Toxicity Testing and Benthic Infuana Assessment Appendix E: Supporting Documents for Chemical Analysis Appendix F: Example Field Log Sheet and Chain-of-Custody Form Appendix G: Calculations for Data Quality Assessments Appendix H: Chapter 13 QA/QC Data Evaluation from Caltrans Guidance Manual: Stormwater Monitoring Protocols, 2nd Edition Appendix I:April 24, 2007 Comment Letter from the Los Angeles Regional Water Quality Control Board and Response to Comments CCWTMP QAPP 2 August 15,2007 Revision 1 3. Distribution List Name Agency Contact E-mail Number Sam Unger Los Angeles Regional Water Quality 213-576-6622 sunger @waterboards.ca.gov Control Board Thanhloan Los Angeles Regional Water Quality 213-576-6690 tnguyen @waterboards.ca.gov Nguyen Control Board Yanjie Chu Los Angeles Regional Water Quality 213-576-6681 ychu @waterboards.ca.gov Control Board Don Kendall Chair, Calleguas Creek Water 805-526-9323 DKendall @calleguas.com Resources/Quality Subcommittee To be determined Fiscal Agent/Contract Manager To be determined City of Camarillo To be determined City of Moorpark To be determined City of Oxnard To be determined City of Simi Valley To be determined City of Thousand Oaks To be determined County of Ventura To be determined Ventura County Waterworks District No. 1 To be determined Camrosa Water District To be determined Camarillo Sanitary District To be determined U.S. Dept.of Navy To be determined California Department of Transportation To be determined Ventura County Agricultural Irrigated Lands Group within the Calleguas Creek Watershed, a subdivision of the Farm Bureau of Ventura County To be determined Project Manager To be determined Project Quality Assurance Manager Jeff Cotsifas Toxicity Lab—Pacific EcoRisk (925) 313- cotsifas @pacificecorisk.com 8080 Rich Gossett Analytical Lab—CRG Marine (310) 533- crglabs @sbcglobal.net Laboratory 5190 CCWTMP QAPP 3 August 15,2007 Revision 1 4. Project Organization The Basin Plan Amendments (BPA) for each Total Maximum Daily Load (TMDL) in the Calleguas Creek watershed (CCW) identifies individual responsible parties. Implementation Plans outlined in the BPAs for the following three adopted TMDLs for the CCW require the development and implementation of monitoring programs: • Nitrogen Compounds and Related Effects in Calleguas Creek(Nitrogen TMDL) • Organochlorine (OC) Pesticides, Polychlorinated Biphenyls (PCBs) and Siltation in Calleguas Creek, its Tributaries, and Mugu Lagoon (OCs TMDL) • Toxicity, Chlorpyrifos, and Diazinon in the Calleguas Creek, its Tributaries and Mugu Lagoon (Toxicity TMDL) The QAPP is intended to allow for the inclusion of additional monitoring requirements identified in the Metals and Selenium TMDLs and as yet to be adopted TMDLs (e.g., bacteria). The CCW TMDL Monitoring Program (CCWTMP) is a coordinated effort with the various stakeholders that make up the Calleguas Creek Watershed Management Plan (CCWMP)and the Water Quality/Water Resources Subcommittee. Responsible parties identified in the TMDL have developed a Memorandum of Agreement(MOA)that outlines an agreement to implement the CCWTMP QAPP. The responsible parties identified in the organizational structure illustrated in Figure 1 have formally joined together to fulfill their monitoring requirements as outlined in the BPAs. The CCWTMP QAPP is intended to fulfill the TMDL monitoring requirements for only those parties which are part of the MOA or otherwise identified by the participants of the MOA. Monitoring efforts will be coordinated by the parties to the MOA grouped as follows: • POTWs: consisting of Camrosa Water District, Camarillo Sanitary District, Ventura County Waterworks District No. 1, and the Cities of Simi Valley and Thousand Oaks; • Urban Dischargers: consisting of the Cities of Simi Valley, Thousand Oaks, Camarillo, Moorpark and Oxnard and the County of Ventura Public Works Agency; • Agricultural Dischargers: consisting the entities represented by the Ventura County Agricultural Irrigated Lands Group within the Calleguas Creek Watershed, a subdivision of the Farm Bureau of Ventura County; and • Other Dischargers: consisting of the U.S. Department of Navy and Caltrans. Per the MOA, a Management Committee consisting of one representative each from the POTWs, Urban Dischargers and Other Dischargers groups and two representatives from the Agricultural Dischargers group will oversee the CCWTMP and make decisions to assure the CCWTMP is carried out in a timely, accountable fashion. Management Committee, contract and laboratory staff will have the following roles: • Fiscal Agent/Contract Manager: To be determined. The Fiscal Agent/Contract Manager will contract with the selected Contractors to implement the CCWTMP consisting of monitoring, laboratory services, data management and reporting and act as the liaison between the Management Committee and Contractors. • Project Manager: To be determined. The Project Manager will be a Contractor CCWTMP QAPP 4 August 15,2007 Revision 1 responsible with overseeing the day to day activities of implementing the CCWTMP QAPP and report directly to the Fiscal Agent/Contract Manager. • Project Quality Assurance Manager: To be determined. The Project Quality Assurance Manager will conduct quality assurance oversight for the project independently from project management and from the project's monitoring program. • Laboratory Quality Assurance Officer, Toxicity Testing: Jeff Cotsifas (Pacific EcoRisk) • Laboratory Quality Assurance Officer, Chemistry: Rich Gossett(CRG Marine Laboratory) • Sample Collection: To be determined. The Project Manager will be responsible for updating the QAPP, as necessary, and ensure sufficient review is conducted and signatures are obtained. The various Elements (or sections)of the QAPP describe the quality assurance requirements for the CCWTMP developed to comply with the requirements of the aforementioned BPAs. All contractors selected to perform the sampling and laboratory analyses must meet the quality control criteria necessary to satisfy the data quality objectives of this program, including those for precision, accuracy, detection and reporting. This QAPP is based on the State's Surface Water Ambient Monitoring Program (SWAMP) Quality Assurance Management Plan (Pucket, 2002) and prepared in accordance with the State Water Resources Control Board's SWAMP QAPP Template (SWRCB, 2004a) and the SWAMP-QA Checklist(SWRCB, 2004b). CCWTMP QAPP 5 August 15,2007 Revision 1 Calleguas Creek Watershed TMDL Monitoring Program- Responsible Agencies Cities of Camarillo, Moorpark, Oxnard, Simi Valley and Thousand Oaks, County of Ventura;Ventura County Waterworks District No. 1; Camrosa Water District, Camarillo Sanitary District, U.S. Dept.of Navy; California Department of Transportation; and the Ventura County Agricultural Irrigated Lands Group within the Calleguas Creek Watershed, a subdivision of the Farm Bureau of Ventura County LARWQCB LARWQCB QA Officer Project Manager Yanjie Chu Thanhloan Nguyen Management Committee From MOA Groups 1 from POTW 1 from Urban Dischargers 2 from Agricultural Dischargers 1 from Other Dischargers Regional Board Point of Contact Don Kendall, Chair Calleguas Creek Watershed Water Resources/Quality Subcommittee Fiscal Agent/Program Manager To be determined ----------------------------------------I--------- --------------------------------- [::To oject Manager CONTRACTORS be determined Field Sampling Laboratories QA Manager Crews Pacific EcoRisk To be determined To be determined and CRG Figure 1. Calleguas Creek Watershed TMDL Monitoring Program Management Structure CCWTMP QAPP 6 August 15,2007 Revision 1 5. Problem Definition/Background Located in Ventura County California, the Calleguas Creek Watershed (CCW), though relatively small in area, suffers from more water quality impairments than most California watersheds, as defined by the USEPA's 303(d) list. Calleguas Creek drains an area of approximately 343 square miles from the Santa Susana Pass in the east to Mugu Lagoon in the southwest. The main surface water system drains from the mountains in the northeast part of the watershed toward the southwest where it flows through the Oxnard Plain before emptying into the Pacific Ocean through Mugu Lagoon. The watershed, which is elongated along an east-west axis, is about thirty miles long and fourteen miles wide. The Santa Susana Mountains, South Mountain, and Oak Ridge form the northern boundary of the watershed; the southern boundary is formed by the Simi Hills and Santa Monica Mountains. The Clean Water Act requires TMDLs be developed to restore 303(4) listed waterbodies, and the State of California Porter-Cologne Water Quality Act requires that an Implementation Plan be developed to achieve water quality objectives. States must develop water quality management plans to implement the TMDL (40 CFR 130.6). The USEPA has oversight authority for the 303(d) program and is required to review and either approve or disapprove the TMDLs submitted by states. If the USEPA disapproves a TMDL submitted by a state, USEPA is required to establish a TMDL for that waterbody. Figure 2 depicts the CCW and Table 1 presents the reaches of the CCW as identified in the TMDLs. CCWTMP QAPP 7 August 15,2007 Revision 1 C) N D� 23 Tapo Canym °, s Arroyo Simi n (off yo F V 51 t Fr ' Simi 3} it ey am r#it a ITI Conoo ) Creek(14) hP North w ryxnaed` k(86) (112) Conk► S"Fo* )otredt p). wm poll Ileguas Cr44k e�sw casee �. Uas.. , 01 ( ) � �04 1 a z � � 0 2.5 5 Miles 23 < cn s Calleguas Creek Watershed (-' CC W Reaches Major Roadways ,1, Calleguas Creek Watershed ) Ys Agriculture-Row Crops,Nursery,Other y ° CD Calleguas Subwatersheds Streams/Channels e� �►Ventura County Agriculture-Lemon,Orange,Avocado - - Reach Break Laity Walker Associates July,2006 Figure 2. Calleguas Creek Watershed Table 1. Description of CCW Reaches Based on 2002 303(d) List Reach OCs and Reach Name Reach as No. Reach Name Toxicity TMDLs Listed in the 1999 Geographic Description Subwatershed Consent Decree 1 Mugu Lagoon Mugu Mugu Lagoon Lagoon fed by Calleguas Creek Calleguas Calleguas Creek Reach Downstream(south)of Potrero 2 Creek South Calleguas 1 and Reach 2(Estuary Rd to Potrero Rd.) Calleguas Calleguas Creek Reach Potrero Rd. upstream to 3 Creek North Calleguas 3(Potrero to Somis Rd.) confluence Conejo Creek Revolon Revolon Slough Main Revolon Slough from 4 Slough Revolon Branch confluence with Calleguas Creek to Central Ave Beardsley Beardsley Channel Revolon Slough upstream of 5 Channel Revolon Central Ave. Arroyo Las Posas Reach Confluence with Calleguas Arroyo Las 1 and Reach 2(Lewis Creek to Hitch Road 6 Posas Las Posas Somis Rd.to Moorpark Fwy(23)) Arroyo Simi Reach 1 End of Arroyo Las Posas 7 Arroyo Simi Arroyo Simi and Reach 2(Moorpark (Hitch Rd)to headwaters in Fwy(23)to Headwaters) Simi Valley. 8 Tapo Canyon Arroyo Simi Tapo Canyon Reach 1 Confluence w/Arroyo Simi up and Reach 2 Tapo Cyn to headwaters Conejo Creek Reach 1 Extends from the confluence 9A Conejo Creek Conejo (Confl with Calleguas with Arroyo Santa Rosa Creek to Santa Rosa downstream to the Camrosa Rd.) Diversion. Conejo Creek Reach 1 Extends from Camrosa 9B Conejo Creek Conejo and Reach2(Confl with Diversion to confluence with Calleguas Creek to Tho. Calleguas Creek. Oaks city limit) Hill Canyon Conejo Creek Reach 2 Confluence w/Arroyo Santa 10 reach of Conejo and Reach 3(Santa Rosa to confluence w/N. Fork; Conejo Creek Rosa Rd.to Lynn Rd.) and N. Fork to just above Hill Canyon WTP Arroyo Santa Conejo Arroyo Santa Rosa Confluence w/Conejo Creek 11 Rosa to headwaters North Fork Conejo Creek Reach 3 Confluence w/Conejo Creek to 12 Conejo Creek Conejo (Tho.Oaks city limit to headwaters Lynn Rd.) Arroyo Conejo Conejo Creek Reach 4 Confluence w/N.Fork to 13 (South Fork Conejo (Above Lynn Rd.) headwaters—two channels Conejo Creek) CCWTMP QAPP 9 August 15,2007 Revision 1 Monitoring Questions The CCW TMDL Monitoring Program (CCWTMP)was developed to meet the monitoring requirements for the three aforementioned TMDLs. The goals of the CCWTMP include: 1. To determine compliance with numeric targets, waste load and load allocations. 2. To test for sediment toxicity at sediment monitoring stations. 3. To identify causes of unknown toxicity. 4. To generate additional land use runoff data to better understand pollutant sources and proportional contributions from various land use types. 5. To monitor the effect of implementation actions by urban, POTW, and agricultural dischargers on in-stream water, sediment, and fish tissue quality. 6. To implement the program consistent with other regulatory actions within the CCW. The CCWTMP is intended to answer the following monitoring questions to meet the goals of the program: 1. Are numeric targets and allocations met at the locations indicated in the TMDLs? 2. Are conditions improving? 3. What is the contribution of constituents of concern from various land use types? Water, sediment, and fish tissue samples collected throughout the watershed will be analyzed to determine whether targets and allocations are being met. Data collected through the CCWTMP will be used with historic data to evaluate whether conditions are improving. Samples collected at land use sites will provide data to evaluate the contribution of constituents of concern from each type of land use to receiving waterbodies. Lastly, the data will be used to evaluate the CCWTMP's effectiveness at answering the monitoring questions and provide guidance for modifications. Water quality or regulatory criteria The Basin Plan Amendments (BPA)for each TMDL provides the applicable allocations and criteria. Data collected through the CCWTMP will be compared against allocations and criteria provided in the BPA to evaluate compliance with the TMDLs. Appendix B contains a copy of the BPA for each TMDL addressed in the CCWTMP. The QAPP is intended to allow for the inclusion of additional monitoring requirements such as those identified in recently adopted TMDLs (e.g., metals and selenium) and as yet to be adopted TMDLs (e.g., metals and bacteria). 6. Project Description The primary purpose of the QAPP is to outline the process for collecting data to meet the goals of the CCWTMP. Data collected through previous studies were compiled for use in developing the TMDLs and will be considered along with data collected through the CCWTMP. Monitoring is currently being undertaken by various groups including participants in the Ventura County Agricultural Irrigated Lands Group (VCAILG) under the Conditional Waiver for Irrigated Agricultural Lands program (Ag Waiver) and NPDES POTW and MS4 Permittees. Additionally, the Nutrients, Toxicity, and OCs TMDL Implementation Plans call for special studies to be completed to investigate a range of issues. A summary of special studies is provided in this section and Appendix B contains the BPAs which outline the requirements for the special studies. CCWTMP QAPP 10 August 15,2007 Revision 1 The CCWTMP provides a means for integration of the information developed through these efforts. Data collected through the Ag Waiver, NPDES POTW and MS4 Permittees, and special studies will be incorporated to the extent practicable. The extent practicable will be dictated by the cost of gathering and compiling information from outside programs. It is not the intent or purpose of the CCWTMP to compile and analyze all available data. The QAPP identifies three categories of monitoring: • Required—Required monitoring is intended to determine compliance with the TMDL and meet the BPA monitoring requirements. • Optional—Optional monitoring is monitoring, identified by the responsible parties, which may provide additional relevant information, but is not required to determine compliance with the TMDL or meet the BPA monitoring requirements. • Special Studies—Special studies monitoring is intended to address sample collection for special studies identified in the BPAs or developed through other processes. The QAPP provides information on sample collection and analysis methodologies relevant to all three categories of monitoring. However, it is the intent of the descriptions contained in the following sections to distinguish between what monitoring falls within each category. It is the following descriptions that indicate whether sampling is required, optional, or a special study not a discussion presented later in the QAPP. Required Monitoring Elements The following environmental monitoring elements are required by the BPAs and are included in the CCWTMP: • General water and sediment quality constituents; • Water column and sediment toxicity; • Pesticides in water, sediment, and fish tissue; and, • Nitrogen and phosphorus compounds in water. Table 2 lists the constituents for which analysis will be conducted, all of which are considered critical as discussed in Element 14 (Quality Control). Table 2 also provides a general sampling frequency. Element 10 (Sampling Process Design) presents the approach to determining sampling frequency, the sample frequency for each site, site selection, and descriptions and maps of site locations. Elements 11 (Sampling Methods)and 13 (Analytical Methods)outline the measurement processes and techniques that will be used to collect information. Additional constituents may be required in the future, dependent on additional TMDLs, the results of Toxicity Identification Evaluations (TIEs), or other unforeseen reasons. In these cases, the QAPP will be amended to provide adequate guidance, as necessary. Constituents that are not identified in Table 2 may be reported as these constituents are typically analyzed along with a suite of constituents. These additional constituents are not considered critical and are above and beyond those required to meet TMDL monitoring requirements. However, they will be reported if analyzed. CCWTMP QAPP 11 August 15,2007 Revision 1 Table 2. Constituents and Monitoring Frequency for CCWTMP (varies by site) Constituent Frequency Chronic Aquatic Toxicity Quarterly+Two wet events General Water Quality Constituents(GWQC) Flow,pH,Temperature, Dissolved Oxygen,Conductivity,Total Suspended Solids Quarterly+Two wet events (TSS) and Hardness Nutrients Ammonia Nitrogen, Nitrate Nitrogen, Nitrite Nitrogen,Organic Nitrogen,Total, Quarterly Kjehdahl Nitrogen(TKN),Total Phosphorus,Orthophosphate-P Organic Constituents In Water Quarterly+Two wet events OC Pesticides'and PCBs2, OP3,Triazine4,and Pyrethroid5 Pesticides Chronic Sediment Toxicity Annually (Every three years in Lagoon) General Sediment Quality Constituents(GSQC) Annually Total Ammonia, Percent Moisture,Grain Size Analysis,Total Organic Carbon(TOC) (Every three years in Lagoon) Organic Constituents In Sediment Annually OC Pesticides' and PCBs2,OP Pesticides3,and Pyrethroids5 (Every three years in Lagoon) Additional Constituents For Mugu Lagoon Sediment Every three years Metals? Tissue Annually Percent Lipids,OC Pesticides' and PCBs6,and OP Pesticides3 (Every three years in Lagoon) 1 OC Pesticides considered: aldrin,alpha-BHC,beta-BHC,gamma-BHC(lindane),delta-BHC,chlordane-alpha, chlordane-gamma,2,4'-DDD,2,4'-DDE,2,4'-DDT,4,4'-DDD,4,4'-DDE,4,4'-DDT,dieldrin,endosulfan I and II, endosulfan sulfate,endrin,endrin aldehyde,endrin ketone,and toxaphene 2 PCBs in water and sediment considered: Aroclors identified in the CTR(1016, 1221, 1232, 1242, 1248, 1254,and 1260). 3 OP Pesticides considered: chlorpyrifos,diazinon,and malathion. Chlorpyrifos is the only OP pesticide that will be measured in tissue as it is the only OP listed in tissue. 4 Triazine Pesticides considered: atrazine,prometryn,and simazine. 5 Pyrethroid Pesticides considered: bifenthrin,cyfluthrin,cypermethrin,deltamethrin,and permethrin 6 PCBs in tissue considered: individual congers. 7 Metals included in this program are: arsenic,cadmium,copper,lead,nickel,and zinc. These metals were selected as they have been found in previous sediment studies conducted in Mugu Lagoon to exceed guideline values used to interpret the relationship between sediment chemistry and biological impacts. Additional metals and/or selenium may be added in the future to address the needs of the Metals TMDL. Optional Monitoring Elements All optional monitoring is considered above and beyond what is necessary to meet the requirements of the BPAs and answer the monitoring questions. Optional monitoring is presented in the QAPP so the procedures for conducting the monitoring are available should the Management Committee decide to conduct the monitoring. The following environmental monitoring elements are considered optional: • Grain size fraction analysis of bed sediment and stormwater. Grain size fraction analysis is not necessary to determine compliance with water and sediment wasteload allocations as OC and Toxicity TMDL allocations are set for whole samples not the various fractions within a sample. The various fractions (aqueous and sediment and the two grain size fractions) may assist in developing an understanding of how target organic constituents are transported through the watershed. Grain size fraction analysis is further described in the Grain Size Fraction Analysis section of Element 13 (Analytical Methods). CCWTMP QAPP 12 August 15,2007 Revision 1 • Toxicity to either Mytilus edulis or Crassostrea gigas embryo due to exposure to Mugu Lagoon sediments. Embryo testing is not necessary to evaluate the presence or absence of sediment toxicity as the standard method for testing sediments for toxicity in saltwater, which is the use of a standard test species such as Eohaustorius estuarius, is scheduled to occur through the Required Monitoring Element of the QAPP. Embryo testing provides additional information for comparison to the California Sediment Quality Guidelines, which are currently under development and are applicable only to subtidal environments. Embryo toxicity testing is further described in the Toxicity Testing and Toxicity Identification Evaluations (TIEs)section of Element 13 (Analytical Methods). • Macrobenthic community assessment in Mugu Lagoon. Macrobenthic community assessment is intended to provide additional information to evaluate toxicity in Mugu Lagoon. Similar to the embryo toxicity testing, this assessment is not necessary to evaluate the presence or absence of sediment toxicity rather it provides additional information for comparison to the California Sediment Quality Guidelines. Macrobenthic community assessment in Mugu Lagoon is further described in the Macrobenthic Community Assessment section of Element 13 (Analytical Methods). The Management Committee will determine when any optional monitoring elements will be included. The Project Manager will provide recommendations on optional monitoring elements to the Management Committee at a minimum annually. The Management Committee will determine each year whether the optional monitoring should be initiated, modified, or eliminated (although optional monitoring may be revised more frequently if approved by the Management Committee). Modifications to optional monitoring elements will be documented in the Annual Report. The decision to initiate, modify, or eliminate optional monitoring shall be communicated to the Regional Board Project Manager so the Regional Board is clearly informed of the monitoring that is to occur. Table 3 lists the constituents and analysis which are considered optional. These constituents and analysis are not considered critical as discussed in Element 14 (Quality Control). Table 3 also provides a general sampling frequency. Element 10 (Sampling Process Design) presents the approach to determining sampling frequency, the sample frequency for each site, site selection, and descriptions and maps of site locations. Elements 11 (Sampling Methods) and 13 (Analytical Methods) outline the measurement processes and techniques that will be used to collect information. Table 3. Optional Constituents and Monitoring Frequency for CCWTMP (varies by site) Constituent Frequency Organic Constituents In Water-Grain Size Fractions' One wet event annualy OC Pesticides and PCBs,OP,Triazine,and Pyrethroid Pesticides Organic Constituents In Sediment-Grain Size Fractions' Annually OC Pesticides and PCBs, OP,Triazine,and Pyrethroid Pesticides (Every three years in Lagoon) Additional Constituents For Mugu Lagoon Sediment Macrobenthic community assessment Every three years Sediment Toxicity-Embryo Mytilus edulis or Crassostrea gigas 1 Please see Table 2 for a list of individual constituents in each suite. CCWTMP QAPP 13 August 15,2007 Revision 1 Special Studies The Nutrients, Toxicity, and OCs TMDL Implementation Plans identify required and optional special studies to investigate a range of issues (Appendix B). As the primary purpose of the QAPP is to outline the process for collecting data, the QAPP is an appropriate place to include information on sample collection and analysis methodologies used in special studies. No specific special studies are incorporated into the QAPP at this time; however, a summary of special studies that may be incorporated at a later date are provided below. Work plans for specific special studies will be submitted to the Regional Board Executive Officer for approval per the BPAs. Additional special studies may be added as other TMDLs are completed (e.g., bacteria)or developed through other processes. Nutrient TMDL Special Studies • Determine the effectiveness of agricultural BMPs in reducing nutrient loadings. • Monitoring of minor point sources for nutrients to confirm assumptions that the loadings from these sources are minor; • Monitoring of greenhouse discharges and runoff to assess loadings from these sources; • Monitoring of groundwater extraction and discharges in the Arroyo Santa Rosa subwatershed and other areas that may add significant nutrient loadings to Calleguas Creek; and • Additional studies of the type and extent of algae impairment in Calleguas Creek and Mugu Lagoon. OCs and PCBs TMDL Special Studies • Quantify sedimentation in Watershed and evaluate management methods, targets and allocations for siltation/sedimentation. • Evaluate the concentration of OCs in sediments from various sources/land use types. • Identify land areas with high OCs concentrations. • Evaluate natural attenuation rates and evaluate methods to accelerate OCs attenuation and examine the attainability of allocations. • Examine the food web and bioconcentration relationships to evaluate the Linkage Analysis. This special study is identified as optional in the BPA. Toxicity TMDL Special Studies • Investigate diazinon and chlorpyrifos replacement pesticides. • Consider results of OCs special studies. Project Schedule The Effective Date of the Toxicity and OCs TMDLs is March 26, 2006. Per the BPAs, Responsible Parties must finalize and submit a workplan for a Monitoring Program for approval by the Regional Board Executive Officer(EO) six months after the effective date, which is September 26, 2006. The QAPP was submitted by the Stakeholders on September 26, 2006 to meet the BPA deadline. Comments provided by the Regional Board were received by Stakeholders on April 24, 2007. Table 4 outlines the deliverable schedule for the first year of monitoring. However, this schedule assumes EO approval of the Monitoring Program within one month of the submittal of this version (Revision 1)of the QAPP. If EO approval is delayed, the project deliverable schedule will be modified. The Annual Report for the first year of monitoring will be submitted so that it CCWTMP QAPP 14 August 15,2007 Revision 1 encompasses a single water year(October through September). In the case of the first year of monitoring, if monitoring were to be initiated in April 2008, as presented in Table 4, the first year Annual Report would be submitted in February 2009. Table 4.Year 1 Project Deliverable Schedule for CCWTMP Deliverable Anticipated Date of Initiation Anticipated Date of Completion QAPP April 2006 September 2007 1st Cycle of Monitoring' April 2008 September 30,2009 Review of 1st Set of Data May 2008 December 31,2009 1st Annual Report2 December 31,2009 February 27,2010 1 Monitoring must be initiated within six months after EO approval of the QAPP. All dates after QAPP submission will be tied to EO approval. 2 Data will be delivered in an electronic format along with the Annual Report. 7. Quality Objectives and Criteria for Measurement Data The objective of the monitoring program, in terms of data quality, is to produce data that represent as closely as possible, in situ conditions of the CCW. This objective will be achieved by using accepted methods for sample collection and laboratory analysis. Assessing the program's ability to meet this objective will be accomplished by evaluating the resulting laboratory measurements in terms of reporting limits, precision, accuracy, representativeness, comparability, and completeness, as presented in Section B. Table 5 lists the constituents that will be measured through this monitoring program. Table 5 lists constituents that were not identified in Table 2 as these constituents are typically analyzed along with a suite of constituents. The additional constituents listed in Table 5 are not considered critical and are above and beyond what are required to meet TMDL monitoring requirements. CCWTMP QAPP 15 August 15,2007 Revision 1 Table 5. Data Quality Objectives Parameter Accuracy Precision Recovery Target Reporting Completeness Limits Field Measurements Water Velocity(for Flow calc.) +2% NA NA 0.05 ft/sec pH +0.2 pH units +0.5 pH units NA NA Temperature +0.5 oC +5% NA NA Dissolved Oxygen +0.5 mg/L + 10% NA 0.5 mg/L Turbidity + 10% + 10% NA 0.2 NTU Conductivity +5% +5% NA 2.5 umhos/cm Laboratory Analyses—Water Aquatic Toxicity [1] [2] NA NA Hardness 70-130% 0-30% 70—130% 5 mg/L Total Suspended Solids(TSS) NA 0-30% NA 1 mg/L Ammonia Nitrogen 70-130% 0-30% 70—130% 0.1 mg/L Nitrate Nitrogen 70-130% 0-30% 70—130% 0.1 mg/L Nitrite Nitrogen 70-130% 0-30% 70—130% 0.05 mg/L Organic Nitrogen NA NA NA NA Total Kjehdahl Nitrogen(TKN) 70-130% 0-30% 70—130% 0.5 mg/L Total Phosphorus 70-130% 0-30% 70—130% 0.1 mg/L Orthophosphate-P 70-130% 0-30% 70—130% 0.01 mg/L OC Pesticides3 MDL—155% 0-30% MDL—155% See Element 13 PCB CongenerS3 60-125% 0-30% 60—125% See Element 13 PCB Aroclors3 65-135% 0-30% 65—135% See Element 13 OP Pesticides3 45-125% 0-30% 45—125% See Element 13 See Element 14 Pyrethroids3 65-125% 0-30% 65—125% See Element 13 (Quality Control) TriazineS3 70-130% 0-30% 70—130% See Element 13 Laboratory Analyses—Sediment Sediment Toxicity [1] [21 NA NA Macrobenthic Community Assessment NA NA NA lowest practical taxonomic level Total Ammonia in Sediment 70-130% 0-30% 70—130% 0.05 mg/wet kg Percent Moisture NA 0-30% NA 0.1% Particle Size Distribution NA 0-30% NA 0.04 um Total Organic Carbon(TOC) NA 0-30% MA 0.05%Dry Weight OC Pesticides3 25-145% 0-30% 25—145% See Element 13 PCB CongenerS3 60-125% 0-30% 60—125% See Element 13 PCB Aroclors3 65-135% 0-30% 65—135% See Element 13 OP Pesticides3 35-135% 0-30% 35—135% See Element 13 Pyrethroids3 55-130% 0-30% 55—130% See Element 13 MetalS3 10-180% 0-30% 10—180% See Element 13 Laboratory Analyses—Tissue Percent Lipids NA 0-30% NA 0.05% OC Pesticides3 MDL—155% 0-30% MDL—155% See Element 13 PCB Congeners3 60-125% 0-30% 60—125% See Element 13 PCB Aroclors3 65-135% 0-30% 65—135% See Element 13 OP Pesticides3 45-125% 0-30% 45—125% See Element 13 1 Must meet all method performance criteria relative to the reference toxicant test. 2 Must meet all method performance criteria relative to sample replicates. 3 Please see Table 2 for a list of individual constituents in each suite. CCWTMP QAPP 16 August 15,2007 Revision 1 8. Training and Certification No specialized training or certifications are required for sampling personnel. However, staff that will perform field sampling should receive annual refresher training to ensure the samples are collected correctly and safely. The Project Manager, or designee, will provide training prior to initiation of sampling and will document training of staff. Documentation will consist of a sign in sheet, time and date, and instructor. The documentation will be maintained in the project files of the Project Manager. All sampling shall be performed under the supervision of experienced staff. No volunteers will be used for sampling. At minimum, laboratories selected to perform analysis for this program must maintain current certification through the California Department of Health Services—Environmental Laboratory Accreditation Program (ELAP)or the National Environmental Laboratory Accreditation Program (NELAP). Pacific EcoRisk(toxicity testing laboratory) and CRG Marine Laboratories(chemistry laboratory) are both certified by the NELAP; their certificate numbers are 04225CA and 2261, respectively. Any additional laboratories used to conduct analysis on CCWTMP samples will be accredited by ELAP and/or NELAP and meet the requirements outlined in the QAPP. Toxicity and chemistry laboratories are required to maintain records of analyst training and will make these records available upon request. 9. Documents and Records Documents and records generated and maintained for the CCWTMP include the following: Event Summary Reports, Analytical Data Reports, QAPP, and the Annual Report. The Event Summary Reports, Analytical Data Reports, and QAPP are discussed in detail in this section. The Annual Report is discussed in detail in Element 21 (Reports to Management). Event Summary Reports Event Summary Reports will be created by the field crew and submitted to the Project Manager and Project QA Manager, or designee, within one week of the completion of each sampling event, and will consist of the following: 1. A brief(one to two page) narrative summary of samples successfully collected; 2. A summary of any deviations from the QAPP; 3. A discussion of any problems encountered during the sample event; 4. A discussion of any follow up action required (e.g., follow up toxicity analysis); and, 5. A copy of the field log book and Chain-of-Custody(COC)forms. The field log book and COCs will be scanned into PDFs and stored in electronic format by the Project Manager and in hard copy by the field crew lead. The field log book and COC forms are discussed in Element 12 (Sample Handling and Custody). Analytical Data Reports Analytical data reports will consist of a hardcopy report in each laboratory's standard format and in an electronic format approved by the Project Manager. All final data reports will include the results of Quality Assurance analyses and a narrative summary of Quality Control data for the CCWTMP QAPP 17 August 15,2007 Revision 1 r environmental results reported. Results of chemical analyses, toxicity testing, and any Toxicity Identification Evaluations (TIEs) performed will be provided to the Project QA Manager, or designee, in the laboratory's standard report format within 30 days of sample delivery and in an approved electronic data format. In addition to the laboratory's standard reporting format, all results meeting data quality objectives and results having satisfactory explanations for deviations from data quality objectives shall be reported in tabular format on electronic media. For each sample analyzed, the analyzing laboratory shall provide the following information: • Lab Name • CAS number • Client Sample ID • Analytical method(s) • Lab Sample ID • Method detection limit(MDL), if applicable • Date of sample receipt • Reporting limit(RL), if applicable • Date and time of collection • Measured value of the analyte or parameter • Date of sample preparation, if applicable • Units • Parameter • Relative percent differences, if applicable • Batch Number • Percent recovered, if applicable • Method of sample preparation, if applicable • Dilution factor, if applicable • Date(s) of analysis • Matrix In addition, the analyzing laboratory shall provide results from all laboratory QC procedures (blanks, duplicates, spikes, reference materials, etc.) and the sample IDs associated with each sample batch. Data reports will be compiled in a database as described in Element 19 (Data Management). The CAS number may be added during the data compilation process if the laboratory is not set up to provide the number in their data report. QAPP The Project Manager or designee is responsible for the development, distribution, and management of the QAPP. Distribution and Management of Documents The Project Manager, or designee, is responsible for the development, distribution, and management of the approved QAPP, Annual Report(including the database), and other relevant documentation to all individuals listed in Element 3 of this document. All hard copy and electronic data will be stored by the Project Manager, or designee. Data will be maintained for the length of the program and will be available for review. A backup copy of each data report will be placed on an external storage device (i.e., compact disc). Upon completion of the CCWTMP, hard copy data will be retained for an additional five years. B. DATA GENERATION AND ACQUISITION Sample collection and analysis will be the most involved and resource intensive aspect of the monitoring program. The numerous requirements and considerations which must be taken into account are described below. CCWTMP QAPP 18 August 15,2007 Revision 1 10. Sampling Process Design The following Element provides a description and justification for the sampling design strategy and site selection. The primary driver in designing the monitoring outlined in the QAPP is to meet the monitoring requirements of the TMDL implementation plans. Toxicity, OCs, and Nutrients TMDL monitoring requirements can be broken out into two types: compliance and investigation. In addition to the monitoring sites sampled as part of the CCWTMP, an effort will be made to obtain data from other monitoring programs in the watershed. Additionally, results generated through the CCWTMP may be used by other programs. Element 18 (Non-Direct Measurements) describes the process for including data collected through other programs. These programs include NPDES permitted entities and Ag Waiver program participants. It is the desire of the responsible entities to avoid duplicative sampling efforts and additional coordination will occur as each program develops. Optional monitoring is included in the QAPP and identified as such. Optional monitoring may be conducted to provide supplementary information to assist in developing a more complete understanding of the watershed. However, as certain components of monitoring are above and beyond what is required in the TMDL these components may be may be modified or eliminated by the Management Committee per the process outlined in the Optional Monitoring Elements section of the Project Description (Element 6). Changes to aspects of the sampling process design related to meeting the monitoring requirements of the TMDL implementation plans will be recommended in the Annual Report and agreed upon by the Management Committee identified in Element 4 (Project Organization) and the Regional Board Project Manager. Additional changes may be required in the future, dependent on additional TMDLs (e.g., metals and bacteria), the results of Toxicity Identification Evaluations (TIEs), or other unforeseen reasons. In these cases, the QAPP will be amended to provide adequate guidance, as necessary. Compliance Monitoring For compliance monitoring, in-stream water column samples will be collected quarterly for analysis of water column toxicity, general water quality constituents (GWQC), target organic constituents, and nutrients. Target organic constituents for the OCs TMDL include the OC Pesticides and PCBs listed as a footnote in Table 2. Target organic constituents for the Toxicity TMDL include the OP, pyrethroid, and triazine pesticides listed as a footnote in Table 2. Although pyrethroids are not on the 303(4) list and have not been identified as contributing to toxicity in the CCW, they have been identified as contributing to sediment toxicity elsewhere in California as the use of this group of pesticides increases (Weston et al., in press). Triazine herbicides are not on the 303(4) list and have not been identified as contributing to toxicity in the CCW, however they are included because the potential exists for toxicity caused by chlorpyrifos and diazinon to be increased in their presence (Anderson and Lydy, 2002). In-stream water column samples to measure compliance for the Toxicity and OCs TMDLs will generally be collected at the base of each of the subwatersheds used to assign waste load and load allocations, per the BPAs. In-stream water column samples to measure compliance for the Nutrients TMDL will generally be collected at the base of each listed reach. Site selection CCWTMP QAPP 19 August 15,2007 Revision 1 procedures and the locations of the compliance monitoring sampling stations are discussed in subsequent sections. Toxicity identification evaluations (TIEs)will be conducted on toxic samples as outlined in the Toxicity Testing and TIE section of Element 13 (Analytical Methods). For organic constituents, environmentally relevant detection limits will be used to the extent practicable. Detection limits will be the lower of either the allocations or the numeric targets presented in the TMDLs, if attainable at a commercial laboratory through standard analytical techniques. Additionally, POTW effluent will be monitored for compliance with the effluent limits presented in the Toxicity and OCs TMDL BPAs. Nutrients will not be monitored through the CCWTMP as the POTWs are currently monitoring for all nutrient constituents identified in Table 2. However, the data collected by the POTWs will be considered in the TMDL Annual Report. All efforts will be made to include two additional wet weather water sampling events for compliance monitoring for the OCs and Toxicity TMDLs during targeted storm events between October and April. Wet weather sampling conditions are discussed in the Sampling Schedule section of this Element. Wet weather water samples will not be collected at POTWs as POTW effluent during wet weather was not identified as a significant source of constituents identified in the TMDLs. Streambed sediment samples will be collected annually for analysis of sediment toxicity, general sediment quality constituents (GSQC), and target organic constituents in the freshwater monitoring sites in the watershed. An annual frequency was selected as it will provide sufficient data over the implementation timeframe (20 years for the OCs TMDL) to evaluate changes in sediment quality due to implementation actions. Additionally, an annual frequency is consistent with similar monitoring programs conducted in California, including the Central Coast Agricultural Conditional Waiver for Irrigated Lands Monitoring Program and the San Gabriel River Regional Monitoring Program. Sediment samples will be collected in Mugu Lagoon once every three years for similar analysis. A frequency of every three years was selected for Mugu Lagoon sediment sampling due to the relatively slow sedimentation rates in the lagoon. A model developed to simulate hydrodynamics and sediment transport in Mugu Lagoon estimated sedimentation deposition rates which varied across the lagoon from less than 0.6 to greater than 3 centimeters (cm) per year(RMA, 2003). Collection of sediment samples, which for most parameters occurs in the top two to three cm, would exceed annual deposition rates within portions of the lagoon resulting in the characterization of current and historic deposits. The time period represented in samples would vary from site to site based on deposition rates. In addition, pollutants identified as causing toxicity may be related to historic deposits. Although identifying the presence and cause of toxicity, even if related to historic deposits, provides information on current conditions in the lagoon it does not provide the information needed to implement or modify BMPs. Fish tissue samples will be collected annually in freshwater portions of the watershed to assess changes in concentrations of target organic constituents. Fish tissue samples will be collected every three years in Mugu Lagoon. The same reasoning used for establishing sediments sampling frequency was used to establish fish tissue sample collection frequency. CCWTMP QAPP 20 August 15,2007 Revision 1 Investigation Monitoring Investigation monitoring focuses on investigating the contribution of constituents of concern from various land uses in the watershed and several areas where toxicity has been observed to occur in the past that are not addressed by compliance monitoring. Additional investigation monitoring will focus on evaluating nutrient loading during wet weather. Land Use Discharge Investigation Land use discharge samples will generally be collected concurrently(on the same day when possible)with compliance monitoring at representative agricultural and urban discharge sites generally located in each of the subwatersheds and analyzed for selected GWQC and target organic constituents. Land use sampling stations are generally located at a point where water from a representative group of similar land uses discharges to one of the major reaches of the CCW listed in Table 1. Nutrient Investigation Sampling in support of nutrient investigation monitoring will focus on evaluating urban land use and open space contributions of nutrients and nutrient loads in receiving waters during wet weather. The urban land use component of nutrient investigation monitoring is addressed through the land use discharge investigation discussed above. An open space site was selected at a location in the watershed where flows are present throughout the year from a drainage that is comprised entirely of open space. Evaluation of nutrient loading during wet weather will be addressed through collecting samples at compliance monitoring sites and urban, agricultural, and open space land use monitoring sites. Nutrient investigation monitoring is intended to occur during the first year of the CCWTMP, unless results suggest continuing at one or more sites. Toxicity Investigation For water toxicity investigation monitoring, in-stream water column samples will be collected at two sites where the cause(s) of water toxicity have not been identified. The locations of toxicity investigation sampling sites are discussed in the following Sampling Sites section. These samples will be analyzed for the same constituents as toxicity compliance monitoring, and TIEs will be conducted on toxic samples as outlined in the Toxicity Testing and TIE section of Element 13. All efforts will be made to include two additional wet weather water sampling events for toxicity and land use investigation monitoring during targeted storm events between October and April. Wet weather sampling conditions are discussed in the Sampling Schedule section of this Element. For sediment toxicity investigation monitoring, streambed sediment samples will be collected in two reaches of the CCW where the cause(s)of sediment toxicity have not been identified. These samples will be analyzed for the same constituents as toxicity compliance monitoring, and TIEs will be conducted on toxic samples as outlined in the Toxicity Testing and TIE section of Element 13. Sampling Sites Compliance monitoring sampling sites for the Nutrients TMDL are generally located at the base of each listed reach. Compliance monitoring sampling sites for the OCs and Toxicity TMDLs are generally located at the base of each of the six subwatersheds and at the POTW effluent discharge locations. In the case of the Revolon Slough and Calleguas Subwatersheds, compliance CCWTMP QAPP 21 August 15,2007 Revision 1 monitoring sampling sites are located upstream of the base of the subwatersheds as 1) these locations are not tidally influenced and 2)the majority of the toxicity, OCs and PCBs data in these subwatersheds have been collected at the upstream locations. Compliance monitoring sampling sites for sediment toxicity are located in the Revolon Slough, Calleguas, and Mugu Lagoon Subwatersheds. Fish tissue samples in the freshwater portion of the CCW will be collected near the water compliance monitoring sampling sites, to the extent practicable. In the case of the Mugu Lagoon Subwatershed, compliance with water targets will be measured at the base of the upstream subwatersheds to the lagoon. Compliance with sediment targets will be measured in several zones throughout the lagoon in subtidal areas that consistently maintain a salinity level of greater than 25 ppt. Sediment sampling zones were located in subtidal areas with salinity level of greater than 25 ppt so that data could be compared to the California Sediment Quality Objectives, which are currently under development. Because of shifting shoals and sand bars in the lagoon, sediment samples will be collected from the deepest part of the channel in the sampling zones instead of reoccupying stations based only on GPS coordinates. Fish tissue samples will be collected from the central portion and the western arm of the lagoon. As discussed previously, monitoring programs such as the Ag Waiver Program and NPDES programs (POTW and Stormwater)collect water samples throughout the CCW. In some instances sites associated with other programs overlap with CCWTMP sites. In other instances, sites for other programs are located in areas where there are currently no CCWTMP sites. For example, there are Ag Wavier sites that measure toxicity in the Beardsley Wash (Reach 5) area and POTW sites that measure for OC pesticides in the Hill Canyon area of Conejo Creek (Reaches 10 and 12). These data will be considered with data collected through the CCWTMP as discussed in Element 18 (Non-Direct Measurements). Table 6 presents information on compliance monitoring sites and sample collection frequency. Figure 3 through Figure 5 present the general locations of the receiving water compliance monitoring sites for water, sediment, and fish tissue, not including Mugu Lagoon. Figure 6 presents the general locations of the POTW effluent discharge sites. Figure 7 and Figure 8 present the general locations of the compliance monitoring zones in Mugu Lagoon for sediment and fish tissue, respectively. Nutrient investigation sites, which are not land use sites, correspond to existing nutrient compliance monitoring sites and are presented in Figure 3. Table 6 presents information on nutrient investigation monitoring sites and sample collection frequency. The water and sediment toxicity investigation sampling sites coincide with current and previous sampling programs in the CCW. Figure 9 presents the general locations of the water and sediment toxicity investigation sampling sites in the CCW. Table 7 lists the water and sediment toxicity investigation sampling sites and sampling frequency. At least one agricultural and urban discharge land use sampling station is located in each subwatershed. Land use sampling stations are generally located at a point where water from a representative group of similar land uses discharges to one of the major reaches of the CCW listed in Table 1. An open space land use site is also included for evaluating nutrient loadings as part of the nutrient investigation. Land use sampling sites coincide with current and previous sampling programs in the CCW, where available. Figure 10 presents the general locations of the land use sampling sites in the CCW. Table 8 presents land use sampling stations and sampling frequency. CCWTMP QAPP 22 August 15,2007 Revision 1 The process for selection of appropriate sites was based on location within a subwatershed for which waste loads and loads were allocated, existing data, and access considerations. Current or previously used sampling sites were selected whenever practical to save time and resources, and to provide historical data. Selecting sites previously or currently in use for other monitoring efforts ensures that they are easily accessible and maximizes opportunities for future cost sharing. Waste load and load allocations were assigned by 303(d) listed reach in the Nutrients TMDL. Accordingly, at least one compliance monitoring site is located in each 303(4) listed reach. Waste load and load allocations were assigned by modeling subwatersheds in the Toxicity and OCs TMDL. Accordingly, at least one compliance monitoring site is located in each modeling subwatersheds. Investigation sites for water and sediment toxicity were selected based on existing data suggesting impairment. Investigation sites for various land use sites were selected based on land use, existing data, and access considerations. Investigation sites for nutrients were selected based on land use and existing data suggesting impairment. The number and location of sites may be revised if existing sites become inaccessible, if it is determined that alternative locations are needed, or if the number of land use stations needed to appropriately characterize discharges needs modification. At such a time as numeric targets are consistently met, an additional site or sites within the subwatershed will be considered for monitoring to ensure allocations are met throughout the subwatershed. Any changes with regard to the number and location of sites will be determined through discussions between the Project Manager, Project QA Manager, and field staff and will be documented in the Annual Report. Sites are identified with a unique identification code to assist in identifying the location and purpose of the site and to ensure results are properly assigned. Sites are identified such that the reach, location identifier(such as a cross street, where available), and site type (receiving water, discharge, or tributary) can be distinguished. The format for Site ID codes is##X_AAAA, where: • ##indicates the reach in which the site is located, or in the case of a discharge or tributary sites, the reach to which the discharge or tributary drains to. • X identifies whether the site is a discharge site(D), and tributary site (T), or a receiving water site (in which case no identifier is used). • AAAA indicates the cross street, where available, such as WOOD for Wood Road on the Oxnard Plain. In some instances a cross street is not available and another location identifier is used to provide an indication of site location. Appendix A presents detailed descriptions of and directions to the sampling sites identified in this plan. CCWTMP QAPP 23 August 15,2007 Revision 1 Table 6. CCWTMP Compliance Monitoring and Nutrient Investigation Sites and Annual Sampling Frequency GPS Coordinates Water Sediment Tissue' Subwatershed Site ID Reach Site Location Lat Lon Tox2 Pests/ Nutrients2 Gen Tox Pests/ Pests/ 9 PCBs2 Chem2 PCBs PCBs 01 RR BR 1 Ronald Reagan St Bridge 34.1090 -119.0916 6 6 6 6 NA NA NA 01 BPT 3 1 Located in Eastern Arm General site locations NA NA NA NA 01_BPT_6 1 Located in Eastern Part of Western Arm are provided as each NA NA NA NA Once 01 BPT_14 1 Located in the Central part of the Western Arm site represents a NA NA NA NA Mugu Lagoon 01_BPT_15 1 Located in Central Lagoon generalized sample NA NA NA NA Once every every 01_SG_74 1 Located in Central Lagoon,South of Drain#7 collection zone in NA NA NA NA three years three which a sample will be years Central Lagoon 1 Sampled in Central Lagoon P NA NA NA NA Western Arm 1 Sampled in Western Arm of the Lagoon collected. NA NA NA NA Revolon 04 WOOD 4 Revolon Slough East Side of Wood Road 34.1703 -119.0953 6 6 6 6 1 1 1 Slough 05_CENTR 5 Beardsley Wash at Central Avenue 34.2300 -119.1128 NA NA 6 NA NA NA NA 02_PCH 2 Calleguas Creek Northeast Side of Hwy 1 Bridge 34.1119 -119.0818 NA NA 4 NA NA NA NA 03_UNIV 3 Calleguas Creek At University Drive 34.1798 -119.0441 6 6 6 6 1 1 1 Calleguas 03D_CAMR 3 Camrosa Water Reclamation Plant 34.1679 -119.0530 4 4 NA 4 NA NA NA 9A_HOWAR 9A Conejo Creek at Howard Road Bridge 34.1931 -119.0025 NA NA 4 NA NA NA NA 9AD CAMA 9A Camarillo Water Reclamation Plant 34.1938 -119.0017 4 4 NA 4 NA NA NA 9B_ADOLF 9B Conejo Creek At Adolfo Road 34.2125 -118.9894 6 6 6 6 NA 1 1 10 GATE 10 Conejo Creek Hill Canyon Below N Fork 34.2178 -118.9281 NA NA 6 NA NA NA NA Conejo 10D HILL 10 Hill Canyon Wastewater Treatment Plant 34.2131 -118.9250 4 4 NA 4 NA NA NA 12 PARK 12 Conejo Creek North Fork Above Hill Canyon 34.2144 -118.9150 NA NA 4 NA NA NA NA 13 BELT 13 Conejo Creek S Fork Behind Belt Press Building 34.2078 -118.9194 NA NA 4 NA NA NA NA Las Posas 06_SOMIS 6 Arroyo Las Posas Off Somis Road 34.2540 -118.9927 6 6 6 6 NA 1 1 06D MOOR 6 Ventura County Wastewater Treatment Plant 34.2690 -118.9330 4 4 NA 4 NA NA NA 07 HITCH 7 Arroyo Simi East Of Hitch Boulevard 34.2717 -118.9228 6 6 6 6 NA 1 1 Arroyo Simi 07_MADER 7 Arroyo Simi at Madera Avenue 34.2778 -118.7958 NA NA 6 NA NA NA NA 07D_SIMI 7 Simi Valley Water Quality Control Plant 34.2814 -118.8150 4 4 NS 4 NS NS NS 1 Tissue samples will be collected in the same location as water and sediment samples. Samples may be collected elsewhere if no fish are found at pre-established sample stations. 2 Includes two wet events per site(Bolded sites indicate the sites selected for the nutrient investigation monitoring). NA-Not Analyzed Tox-Samples will be analyzed for toxicity and OP,triazine,and pyrethroid pesticides as listed in Table 2. Toxicity in water will not be analyzed at 01_11_BR or at the POTWs. Pests/PCBs-Samples will be analyzed for OC pesticides and PCBs as listed in Table 2. Chlorpyrifos will be analyzed in tissue at 04_WOOD as it is listed in this reach.Nutrients-Samples will be analyzed for Nutrients as listed in Table 2. Gen Chem-Samples will be analyzed for General Parameters as listed in Table 2. CCWTMP QAPP 24 August 15,2007 Revision 1 Table 7.Toxicity Investigation Monitoring Sites and Sampling Frequency Subwatershed Site ID Reach Site Location L PS Coordinate Tox Pests/PCBs Gen Chem t Long Sediment Toxicity Investigation 02_PCH 2 Calleguas Creek Northeast Side Of Highway 1 34.1119 -119.0818 1 1 1 Calleguas Bridge 9A_HOWAR 9A Conejo Creek At Howard Road Bridge 34.1931 -119.0025 1 1 1 Water Toxicity Investigation' Tox Pests/PCBs Gen Chem 10_GATE 10 Conejo Creek Hill Canyon Below North Fork 34.2178 -118.9281 5 5 5 Conejo Of Conejo Creek 13 BELT 13 Conejo Creek South Fork Behind Hill Canyon 34.2078 -118.9194 4 4 4 Belt Press Building 1 Includes two wet events per site. Tox—Samples will be analyzed for toxicity,OP,triazine,and pyrethroid pesticides in water and toxicity,OF and pyrethroid pesticides in sediment as listed in Table 2 Pests/PCBs—Samples will be analyzed for OC pesticides and PCBs as listed in Table 2. Gen Chem—Samples will be analyzed for General Parameters as listed in Table 2. CCWTMP QAPP 25 August 15,2007 Revision 1 r Table 8. CCWTMP Land Use Monitoring Sites and Sample Frequency Subwatershed Site ID Reach Site Site Location GPS Coordinates Pests/ Nutrients Gen Type' Lat Long PCBs1 Chem' Mugu Lagoon 01T_ODD2_DCH 1 Ag Duck Pond/Mugu/Oxnard Drain#2 S.of Hueneme Rd 34.1395 -119.1183 6 6 6 04D_WOOD 4 Ag Agricultural Drain on E.Side of Wood Rd N.of Revolon 34.1707 -119.0960 6 6 6 Revolon 05D_SANT_ 5 Ag Santa Clara Drain at VCWPD Gage 781 prior to 34.2425 -119.1114 6 6 6 Slough VCWPD confluence with Beardsley Channel 04D VENTURA 4 Urban Camarilo Hills Drain at Ventura Blvd and Las Posas Rd 34.2161 -119.0675 6 6 6 at VCWPD Gage 835 Calleguas 02D_BROOM 2 Ag Discharge to Calleguas Creek at Broome Ranch Rd. 34.1434 -119.0711 NA NA NA 9BD_GERRY 9B Ag Drainage ditch crossing Santa Rosa Rd at Gerry Rd 34.2369 -118.9473 6 6 6 Conejo 913D_ADOLF 9B Urban Urban storm drain passing under N.side of Adolfo Rd 34.2148 -118.9951 6 6 6 approximately 300 meters from Reach 9B 13_SB_HILL 13 Urban South Branch Arroyo Conejo on S.Side of W Hillcrest 34.1852 -118.9074 6 6 6 Las Posas 06T_FC_BR 6 Ag Fox Canyon at Bradley Rd-just north of Hwy 118 34.2646 -119.0115 6 6 6 07D HITCH 2nd corrugated pipe discharging on north side of Arroyo LEVEE-2 7 Ag Simi flood control levee off of Hitch Blvd just beyond 1 I 34.2714 -118.9205 6 6 6 power pole. Arroyo Simi 07D_CTP 7 Urban Flood control channel in Country Trail Park 34.2646 -118.9072 6 6 6 07T_DC_H 7 Urban Dry Canyon at Heywood Street 34.2682 -118.7599 6 6 6 07T_LL_RC 7 Open Las Llajas at Road Crossing 34.3005 -118.6806 NA 6 6 Ag=Agricultural Land Use Site Urban=Urban Land Use Site Open=Open Space Land Use Site(Established for the nutrients investigation monitoring) 1 Includes two wet events per site. Station IDs indicated in bold type represent CCWTMP sites that correspond to sites identified in the Ventura County Irrigated Lands Group QAPP(LWA 2006). 02D_BROOM will be sampled by the VCAILG and will be considered in the CCWTMP Annual Report. Pests/PCBs-Samples will be analyzed for Organochlorine Pesticides and PCBs, OP,triazine,and pyrethroid pesticides as listed in Table 2. Nutrients-Samples will be analyzed for Nutrients as listed in Table 2. Gen Chem-Samples will be analyzed for General Parameters as listed in Table 2. CCWTMP QAPP 26 August 15,2007 Revision 1 C) n D 23 07_MADER 08 07 HITC II i I 07 Y 06 11 23 „06_SOMIS �„53 98 B o Lr 10 GATE 10 12_PARK v 12 z x t _BELT 13 ri 'HOWAR Oa 101 01_RR_B C" d� Je�`JCa e`e 23 Pp0 0 2.5 5 cos 11.��J I I t Miles i) D <.(0 CCWTMP Compliance Monitoring Sampling Sites -Receiving Water En Subwatersheds Notes: "' Arroyo Simi Las Posas Toxicity,OCs,and Nutrients TMDL Sampling Site 1.Toxicity TMDL analysis includes-Aquatic Toxicity N and OP,Pyrethroid,and Triazine Pesticides -- o Calleguas J Mugu Lagoon Nutrients TMDL Sampling Site 2.00s TMDL analysis includes-OC Pesticides and PCBs 3.Nutrients TMDL analysis includes-Nitrogen and Conejo Revolon Slough Major Drainages Phosphorus Compounds Major Roads Larry Walker Associates June,2007 Figure 3. CCWTMP Compliance Monitoring Sampling Sites— Receiving Water n Cn C 16a 126 23 07 HITC 1a 3 06 11 10 BB 12 9B ADOLF 00 - 13 04n 1a1 1 27 �eS� e\Q5 23 SPCA 0 2.5 5 I Miles I7 D <p c �= CCWTMP Compliance Monitoring Receiving Water Sampling Sites - Freshwater Sediment Subwatersheds cn Notes:I A Toxicity and OCs TMDL Sampling Site 1.Toxicity TMDL analysis includes-Sediment Toxicity and OP ^� Arroyo 51m1 1 Las Posas Y y Y' � OCs TMDL Sampling Site and Pyrethroid Pesticides Calleguas Mugu Lagoon 2.OCs TMDL analysis includes-OC Pesticides and PCBs E_- ___] Conejo ® Revolon Slough Major Drainages Major Roads Larry Walker Associates JuIV,2006 Figure 4.CCWTMP Compliance Monitoring Receiving Water Sampling Sites-Freshwater Sediment c� ,C„I 15 126 � ywy g 23 00 07 HITC 32 06 �16_SOMIS 11 n 8B 1Q t 9B_ADOLF 12 st 13 4 , a -° 01 R. 27 �a G° �e(1tJ a�iy 25 0 2.5 5 I I I Miles v �7 D <D = CO CCWTMP Compliance Monitoring Receiving Water Sampling Sites- Freshwater Fish Tissue Subwatersheds Notes: N . Arroyo Simi Las Posas A Toxicity and OCs TMDL Sampling Site 1.Toxicity TMDL analysis includes-Chlorpyritos C) x 2.OCs TMDL analysis includes-OC Pesticides and PCBs 0 OCs TMDL Sampling Site Calleguas I--- J Mugu Lagoon Major Drainages Conejo Revolon Slough Major Roads Larry walker Associates July.2006 Figure 5.CCWTMP Compliance Monitoring Receiving Water Sampling Sites—Freshwater Fish Tissue 0 15 126 2J •e 1 06D—MOOR 7D SI 07 3 11 23 9B 10 10D_HIL 12 w w 13 ` ' 4D_CAMA q 191 �s 1 P 27 ta(-P c J 0 c 23 voSP 0 2.5 5 I I I Miles �7 D (D c CCWTMP Compliance Monitoring Sampling Sites- POTW Effluent o. Subwatersheds Notes: N3 Arroyo Simi `� Las Posas A Toxicity and OCs TMDL Sampling Site 1.Toxicity TMDL analysis includes-OP,Pyrethroid,and o Triazine Pesticides ov Calleguas Mugu Lagoon Major Drainages 2.OCs TMDL analysis includes-OC Pesticides and PCBs Major Roads Conejo - Revolon Slough Larry Walker Associates July,2006 Figure 6. CCWTMP Compliance Monitoring Sampling Sites—POTW Effluent CCWTMP Compliance Monitoring Sampling Zones - Mugu Lagoon Sediment t b., u r i # is 3 R m a �. x %a CD D < c � c O� N O O v Figure 7.CCWTMP Compliance Monitoring Sampling Zones—Mugu Lagoon Sediment n CCWTMP Compliance Monitoring Sampling Zones - Mugu Lagoon Tissue Pr 2 / P �. y � P '� ''tai in `,s`�-��, �z v� �s��;{:� �` ���!• �' o � .tea CD D < c o' N O O v Figure 8. CCWTMP Compliance Monitoring Sampling Zones— Mugu Lagoon Tissue C) C) 160 p 23 126 08 118 t Q7 oa - y 11 23 g' s 8B 10 i ' 10_GATE 13 BELT 12 w w 13 161 3 � 27 f G°J�ri J�C� 23 0 2.5 5 X05 I 1 1 Miles �7 D CCWTMP Toxicity Investigation Receiving Water Sampling Sites-Water and Sediment Subwatersheds Notes U' Arroyo Simi Las Posas Water Sampling Site 1.Water analysis includes-Aquatic Toxicity and OP,Pyrethroid, — -.a and Triazine Pesticides o Sediment Sampling Site 2.Sediment analysis includes-Sediment Toxicity and OP and C) Calleguas Mugu Lagoon Y Y I M P rethroid Pesticides Conejo ® Revolon Slough Major Drainages Y --- Major Roads Larry Walker Associates July,2006 Figure 9.CCWTMP Toxicity Investigation Receiving Water Sampling Sites—Water and Sediment n c) r ISO 21 r12b OS 0 07D HITCH 07T_LC_RC LEVEE-2_ "8 06 V 07D_CTP 07T—DC—Hu 23 j 98D_GERRY 11 r. .., za 10 9B 913D_ADOLF 12 w 13 Ir 13_SB_HILL i ROP 101 r "E 01T ODD_2 .. DCH 27 CP SP 0 Je ��ee 23 �oSP ` 0 2.5 5 (,1NJ I I I Miles �7 D <D c ` 6 `° CCWTMP Land Use Sampling Sites Notes: °_ Subwatersheds 1.Agricultural and Urban Discharge Sampling Site analysis for Toxicity,OCs and ° 0 Open Space Sampling Site L Arroyo Simi Las Posas p p 9 Nutrient TMDLs includes-OP,OC,Pyrethroid,and Triazine Pesticides,PCBs n3 A Agricultural Discharge Sampling Site and Nitrogen and Phosphorus Compounds. °o Calleguas U Mugu Lagoon U Urban Discharge Sampling Site 2.Open Space Sampling Site analysis for Nitrogen and Phosphorus Compounds. 3.Agricultural and Urban Discharge Sampling Sites are generally located at a uConejo ® Revolon Slough Major Drainages point where water from a representative group of similar land uses discharges Major Roads to one of the subwatershed reaches. Larry Walker Associates June,2007 Figure 10. CCWTMP Land Use Sampling Sites Sampling Schedule Dry weather water column samples shall be collected quarterly. Table 9 presents the sampling schedule. The sampling schedule was established in an attempt to characterize months in which toxicity of unknown causes was observed in previous studies. Dates will be finalized during coordination with other monitoring efforts (NPDES POTW and Stormwater monitoring and the Ag Waiver program) in order to minimize duplication of effort and to develop a representative data set. All efforts will be made to include two additional wet weather water sampling events for toxicity and selected organic constituents between October and April during targeted storm events, as described below. Collection of land use and POTW samples will coincide with compliance monitoring and wet weather sampling events as outlined in Table 9. Streambed sediment samples in freshwater reaches and Mugu Lagoon will be collected during the summer(June through August)to coincide with a return to base flow conditions and to be consistent with similar efforts in California. Collection of streambed sediment samples may be postponed if storms resulting in scouring of sediments occur late into the spring. The monitoring schedule will be revised if it does not appropriately characterize conditions in the watershed. Any changes with regard to the sample schedule will be determined through discussions between the Project Manager, Project QA Manager, and field staff and will be documented in the Annual Report. Table 9. Compliance,Toxicity, and Nutrient Investigation Monitoring Schedules' Subwatershed Station IN Reach Station Type by TMDL Monthz Tox OCs Nutrients Jan Apr Jul Oct 01_RR_BR 1 C C C, I W W W W 01_BPT_3 1 C C S 01_BPT_6 1 C C S Mugu Lagoon 01_BPT_14 1 C C S 01_BPT_15 1 C C S 01_SG_74 1 C C S Central Lagoon 1 C T Western Arm 1 C T Revolon 04 WOOD 4 C C C, I W W W,S,T W 05_CENTR 5 C, I W W W W 02_PCH 2 1 C W W W, S W Calleguas 03_UNIV 3 C C C, I W W W,S,T W 9A_HOWAR 9A I C W W W, S W 9B_ADOLF 9B C C C, I W W W, S,T W Conejo 10 GATE 10 1 C, I W W W W 12 PARK 12 C W W W W 13 BELT 13 1 C W W W W Las Posas 06_SOMIS 6 C C C, I W W W, S,T W 07 HITCH 7 C C C, I W W W, S,T W Arroyo Simi 07_MADER 7 C, I W W W W 07T LL RC 7 1 W W W W Station Type: C indicates compliance monitoring site; I indicates toxicity or nutrient investigation site Media Type: W indicates water sample;S indicates sediment sample;T indicates tissue sample 1 Collection of land use and POTW samples will coincide with compliance monitoring and wet weather sampling. 2 All attempts will be made to include two wet weather sampling events during the wet season(October through April) for aquatic toxicity and OC, OP,triazine,nutrients, and pyrethroid pesticides and PCBs outlined in Table 2. CCWTMP QAPP 35 August 15,2007 Revision 1 Should measurable precipitation occur during the seven days prior to a scheduled dry weather event, stream gage data within the watershed will be reviewed to determine if flow rates have returned to a pre-storm level. If flow rates have returned to a pre-storm level the sampling event may be conducted as scheduled. If flow rates have not returned to a pre-storm level the sampling event shall be rescheduled to allow for flow rates to return to a pre-storm level or for at least seven days without measurable precipitation prior to sampling, whichever is a shorter time period. All efforts will be made to collect two wet weather samples during the wet season (October through April). Sufficient precipitation is needed to produce runoff, mobilize contaminants, and increase stream flow. The decision to sample a storm event will be made in consultation with weather forecasting information services and after a quantity of precipitation forecast(QPF) has been determined. Wet weather samples will be collected after a targeted storm event, defined as a storm that produces at least 0.5 inches of precipitation. Peak flows shall be targeted, to the extent practicable. Appendix C contains an attachment outlining the procedures for initiating wet weather sampling. Classification of Measurements Because the CCWTMP is intended to be a long term monitoring program, data that are not successfully collected during a specific sample event will not be recollected at a later date. Rather, subsequent events conducted over the course of the program will provide a data set of sufficient size to appropriately characterize conditions at individual sampling sites and in the watershed in general. For this reason, most of the data planned for collection cannot be considered absolutely critical, and it is difficult to set a meaningful objective for data completeness. If, however, sampling sites do not allow for the collection of enough samples to provide representative data due to conditions (i.e., no flow) alternate sites will be considered. Please see Element 14 (Quality Control)for a discussion on data completeness. All information collected as outlined in the QAPP will be reported. Validation of Non-Standard Methods For non-standard sampling and analysis methods, sample matrices, or other unusual situations, appropriate method validation study information shall be documented to confirm the performance of the method for the particular need. The purpose of this validation is to assess the potential impact on the representativeness of the data generated. Such validation studies may include an initial demonstration of capability, split samples sent to another lab for analysis by a standard method, or round-robin studies performed by USEPA or other organizations. If previous validation studies are not available, some level of validation study will be performed during the project and included as part of the annual report. 11. Sampling Methods All samples will be collected in a manner appropriate for the specific analytical methods to be used. Proper sampling techniques must be used to ensure that samples are representative of environmental conditions. Field personnel will adhere to established sample collection protocols in order to ensure the collection of representative and uncontaminated (i.e., contaminants not introduced by the sample handling process itself)samples for laboratory analyses. Deviations from the standard protocols must be documented. Standard operating procedures(SOPs)for collection of samples are provided in Appendix C and summary descriptions are provided below. CCWTMP QAPP 36 August 15,2007 Revision 1 Surface water and sediment samples will be collected for chemical analyses and biological toxicity testing as listed in Table 2. Tissue samples will be collected for chemical analyses as listed in Table 2. Sampling for additional constituents may be required in the future, dependent on additional TMDLs, the results of Toxicity Identification Evaluations (TIEs), or other unforeseen reasons. In these cases, the QAPP will be amended to provide adequate sampling and analytical guidance, as necessary. Field Protocols Briefly, the key aspects of quality control associated with sample collection for eventual chemical and toxicological analyses are as follows: • Field personnel will be thoroughly trained in the proper use of sample collection gear and will be able to distinguish acceptable versus unacceptable water samples in accordance with pre-established criteria. • Field personnel will be thoroughly trained to recognize and avoid potential sources of sample contamination (e.g., engine exhaust, ice used for cooling). • Sampling gear and utensils which come in direct contact with the sample will be made of non-contaminating materials (e.g., borosilicate glass, high-quality stainless steel and/or Teflon TM, according to protocol) and will be thoroughly cleaned between sampling stations according to appropriate cleaning protocol (rinsing thoroughly with laboratory reagent water at minimum). • Sample containers will be of the recommended type and will be free of contaminants (i.e., pre-cleaned). • Conditions for sample collection, preservation and holding times will be followed. Field crews (2 persons per crew, minimum)will only be mobilized for sampling when weather conditions and flow conditions are considered to be safe. For safety reasons, sampling will occur during daylight hours, when possible. Sampling events should proceed in the following manner: 1. Before leaving the sampling crew base of operations, confirm number and type of sample containers as well as the complete equipment list. 2. Proceed to the first sampling site. 3. Fill-out the general information on the field log sheet. 4. Collect the samples indicated on the event summary sheet in the manner described in the QAPP. Collect additional volume and blank samples for field-initiated QA/QC samples, if necessary. Place filled sample containers in coolers and carefully pack and ice samples as described in the QAPP. Using the field log sheet, confirm that all appropriate containers were filled. 5. Collect field measurements and observations, and record these on the field log sheet. 6. Repeat the procedures in steps 3, 4, and 5 for each of the remaining sampling sites. 7. Complete the chain of custody forms using the field log sheets. 8. After sample collection is completed, deliver and/or ship samples to appropriate laboratory. Water Sample Collection The various monitoring programs in the CCW collect grab and composite samples. Table 10 summarizes the sample collection requirements of the various programs. The method by which each program collects samples for specific constituents is indicated in the NPDES permit or in the CCWTMP QAPP 37 August 15,2007 Revision 1 program's monitoring plan. A grab sample is an individual sample. A composite sample is mixture of grab samples collected over a period of time either as time or flow weighted. A time weighted composite is created by mixing multiple aliquots collected at specified time intervals. A flow weighted composite is created by mixing multiple aliquots collected at equal time intervals but then mixed based on flow rate. Table 10. Sample Collection Requirements of Monitoring Programs in the CCW Program Discharge Sites' Receiving Water Sites POTWs Flow and Time Weighted Composite2and Grab3 Grab Stormwater Program Flow weighted composite2 and Grab3 Flow weighted composite2 and Grab3 Mugu Stormwater Program Flow weighted composite2 and Grab3 No sites VCAILG Ag Waiver Grab Grab Program 1 Discharge sites include POTW influent and effluent and agricultural and urban discharge sites. 2 Effluent samples are collected as flow-weighted composites and influent samples are collected as time-weighted. 3 Constituents with relatively short hold times(e.g.,coliform,E.coli,etc.)and those found to be misrepresented by collection through automated composite samplers or use of tubing are collected as grabs. Composite samples are generally considered to be more representative of a given time period and varying conditions over that time period, whereas grab samples represent an instant in time. Because composite samples are more representative of a given time period they are generally used to develop an understanding of pollutant loadings. In the case of TMDL monitoring, allocations in water are primarily set as concentrations which are considered over varying averaging periods (1 hour, 4-day, and 30-day). A composite sample collected over the averaging period timeframe would allow for a direct comparison to allocations. However, there are varying averaging periods for the same constituents that would require multiple composite samples and there are real logistical and hold time issues faced in collection of composites over a 4 or 30-day period. Given the implementation schedules for the Nutrients, Toxicity, and OCs TMDLs are 7, 10, and 20 years, respectively, the frequency of monitoring outlined in the CCWTMP, and the additional monitoring conducted by other programs in the watershed, it is expected that a range of conditions will be evaluated and sufficient data will be available to answer the monitoring questions posed in Element 5 (Problem Definition/Background)without collection of composite samples at this time. Efforts will be made to compare CCWTMP collected grab samples to composites samples collected by other programs in the watershed. This will allow for an evaluation of how data collected using different techniques varies under different conditions. Grab samples will be collected at approximately mid-stream, mid-depth at the location of greatest flow(where feasible) by direct submersion of the sample bottle. This is the preferred method for grab sample collection; however, due to monitoring site configurations and safety concerns, direct filling of sample bottles may not always be feasible, especially during wet events. Monitoring site configuration will dictate grab sample collection technique. Grab samples will be collected directly into the appropriate bottles whenever feasible (containing the required preservatives as outlined in Table 11). Clean, powder-free nitrile gloves will be worn while collecting samples. In the event that a peristaltic pump and priority-cleaned silicone and Teflon TM tubing are used as a last resort to collect samples (i.e., due to unsafe conditions during wet events), the sample collection tubing and CCWTMP QAPP 38 August 15,2007 Revision 1 the sample bottle and lid shall come into contact only with surfaces known to be clean, or with the water sample. Standard operating procedures (SOPs)for collection of surface water samples are provided in Appendix C. The potential exists for monitoring sites to lack discernable flow. The lack of discernable flow may generate unrepresentative data. To address the potential confounding interference that can occur under such conditions, sites sampled through the CCWTMP should be assessed for the following conditions and sampled or not sampled accordingly: • Pools of water with no flow or visible connection to another surface water body should NOT be sampled. The field log should be completed for non-water quality data (including date and time of visit) and the site condition should be photo-documented. • Flowing water(i.e., based on visual observations, flow meter data, and a photo- documented assessment of conditions immediately upstream and downstream of the sampling site) site SHOULD be sampled. It is the combined responsibility of all members of the sampling crew to determine if the performance requirements of the specific sampling method have been met, and to collect additional samples if required. If the performance requirements outlined above or documented in sampling protocols are not met, the sample will be re-collected. If contamination of the sample container is suspected, a fresh sample container will be used. The Project Manager will be contacted if at any time the sampling crew has questions about procedures or issues based on site-specific conditions. Sediment Sample Collection — Freshwater Reaches Collection of in-stream sediment samples for chemical analysis and toxicity testing shall be conducted according to methods developed by the USGS and outlined in Guidelines for Collecting and Processing Samples of Stream Bed Sediment for Analysis of Trace Elements and Organic Contaminants for the National Water Qualify Assessment Program(1994). Sediment sampling sites will encompass a section of the reach approximately 100 meters in length upstream from water-column sampling stations. However, this definition may vary based on conditions at each sampling station. Sediment sampling stations should contain 5 to 10 wadeable depositional zones. Depositional zones are defined as locations in streams where the energy regime is low and fine- grained particles accumulate in the stream bed. Depositional zones include areas on the inside bend of a stream or areas downstream from obstacles such as boulders, islands, sand bars, or simply shallow waters near the shore. The purpose of selecting numerous wadeable depositional zones is to collect a representative sample of each reach. Each depositional zone identified at a sampling station shall be subsampled several times and composited in the field for chemical analysis, or at the lab for toxicity analysis. The number of subsamples collected at each depositional zone shall be based on the size of the zone. If all of the depositional zones within a reasonable distance of the water sampling station have dried, samples should be collected from a partially wetted zone. Wetted zones include areas near the active stream channel. Sediment samples will be collected from the top two to three centimeters (cm) of sediment using CCWTMP QAPP 39 August 15,2007 Revision 1 pre-cleaned stainless steel trowels. Collection of sediments in the top two to three cm is a common approach to conducting sediment sampling for the purpose of sediment toxicity testing. This approach was used in sediment toxicity studies conducted by the Southern California Coastal Water Research Project(SCCWRP) Bight Program and the State Water Resources Control Board Bay Protection and Toxic Cleanup Program (BPTCP), which led to the sediment toxicity listing in Mugu Lagoon. All sediment samples shall be collected directly into a clean polyethylene bag, mixed, and then placed into the appropriate jars as outlined in Table 11. SOPs for collection of sediments in the freshwater portion of the watershed are provided in Appendix C. The Ventura County Watershed Protection District shall be contacted at least one month prior to monitoring to determine if there is a potential for sediment removal activities to affect sediment sample collection. Sediment Sample Collection — Mugu Lagoon Sediment samples from Mugu Lagoon will be collected in subtidal areas to allow the data to be compared to the California Sediment Quality Guidelines, which are currently under development. Divers will collect sediments for chemical and toxicity analysis at all stations in situ. This process will eliminate the need for multiple grab sets from the small sampling boat and be more efficient for the amount of sediment needed for analysis. In addition, diver sampling will allow for more precise sediment collection at the station location. In situ sediment samples will be collected directly with the sample storage and transport container, eliminating the potential for metal contamination from grab samplers, and reduce handling and transferring otherwise required after sample collection. If the optional monitoring is initiated by the Management Committee as described in Element 6 (Project Description) benthic samples for infaunal community analysis will be collected in conjunction with the sediment and toxicity sampling throughout Mugu Lagoon. In the central lagoon and eastern arm, benthic sample collection will be accomplished using a 0.1-m2, chain- rigged Van Veen grab deployed from the small sampling boat. One Van Veen grab will be collected at each station in the eastern arm of the lagoon. Once on station, the Van Veen grab will be lowered at a rate not to exceed 1 m/sec to ensure proper deployment. On the bottom, moderate cable tension will be maintained to prevent the sampler from toppling. The grab will be slowly raised until free from the bottom to ensure that an acceptable sample is collected. The grab will continue to be slowly raised until the grab breaks the surface and is safely retrieved. If the western arm or other areas are not accessible to a boat large enough to deploy the Van Veen grab, benthic infauna samples will be collected by divers. At these stations a diver will place a box quadrant with the same surface area as the Van Veen on the bottom, and sediments will be carefully removed, so that no sediments or organisms are lost. Sediments within this quadrant will be excavated to a depth consistent with that collected by the Van Veen grab. As discussed previously, the frequency for sampling Mugu Lagoon sediment is predicated on the relatively slow sedimentation rates in the several parts of the lagoon. In an attempt to gain an understanding of sedimentation rates at the sampling sites, transects may be established at sites where feasible (i.e., sites where transects will not be swept away during high flow events). The number and location of transects will be determined in the field during the first event in consultation with Navy environmental staff familiar with the lagoon. SOPs for collection of sediments in Mugu Lagoon are provided in Appendix C. CCWTMP QAPP 40 August 15,2007 Revision 1 Fish Tissue Sample Collection — Freshwater Reaches According to USEPA guidance (2000), the target fish species for sample collection in inland freshwaters should be the largest individual fish captured from both 1) the highest trophic level sampled (e.g., predatory species) and 2) a bottom feeder. The USEPA guidance document lists bass, crappie, walleye, yellow perch, common carp, suckers, catfish, and trout among its recommended target species for inland freshwaters. Fish species collected in the past in the freshwater portion of the CCW include goldfish, fathead minnow, black and brown bullhead, arroyo chub, mosquito fish, and green sunfish. All attempts will be made to collect fish to meet the requirements of the USEPA guidance; however, other species not listed above may be collected if they are species known to be consumed by people in the CCW, are within the size range typically kept for consumption, and are predatory or bottom-feeding species. Fish will be collected using gear appropriate to the collection site and the species being targeted. Sampling gear may include electrofishing boats, backpack electrofishers, seine nets, gill nets, trap nets, hook and line, or other equipment as required. Larger species are collected as individuals for filleting to allow for an evaluation of human health risks. Small species are collected as bulk samples as the whole body tissue is analyzed which will potentially allow for an evaluation of ecological risk. Tissue monitoring will involve the field-collection of fish and the obtaining and storing of tissue samples to be analyzed for trace levels of target organics, using protocols detailed in CDFG's (2000) standard operating procedures for tissue sample collection and preparation. Appendix C provides a summary of CDFG protocols and protocols for collection of tissue samples. Fish Tissue Sample Collection — Mugu Lagoon For Mugu Lagoon, species with the potential for human and wildlife consumption will be targeted. As in freshwater systems, estuary fish species compositions can be variable from year-to-year. For this reason, it is proposed that target species in the estuary are selected based on the local abundances and fish size at the time of field collection. Fish targeted to evaluate potential impacts to human health will be limited to species more commonly consumed by humans. Predatory species likely to occur in the lagoon include kelp bass, sand bass, spotted bay bass, croaker and halibut. Benthic-feeding fish species are likely to include diamond turbot, spotted turbot, or speckled sand dab. Tissues analyzed will be based on most common preparation for the selected fish species, so for larger species such as bass and halibut, muscle tissue will be filleted and analyzed with skin on, while smaller species such as sand dab, will be cleaned with head, guts and tails removed before analysis (SWRCB, 1998). To further assess potential human impacts, tissues from resident California or bay mussels will also be evaluated. To evaluate potential wildlife impacts to sensitive bird species, a common schooling fish prey species will also be targeted for tissue analysis. As with other estuary species, abundances and species composition can vary year-to-year; however, species likely to be present include topsmelt, slough anchovies, deep body anchovies, or shiner surfperch. Field crews will target the most abundant prey species during each sampling event. Prey species will be analyzed whole-body. Fish for tissue analysis for human and wildlife consumption will be collected in the central portion of Mugu Lagoon by 16-ft otter trawl. Tows will be conducted until a sufficient number of fish are caught for analysis purposes, Fish for tissue analysis for wildlife consumption will be collected in the western arm of Mugu Lagoon by seine or trap net. Because of limited access and CCWTMP QAPP 41 August 15,2007 Revision 1 maneuverability in the western arm, it is unlikely that it will be possible to use the otter trawl in the area. Actual collection techniques will be developed in the field based on what works at the time. Fish sampling in this area will be limited to schooling species that provide forage for local bird species. Because of local conditions and abundances, the most abundant prey fish species collected in the western arm may differ from the most abundant species collected in the eastern arm. A summary of protocols for field-collection of fish and resident California muscles in the lagoon is also provided in Appendix C. Quality Control Sample Collection Quality control samples will be collected in conjunction with environmental samples to verify data quality. Quality control samples collected in the field include field blanks and duplicates. The frequency of quality control sample collection is presented in Element 14 (Quality Control). Field Measurements and Observations Field measurements (listed in Table 5)will be collected and observations made at each sampling site (water and sediment) after a sample is collected. Field measurements will include dissolved oxygen, temperature, conductivity, pH, turbidity, and flow. Measurements (except for flow) will be collected at approximately mid-stream, mid-depth at the location of greatest flow (if feasible)with a Hydrolab DS4 multi-probe meter, or comparable instrument(s). Field monitoring equipment must meet the requirements outlined in Table 5. Field measurements for sediment samples shall be collected from within one meter of the sediment. All field measurement results and field observations will be recorded on a field log sheet similar to the one presented in Appendix F. Flow will be estimated using a velocity meter and channel cross-sectional area, or will be estimated by other means at each sampling station after a sample is collected. Appendix C contains the flow measurement SOP. Regardless of measurement technique used, if a staff gage is present the gage height will be noted. If at any time the collection of field measurements by wading appears to be unsafe, field crews will not attempt to collect mid-stream, mid-depth measurements. Rather,field measurements will be made either directly from a stable, unobstructed area at the channel edge, or by using a telescoping pole and intermediate container to obtain a sample for field measurements and for filling sample containers. Use of sample collection methods other than the mid-stream, mid-depth method will be documented on the field log sheet. Field crews may not be able to measure flow at several sites during wet weather because of inaccessibility of the site. If this is the case, site inaccessibility will be documented on the field log sheet. The field sampling crew has primary responsibility for responding to failures in the sampling or measurement systems. Deviations from established monitoring protocols and this QAPP will be documented in the comment section of the field log sheet. If monitoring equipment fails, monitoring personnel will report the problem in the notes section of the field log sheet and will not record data values for the variables in question. Broken equipment will be replaced or repaired prior to the next field use. Data collected using faulty equipment will not be used for the CCWTMP. In addition to field measurements, observations shall be made at each sampling station and noted on the field log form. Observations will include color, odor, floating materials as well as observations of contact and non-contact recreation. CCWTMP QAPP 42 August 15,2007 Revision 1 12. Sample Handling and Custody Documentation Procedures The Project Manager is responsible for ensuring that each field sampling team adheres to proper custody and documentation procedures. Field log sheets documenting sample collection and other monitoring activities for each site will be bound in a separate master logbook for each event. Field personnel have the following responsibilities: • Keep an accurate written record of sample collection activities on the field log sheets. • Ensure that all field log sheet entries are legible and contain accurate and inclusive documentation of all field activities. • Note errors or changes using a single line to cross out the entry and date and initial the change. • Ensure that a label is affixed to each sample collected and that the labels uniquely identify samples with a sample ID, site ID, date and time of sample collection and the sampling crew initials. • Complete the chain of custody forms accurately and legibly. Field Documentation/Field Log Field crews will keep a field log book for each sampling event. The field log book shall contain a calibration log sheet, field log sheets for all sites, and appropriate contact information. The following items should be recorded in the field log for each sampling event: • Monitoring station location; • Date and time(s) of sample collection; • Name(s)of sampling personnel; • Sample depth; • Sample ID numbers and unique IDs for any replicate or blank samples; • QC sample type (if appropriate); • Requested analyses (specific parameters or method references); • Sample type, (i.e., grab); • The results of any field measurements (e.g., flow, temperature, dissolved oxygen, pH, conductivity, turbidity) and the time that measurements were made; • Qualitative descriptions of relevant water conditions (e.g., water color, flow level, clarity) or weather(e.g., wind, rain) at the time of sample collection; and, • A description of any unusual occurrences associated with the sampling event, particularly those that may affect sample or data quality. The field log will be scanned into a PDF and transmitted along with the Event Summary Report to the Project Manager within one week of the conclusion of each sampling event. Appendix F contains an example of the field log sheet. CCWTMP QAPP 43 August 15,2007 Revision 1 Container Labeling and Sample Identification Scheme All samples must be identified with a unique identification code to ensure that results are properly reported and interpreted. Samples will be identified such that the site, sampling location, matrix, and sample type (i.e., normal field sample or QC sample) can be distinguished by a data reviewer or user. Sample identification codes will consist of a site identification code, a matrix code, and a unique sample ID number assigned by the monitoring manager. The format for sample ID codes is CCWTMP-###-AAAA-XXX, where: • CCWTMP indicates the sample was collected as part of the TMDL Monitoring Program. • ###-identifies the sequentially numbered sample event. Sample events are numbered from 001 to 999 and will not be repeated. • AAAA indicates the unique site identification code assigned to each site. Site identification codes are provided in Table 6 through Table 8. • XXX identifies the sample number unique to a sample bottle collected for a single event. Sample bottles are numbered sequentially from 001 to 999 and will not be repeated within a single event. All sample containers will be pre-labeled before each sampling event to the extent practicable. Pre-labeling sample containers simplifies field activities, leaving only sample collection time and date and field crew initials to be filled out in the field. Custom labels will be produced using blank water-proof labels. This approach will allow the site and analytical constituent information to be entered in advance and printed as needed prior to each sampling event. Labels will be applied to the appropriate sample containers in a dry environment as labels usually do not adhere to wet bottles. The labels will not be applied to container caps. Container labels will contain the following information: • Program Name • Date • Analytical Requirements • Station ID • Time • Preservation Requirements • Sample ID • Sampling Personnel • Laboratory Conducting Analysis Sample Containers, Storage, Preservation, and Holding Times Sample containers must be pre-cleaned and certified free of contamination according to the USEPA specification for the appropriate methods. Sample container, storage and preservation, and holding time requirements are provided in Table 11. The analytical laboratories will supply sample containers that already contain preservative (Table 11), including ultra pure hydrochloric and nitric acid, where applicable. After collection, samples will be stored at 4oC until arrival at the contract laboratory. CCWTMP QAPP 44 August 15,2007 Revision 1 Table 11. Sample Container,Volume, Initial Preservation, and Holding Time Requirements Parameter Sample Sample Immediate Processing Holding Time Container Volume and Storage Water Toxicity Initial Screening Follow-Up Testing F 2 x 40 L Store at 40C 36 hours2 Phase I TIE jerric ned rrican Hardness polyethylene 250 mL Store at 40C,HNO3 180 days Total Suspended Solids(TSS) polyethylene 1 L Store at 40C 7 days Nitrate Nitrogen 48 hours Nitrite Nitrogen polyethylene 250 mL Store at 40C 48 hours Orthophosphate-P 48 hours Ammonia Nitrogen 28 days Total Phosphorus polyethylene 1 L H2SO4 and Store at 40C 28 days Organic Nitrogen 28 days Total Kjehdahl Nitrogen(TKN) polyethylene 500 mL H2SO4 and Store at 40C 28 days Organics6—Dry Weather—PCBs,OPs,OCs, amber glass 2 x 1 L Store at 40C 7/40 days4 Triazines,and Pyrethroids Organics6—Wet Weather—PCBs,OPs,OCs, 4 x 0.5 Pyrethroids,and Triazines in water and PCBs, glass gallon Store at 40C 7/40 days4 OPs,OCs,and Pyrethroids in suspended sediment Sediment Toxicity Initial Screening 4—mil poly 2 L Follow-Up Testing ba g 5 L3 Store at 40C 14 days Phase I TIE 20 L3 4-inch Bivalve Embryo diameter 4 cores Store upright at 40C 14 days push core Benthic Macroinvertebrate Community Assessment glass 0.1 m3 10%formal in-seawater 72 hours Total Ammonia 28 days Percent Moisture 1 year Particle Size Distribution glass 2 x 8 oz jar Store at 40C 6 months Total Organic Carbon 28 days Organics6 1 years Metals6 6 months Tissue Organicsfi and Percent Lipids,per sample teflon sheet 200 g Store on dry ice 1 year if frozen 1 Additional volume may be required for QC analyses. 2 Tests should be initiated within 36 hours of collection.The 36-hour hold time does not apply to subsequent analyses for TIES. For interpretation of toxicity results,samples may be split from toxicity samples in the laboratory and analyzed for specific chemical parameters.All other sampling requirements for these samples are as specified in this document for the specific analytical method. Results of these analyses are not for any other use(e.g.characterization of ambient conditions)because of potential holding time exceedances and variance from sampling requirements. 3 Sample volumes for follow-up testing and Phase I TIEs for sediments may change based on percent solids in previous samples. In addition,collection of sediment for follow-up testing and Phase I TIEs may change based on observations of toxicity in previous sampling events. 4 7/40=7 days to extract and 40 days from extraction to analysis. 5 One year if frozen,otherwise 14 days to extract and 40 days from extraction to analysis. 6 Organics and metals include pesticides, PCBs,and metals presented in Table 2. CCWTMP QAPP 45 August 15,2007 Revision 1 Sample Handling and Shipment The field crews will have custody of samples during each monitoring event. Chain-of-custody (COC)forms will accompany all samples during shipment to contract laboratories to identify the shipment contents. All water quality samples will be transported to the analytical laboratory by the field crew or by overnight courier. The original COC form will accompany the shipment, and a signed copy of the COC form will be sent, typically via fax, by the laboratory to the field crew to be retained in the project file. While in the field, samples will be stored on ice in an insulated container, so that they will be kept at approximately 4°C. Samples that must be shipped to the laboratory must be examined to ensure that container lids are tight and placed on ice to maintain the temperature between PC. The ice packed with samples must be approximately 2 inches deep at the top and bottom of the cooler, and must contact each sample to maintain temperature. The original COC form(s)will be double- bagged in re-sealable plastic bags and either taped to the outside of the cooler or to the inside lid. Samples must be shipped to the contract laboratory according to Department of Transportation standards. The method(s)of shipment, courier name, and other pertinent information should be entered in the"Received By"or"Remarks"section of the COC form. Coolers must be sealed with packing tape before shipping and must not leak. It is assumed that samples in tape-sealed ice chests are secure whether being transported by field staff vehicle, by common carrier, or by commercial package delivery. The laboratory's sample receiving department will examine the shipment of samples for correct documentation, proper preservation and compliance with holding times. The following procedures are used to prevent bottle breakage and cross-contamination: • Bubble wrap or foam pouches are used to keep glass bottles from contacting one another to prevent breakage, re-sealable bags will be used if available. • All samples are transported inside hard plastic coolers or other contamination-free shipping containers. • The coolers are taped shut to prevent accidental opening. • If arrangements are not made in advance, the laboratory's sample receiving personnel must be notified prior to sample shipment. All samples remaining after successful completion of analyses will be disposed of properly. It is the responsibility of the personnel of each analytical laboratory to ensure that all applicable regulations are followed in the disposal of samples or related chemicals. Chain-of-Custody Form Sample custody procedures provide a mechanism for documenting information related to sample collection and handling. Sample custody must be traceable from the time of sample collection until results are reported. A sample is considered under custody if: • It is in actual possession. • It is in view after in physical possession. CCWTMP QAPP 46 August 15,2007 Revision 1 1 • It is placed in a secure area(accessible by or under the scrutiny of authorized personnel only after in possession). A COC form must be completed after sample collection and prior to sample shipment or release. The COC form, sample labels, and field documentation will be cross-checked to verify sample identification, type of analyses, number of containers, sample volume, preservatives, and type of containers. A complete chain-of-custody form is to accompany the transfer of samples to the analyzing laboratory. A typical chain-of-custody form is illustrated in Appendix F. Laboratory Custody Procedures Contract laboratories will follow sample custody procedures as outlined in the laboratory's Quality Assurance (QA) Manual. A copy of each contract laboratory's QA Manual is available at the laboratory upon request. Laboratories shall maintain custody logs sufficient to track each sample submitted and to analyze or preserve each sample within specified holding times. The following sample control activities must be conducted at the laboratory: • Initial sample login and verification of samples received with the COC form; • Document any discrepancies noted during login on the COC; • Initiate internal laboratory custody procedures; • Verify sample preservation (e.g., temperature); • Notify the Project Manager if any problems or discrepancies are identified; and, • Perform proper sample storage protocols, including daily refrigerator temperature monitoring and sample security. Laboratories shall maintain records to document that the above procedures are followed. Once samples have been analyzed, samples will be stored at the laboratory for at least 30 days. After this period, samples may be disposed of properly. 13. Analytical Methods Portable field meters will measure within specifications outlined in Table 12. Analytical methods, method detection limits (MDLs), and reporting limits (RLs) required for samples analyzed in the laboratory are summarized in Table 13. MDLs and RLs are discussed in more detail in this Element. For organic constituents, environmentally relevant detection limits will be used to the extent practicable. The MDLs and/or RLs listed in Table 13 for several OC pesticides (aldrin, alpha-BHC, chlordane, the DDTs, dieldrin and toxaphene) are higher than targets/allocations specified in the BPAs. However, the MDLs and/or RLs listed in Table 13 are lower than detection levels currently attainable at commercial laboratories using standard analytical techniques and represent best available limits. Additionally, the RLs for nitrate as N and total suspended solids (TSS) (0.1 mg/L and 1.0 mg/L, respectively) are higher than the RLs listed in the SWAMP QAPP. However, of the 1,690 nitrate as N data points available in the watershed 98% were detected data with less than 1% of detected data were detected below the RL of 0.1 mg/L proposed in the QAPP. Of the 15,065 TSS data available in the watershed 99% were detected data with only 2% of detected data below the RL of 1 mg/L proposed in the QAPP.A review of the available data does not suggest the reporting limits will led to a significant number of non-detect data. CCWTMP QAPP 47 August 15,2007 Revision 1 Table 13 includes constituents that were not identified in Table 2 as these constituents are typically analyzed along with a suite of constituents. The additional constituents listed in Table 13 are not considered critical and are above and beyond what are required to meet TMDL monitoring requirements. Prior to the analysis of any environmental samples, the laboratory must have demonstrated the ability to meet the minimum performance requirements for each analytical method presented in Table 13. The initial demonstration of capability includes the ability to meet the project-specified Method Detection Limits and Reporting Limits, the ability to generate acceptable precision and accuracy, and other analytical and quality control parameters documented in this QAPP. Data quality objectives for precision and accuracy are summarized in Table 5. Laboratory SOPs are documented in Appendix E. Table 12.Analytical Methods and Project Reporting Limits for Field Measurements Parameter/Constituent Method Range Project RL Flow Electromagnetic -0.5 to+20 ft/s 0.05 ft/s pH Electrometric 0—14 pH units NA Temperature High stability thermistor -5—50 oC NA Dissolved oxygen Membrane 0—50 mg/L 0.5 mg/L Turbidity Nephelometric 0—3000 NTU 0.2 NTU Conductivity Graphite electrodes 0—10 mmhos/cm 2.5 umhos/cm RL—Reporting Limit NA—Not applicable CCWTMP QAPP 48 August 15,2007 Revision 1 Table 13.Analytical Methods and Project Method Detection and Reporting Limits for Laboratory Analysis Para meterlConstituent Method' Units Project MDL Project RL Laboratory Analyses—Water Chronic(7-day)Ceriodaphia dubia EPA-821-R-02-013 and NA NA NA Toxicity EPA-600-4-91-002 Chronic(7-day)Americamysis bahia EPA-821-R-02-014 NA NA NA Toxicity Hardness SM 2340B mg/L 1 5 Total Suspended Solids(TSS) SM 2540D mg/L 0.5 1 Ammonia Nitrogen SM 4500-NH3 F mg/L 0.01 0.1 Nitrate Nitrogen 300.1 mg/L 0.01 0.1 Nitrite.Nitrogen 300.1 mg/L 0.01 0.05 Organic Nitrogen Calculation mg/L NA NA Total Kjehdahl Nitrogen(TKN) 351.3 mg/L 0.455 0.5 Total Phosphorus SM 4500-P C mg/L 0.02 0.1 Orthophosphate-P 300.1 mg/L 0.001 0.01 Organochlorine Pesticides2 Aldrin EPA 625(m)/8270C(m) ng/L 1 5 alpha-BHC EPA 625(m)/8270C(m) ng/L 1 5 beta-BHC EPA 625(m)/8270C(m) ng/L 1 5 gamma-BHC(Lindane) EPA 625(m)/8270C(m) ng/L 1 5 delta-BHC EPA 625(m)/8270C(m) ng/L 1 5 Chlordane-alpha EPA 625(m)/8270C(m) ng/L 1 5 Chlordane-gamma EPA 625(m)/8270C(m) ng/L 1 5 Cis-Nonachlor EPA 625(m)/8270C(m) ng/L 1 5 2,4'-DDD EPA 625(m)/8270C(m) ng/L 1 5 2,4'-DDE EPA 625(m)/8270C(m) ng/L 1 5 2,4'-DDT EPA 625(m)/8270C(m) ng/L 1 5 4,4'-DDD EPA 625(m)/8270C(m) ng/L 1 5 4,4'-DDE EPA 625(m)/8270C(m) ng/L 1 5 4,4'-DDT EPA 625(m)/8270C(m) ng/L 1 5 Dieldrin EPA 625(m)/8270C(m) ng/L 1 5 Endosulfan I EPA 625(m)/8270C(m) ng/L 1 5 Endosulfan II EPA 625(m)/8270C(m) ng/L 1 5 Endosulfan Sulfate EPA 625(m)/8270C(m) ng/L 1 5 Endrin EPA 625(m)/8270C(m) ng/L 1 5 Endrin Aldehyde EPA 625(m)/8270C(m) ng/L 1 5 Endrin Ketone EPA 625(m)/8270C(m) ng/L 1 5 Heptachlor EPA 625(m)/8270C(m) ng/L 1 5 Heptachlor Epoxide EPA 625(m)/8270C(m) ng/L 1 5 Methoxychlor EPA 625(m)/8270C(m) ng/L 1 5 Mirex EPA 625(m)18270C(m) ng/L 1 5 Oxychlordane EPA 625(m)/8270C(m) ng/L 1 5 Heptachlor EPA 625(m)/8270C(m) ng/L 1 5 Toxaphene EPA 625(m)/8270C(m) ng/L 10 50 trans-Nonachlor EPA 625(m)/8270C(m) ng/L 1 5 PCBs Congeners EPA 625(m)/8270C(m) ng/L 1 5 Aroclors3 EPA 625(m)/8270C(m) ng/L 10 20 Continued on next page CCWTMP QAPP 49 August 15,2007 Revision 1 Table 13 (continued from previous page). Analytical Methods and Project Method Detection and Reporting Limits—Laboratory Analysis Parameter/Constituent Method' Units Project MDL Project RL Organophosphorus Pesticides Bolstar(Sulprofos) EPA 625(m)/8270C(m) ng/L 2 4 Chlorpyrifos EPA 625(m)/8270C(m) ng/L 1 2 Demeton EPA 625(m)/8270C(m) ng/L 1 2 Diazinon EPA 625(m)/8270C(m) ng/L 2 4 Dichlorvos EPA 625(m)/8270C(m) ng/L 3 6 Dimethoate EPA 625(m)/8270C(m) ng/L 3 6 Disulfoton EPA 625(m)/8270C(m) ng/L 1 2 Ethoprop(Ethoprofos) EPA 625(m)/8270C(m) ng/L 1 2 Fenchlorophos(Ronnel) EPA 625(m)/8270C(m) ng/L 2 4 Fensulfothion EPA 625(m)/8270C(m) ng/L 1 2 Fenthion EPA 625(m)/8270C(m) ng/L 2 4 Malathion EPA 625(m)/8270C(m) ng/L 3 6 Merphos EPA 625(m)/8270C(m) ng/L 1 2 Methyl Parathion EPA 625(m)/8270C(m) ng/L 1 2 Mevinphos(Phosdrin) EPA 625(m)/8270C(m) ng/L 8 16 Phorate EPA 625(m)/8270C(m) ng/L 6 12 Tetrachlorvinphos(Stirofos) EPA 625(m)18270C(m) ng/L 2 4 Tokuthion EPA 625(m)18270C(m) ng/L 3 6 Trichloronate EPA 625(m)/8270C(m) ng/L 1 2 Pyrethroid Pesticides4 Allethrin 8270C(NCI) ng/L 0.5 2 Bifenthrin 8270C(NCI) ng/L 0.5 2 Cyfluthrin 8270C(NCI) ng/L 0.5 2 Cypermethrin 8270C(NCI) ng/L 0.5 2 Danitol 8270C(NCI) ng/L 0.5 2 Deltamethrin 8270C(NCI) ng/L 0.5 2 L-Cyhalothrin 8270C(NCI) ng/L 0.5 2 Permethrin 8270C(NCI) ng/L 0.5 2 Prallethrin 8270C(NCI) ng/L 0.5 2 Esfenvalerate 8270C(NCI) ng/L 0.5 2 Fenvalerate 8270C(NCI) ng/L 0.5 2 Triazines Ametryn EPA 625(m)/8270C(m) ng/L 5 10 Atraton EPA 625(m)/8270C(m) ng/L 5 10 Atrazine EPA 625(m)/8270C(m) ng/L 5 10 Prometon EPA 625(m)/8270C(m) ng/L 5 10 Prometryn EPA 625(m)/8270C(m) ng/L 5 10 Propazine EPA 625(m)/8270C(m) ng/L 5 10 Secbumeton EPA 625(m)/8270C(m) ng/L 5 10 Simazine EPA 625(m)/8270C(m) ng/L 5 10 Simetryn EPA 625(m)/8270C(m) ng/L 5 10 Terbuthylazine EPA 625(m)/8270C(m) ng/L 5 10 Terbutryn EPA 625(m)/8270C(m) ng/L 5 10 Continued on next page CCWTMP QAPP 50 August 15,2007 Revision 1 Table 13 (continued from previous page).Analytical Methods and Project Method Detection and Reporting Limits-Laboratory Analysis Parameter/Constituent Method' Units Project MDL Project RL Laboratory Analyses—Sediment Chronic(10-day)Eohaustorius estuarius EPA-600-R-94-025 NA NA NA Toxicity 48-hour Bivalve Embryo Toxicity(Mytilus EPA-600-R-95-136 NA NA NA edulis or Crassostrea gigas) Benthic Macroinvertebrate Community NA NA NA NA Assessment Total Ammonia in Sediment SM 4500-NH3 F mg/wet kg 0.01 0.05 Percent Moisture EPA 160.3 % 0.1 0.1 Particle Size Distribution SM 260D um 0.02 0.04 Total Organic Carbon(TOC) EPA 9060A %Dry Weight 0.01 0.05 Organochlorine Pesticides Aldrin EPA 8270C(m) ng/dry g 1 5 alpha-BHC EPA 8270C(m) ng/dry g 1 5 beta-BHC EPA 8270C(m) ng/dry g 1 5 gamma-BHC(Lindane) EPA 8270C(m) ng/dry g 1 5 delta-BHC EPA 8270C(m) ng/dry g 1 5 Chlordane-alpha EPA 8270C(m) ng/dry g 1 5 Chlordane-gamma EPA 8270C(m) ng/dry g 1 5 Cis-Nonachlor EPA 8270C(m) ng/dry g 1 5 2,4'-DDD EPA 8270C(m) ng/dry g 1 5 2,4'-DDE EPA 8270C(m) ng/dry g 1 5 2,4'-DDT EPA 8270C(m) ng/dry g 1 5 4,4'-DDD EPA 8270C(m) ng/dry g 1 5 4,4'-DDE EPA 8270C(m) ng/dry g 1 5 4,4'-DDT EPA 8270C(m) ng/dry g 1 5 Dieldrin EPA 8270C(m) ng/dry g 1 5 Endosulfan I EPA 8270C(m) ng/dry g 1 5 Endosulfan II EPA 8270C(m) ng/dry g 1 5 Endosulfan Sulfate EPA 8270C(m) ng/dry g 1 5 Endrin EPA 8270C(m) ng/dry g 1 5 Endrin Aldehyde EPA 8270C(m) ng/dry g 1 5 Endrin Ketone EPA 8270C(m) ng/dry g 1 5 Heptachlor EPA 8270C(m) ng/dry g 1 5 Heptachlor Epoxide EPA 8270C(m) ng/dry g 1 5 Methoxychlor EPA 8270C(m) ng/dry g 1 5 Mirex EPA 8270C(m) ng/dry g 1 5 Oxychlordane EPA 8270C(m) ng/dry g 1 5 Heptachlor EPA 8270C(m) ng/dry g 1 5 Toxaphene EPA 8270C(m) ng/dry g 10 50 trans-Nonachlor EPA 8270C(m) ng/dry g 1 5 PCBs Congeners EPA 8270C(m) ng/dry g 1 5 Aroclors3 EPA 8270C(m) ng/dry g 10 20 Continued on next page CCWTMP QAPP 51 August 15,2007 Revision 1 Table 13 (continued from previous page). Analytical Methods and Project Method Detection and Reporting Limits-Laboratory Analysis Parameter/Constituent Method' Units Project MDL Project RL Organophosphorus Pesticides Bolstar(Sulprofos) EPA 8270C(m) ng/dry g 5 10 Chlorpyrifos EPA 8270C(m) ng/dry g 5 10 Demeton EPA 8270C(m) ng/dry g 5 10 Diazinon EPA 8270C(m) ng/dry g 5 10 Dichlorvos EPA 8270C(m) ng/dry g 5 10 Dimethoate EPA 8270C(m) ng/dry g 5 10 Disulfoton EPA 8270C(m) ng/dry g 5 10 Eth_oprop(Ethoprofos) EPA 8270C(m) ng/dry g 5 10 Fenchlorophos(Ronnel) EPA 8270C(m) ng/dry g 5 10 Fensulfothion EPA 8270C(m) ng/dry g 5 10 Fenthion EPA 8270C(m) ng/dry g 5 10 Malathion EPA 8270C(m) ng/dry g 5 10 Merphos EPA 8270C(m) ng/dry g 5 10 Methyl Parathion EPA 8270C(m) ng/dry g 5 10 Mevinphos(Phosdrin) EPA 8270C(m) ng/dry g 5 10 Phorate EPA 8270C(m) ng/dry g 5 10 Tetrachlorvinphos(Stirofos) EPA 8270C(m) ng/dry g 5 10 Tokuthion EPA 8270C(m) ng/dry g 5 10 Trichloronate EPA 8270C(m) ng/dry g 5 10 Pyrethroid Pesticides4 Allethrin 8270C(NCI) ng/dry g 0.5 2 Bifenthrin 8270C(NCI) ng/dry g 0.5 2 Cyfluthrin 8270C(NCI) ng/dry g 0.5 2 Cypermethrin 8270C(NCI) ng/dry g 0.5 2 Danitol 8270C(NCI) ng/dry g 0.5 2 Deltamethrin 8270C(NCI) ng/dry g 0.5 2 L-Cyhalothrin 8270C(NCI) ng/dry g 0.5 2 Permethrin 8270C(NCI) n /dry g 0.5 2 Prallethrin 8270C(NCI) ng/dry g 0.5 2 Esfenvalerate 8270C(NCI) ng/dry g 0.5 2 Fenvalerate 8270C(NCI) n /dry g 0.5 2 Metals Arsenic EPA 6020 ug/dry g 0.03 0.05 Cadmium EPA 6020 ug/dry g 0.03 0.05 Copper EPA 6020 Ng/dry g 0.03 0.05 Lead EPA 6020 pg/dry g 0.03 0.05 Nickel EPA 6020 pg/dry g 0.03 0.05 Zinc EPA 6020 ug/dry g 0.03 0.05 Laboratory Analyses•Tissue Percent Lipids Gravimetric % 0.01 0.05 Organochlorine Pesticides Aldrin EPA 8270C(m) ng/wet g 1 5 alpha-BHC EPA 8270C(m) ng/wet g 1 5 beta-BHC EPA 8270C(m) ng/wet g 1 5 gamma-BHC(Lindane) EPA 8270C(m) ng/wet g 1 5 delta-BHC EPA 8270C(m) ng/wet g 1 5 Continued on next page CCWTMP QAPP 52 August 15,2007 Revision 1 Y Table 13 (continued from previous page).Analytical Methods and Project Method Detection and Reporting Limits—Laboratory Analysis Parameter/Constituent Method' Units Project MDL Project RL Chlordane-alpha EPA 8270C(m) ng/wet g 1 5 Chlordane-gamma EPA 8270C(m) ng/wet g 1 5 Cis-Nonachlor EPA 8270C(m) ng/wet g 1 5 2 4'-DDD EPA 8270C(m) ng/wet g 1 5 2,4'-DDE EPA 8270C(m) ng/wet g 1 5 2,4'-DDT EPA 8270C(m) ng/wet g 1 5 4,4'-DDD EPA 8270C(m) ng/wet g 1 5 4,4'-DDE EPA 8270C(m) ng/wet g 1 5 4,4'-DDT EPA 8270C(m) ng/wet g 1 5 Dieldrin EPA 8270C(m) ng/wet g 1 5 Endosulfan I EPA 8270C(m) ng/wet g 1 5 Endosulfan I I EPA 8270C(m) ng/wet g 1 5 Endosulfan Sulfate EPA 8270C(m) ng/wet g 1 5 Endrin EPA 8270C(m) ng/wet g 1 5 Endrin Aldehyde EPA 8270C(m) ng/wet g 1 5 Endrin Ketone EPA 8270C(m) ng/wet g 1 5 Heptachlor EPA 8270C(m) ng/wet g 1 5 Heptachlor Epoxide EPA 8270C(m) ng/wet g 1 5 Methoxychlor EPA 8270C(m) ng/wet g 1 5 Mirex EPA 8270C(m) ng/wet g 1 5 Oxychlordane EPA 8270C(m) ng/wet g 1 5 Heptachlor EPA 8270C(m) ng/wet g 1 5 Toxaphene EPA 8270C(m) ng/wetg 10 50 trans-Nonachlor EPA 8270C(m) ng/wet g 1 5 PCBs Congeners EPA 8270C(m) ng/wet g 1 5 Aroclors3 EPA 8270C(m) ng/wet g 10 20 Organophosphorus Pesticides Chlorpyrifos EPA 8270C(m) ng/wet g 5 10 MDL—Method Detection Limit RL—Reporting Limit NA—Not applicable 1 Standard Methods(SM)or EPA Method number 2 The MDLs and/or RLs listed for several organochlorine pesticides in water(aldrin,alpha-BHC,chlordane, DDTs, dieldrin and toxaphene)are higher than numeric targets specified in the BPAs. However,the MDLs and/or RLs listed herein are significantly lower than levels currently attainable by commercial laboratories using standard analytical test methods and are consistent with the lowest detection limits reported for NPDES monitoring programs. 3 PCB Aroclors include those presented in Table 2. 4 8270C(NCI),where NCI is negative chemical ionization as allowed under the method. Toxicity Testing and Toxicity Identification Evaluations (TIEs) For the CCWTMP, standard test species will be used for toxicity testing. Ceriodaphnia dubia will be used for the aquatic toxicity testing. Hyalella azteca will be used for the bulk sediment and porewater toxicity testing. Eohaustorius estuarius will be used for aquatic, bulk sediment, and porewater toxicity at sampling locations where salinity levels adversely affect the other test species. Americamysis bahia(formerly Mysidopsis bahia)will be used to conduct aquatic toxicity testing if sample salinity exceeds 1 part per thousand (PPT) but is less than 15 PPT. The test species selected are standard USEPA test species considered to be among the most sensitive species to many different types of pollutants. The test species are particularly sensitive to CCWTMP QAPP 53 August 15,2007 Revision 1 t constituents previously identified as contributing to toxicity in water and/or sediment in the CCW. C. dubia is a water flea known to be extremely sensitive to organophosphate pesticides and some metals and also is used as an indicator of ammonia toxicity. H. azteca is a sediment dwelling invertebrate that is sensitive to ammonia and organochlorine pesticides. E. estuarius is a burrowing amphipod that is sensitive to organochlorine and organophosphate pesticides. A. bahia is a shrimp known to be sensitive to organophosphate pesticides. At such a time as toxicity numeric targets are consistently met, alternative species may be considered if it is determined the aforementioned species are not completely assessing toxicity in the CCW. The following is an optional monitoring element as discussed in Element 6 (Project Description). Sediment toxicity testing to either Mytilus edulis or Crassostrea gigas embryos may be conducted for comparison to the California Sediment Quality Guidelines, which are currently under development. Because embryo testing is not required to meet the requirements of the TMDL monitoring, the decision to implement this component of the CCWTMP will be made by the Management Committee per the process outlined in the Optional Monitoring Elements section of the Project Description (Element 6). Water and toxicity testing will be conducted according to current USEPA guidelines. These species are standard USEPA test species considered to be among the most sensitive species to many different types of pollutants. These test species are particularly sensitive to constituents previously identified as contributing to toxicity in water and/or sediment. Chronic tests will be used to assess both survival and reproductive/growth endpoints for each species. Test species may be added or removed in the future to adequately identify the presence/absence of toxicity. Multiple dilution tests on water samples will be conducted to determine the magnitude of toxicity and subsequently the value of the toxic unit chronic(TUc). At the initiation of monitoring the following five dilutions will be used: 100%, 50%, 25%, 12.5%, and 6.25%. The number of dilutions and percent dilutions may be adjusted based on analytical results. The results of toxicity testing will be used to trigger further investigations to determine the cause of observed laboratory toxicity. If testing indicates the presence of significant toxicity in the sample, TIE procedures may be initiated to investigate the cause of toxicity. For the purpose of triggering TIE procedures, significant toxicity is defined as at least 50% mortality. The 50% mortality threshold is consistent with the approach recommended in guidance published by USEPA for conducting TIEs(USEPA, 1996), which recommends a minimum threshold of 50% mortality because the probability of completing a successful TIE decreases rapidly for samples with less than this level of toxicity. A targeted Phase 1 TIE will be conducted to determine the general class of constituent(i.e., non-polar organics)causing toxicity. The targeted TIE will focus on classes of constituents anticipated to be observed in drainages dominated by urban and agricultural discharges and those previously observed to cause toxicity. These classes of constituents are non-polar organics. Phase 2 TIEs may also be utilized to identify specific constituents causing toxicity if warranted. TIE methods will generally adhere to USEPA procedures documented in conducting TIEs (USEPA, 1991, 1992, 1993a-b). For samples exhibiting toxic effects consistent with carbofuran, diazinon, or chlorpyrifos, TIE procedures will follow those documented in Bailey et al. (1996). As stated above, chronic tests will be used to assess both survival and reproductive/growth CCWTMP QAPP 54 August 15,2007 Revision 1 endpoints for each species to allow for an evaluation of compliance with the 1 TUc endpoint in water established in the Toxicity TMDL BPA and in the Conditional Waiver. Therefore, the sensitivity of this endpoint is conserved. Similar to the VCAILG QAPP TIE approach, the 50% mortality endpoint is for TIE initiation only not for assessing compliance with the TMDL. For clarification, a toxic effect(mortality or reduced reproduction/growth)observed in 96 hours or less is typically considered acute. A chronic toxic effect(which can include mortality or reduced reproduction/growth), would be the effect observed over the portion of the test beyond the test duration of an acute test. Any project-specific modifications to these methods will be documented in future amendments to this QAPP. TIE procedures will be initiated as soon as possible after toxicity is observed to reduce the potential for loss of toxicity due to extended sample storage. Substantial work has been completed in the CCW utilizing TIEs conducted on sediment porewater, the most common and accepted approach for the performance of sediment TIEs (USEPA 1991). While there has been significant advancement regarding the application of the TIE process to bulk sediments, USEPA accepted methods for the performance of bulk-sediment TIEs are yet to be finalized and accepted; however, USEPA is planning to update its Sediment TIE Guidance manual in the near future to include methods for performance of bulk-sediment TIEs in addition to the current accepted porewater TIE methods. Until bulk sediment TIE procedures are more completely developed and accepted and/or it is felt their use in the CCW will significantly improve the determination of causes unknown toxicity, the CCWTMP will utilize porewater TIE methods. To address toxicity of unknown causes in sediment, sediment porewater will be extracted and tested for toxicity when significant toxicity, defined as at least 50% mortality, is observed in the bulk sediment sample. If the subsequent sediment porewater toxicity testing results in greater than 50% mortality, a Phase 1 TIE may be initiated on the sediment porewater. The decision to initiate TIE procedures on any sample, including samples exceeding the mortality threshold, as well as the focus and scope of TIE procedures, will be determined through consultation between the Project Manager, the toxicity laboratory, and Regional Board staff. When deciding whether to initiate TIE procedures for a specific site and monitoring event, a number of factors will be considered, including the level of toxicity, history of toxicity at the site, the species and endpoints exhibiting toxic effects, as well as the primary technical basis for triggering TIEs described above. The rationale for initiating TIE procedures for a specific sample will be clearly documented in subsequent reports. Grain Size Fraction Analysis The following is an optional monitoring element as discussed in Element 6 (Project Description). The decision to implement and/or modify the grain size fraction analysis will be made by the Management Committee per the process outlined in the Optional Monitoring Elements section of the Project Description (Element 6). Grain size fraction analysis is not required to meet the requirements of TMDL monitoring. However, the various fractions (aqueous and sediment and the two grain size fractions)could be considered to develop an understanding of how target organic constituents are transported through the watershed. This information can be used to assess the potential effectiveness of best management practices given the association of target organic constituents with the different grain size fractions. Because grain size fraction analysis is not CCWTMP QAPP 55 August 15,2007 Revision 1 required to meet the requirements of the TMDL monitoring and is for investigative purposes only, this component of the CCWTMP may be modified by the Management Committee per the process outlined in the Optional Monitoring Elements section of the Project Description (Element 6). Grain size fraction analysis could be conducted on wet-weather and streambed samples. During one wet-weather sampling event each year, water column samples could be filtered, after which the sediment and aqueous fractions could be analyzed separately for target organic constituents. The sediment fraction could be sieved into two grain size fractions (2mm-63um and less than 63um), after which the whole sample and the two grain size fractions could be analyzed separately. Analysis for general water quality constituents would need to be conducted on the whole sample. During the sediment sampling event, samples could be sieved into two grain size fractions (2mm- 63um and less than 63um), after which the whole sample as well as two grain size categories could be analyzed separately for target organic constituents. Measurements of general sediment quality constituents (GSQC) would need to be conducted on the whole sample. Because grain size fraction analysis is not required to meet the requirements of the TMDL monitoring and is for investigative purposes only, this component of the CCWTMP may be modified by the Management Committee per the process outlined in the Optional Monitoring Elements section of the Project Description (Element 6). . Macrobenthic Community Assessment The following is an optional monitoring element as discussed in Element 6 (Project Description). The decision to implement and/or modify the macrobenthic community assessment will be made by the Management Committee per the process outlined in the Optional Monitoring Elements section of the Project Description (Element 6). Macrobenthic community assessment in Mugu Lagoon is not required to meet the requirements of TMDL monitoring. However, sediment samples collected subtidally in Mugu Lagoon could be analyzed to assess macrobenthic(infaunal) communities, which would develop data that, in conjunction with sediment toxicity and chemistry data, can be compared to the California Sediment Quality Objectives (SQOs),which are currently being developed. Single benthic samples could be collected from each sediment sampling zone in Mugu Lagoon and analyzed for species composition and abundance. Appendix D contains an SOP for analyzing samples to characterize macrobenthic communities. Because macrobenthic community assessment in Mugu Lagoon is not required to meet the requirements of the TMDL monitoring, this component of the CCWTMP may be modified by the Management Committee per the process outlined in the Optional Monitoring Elements section of the Project Description (Element 6). Detection and Reporting Limits Method detection limits (MDL) and reporting limits (RLs) must be distinguished for proper understanding and data use. The MDL is the minimum analyte concentration that can be measured and reported with a 99% confidence that the concentration is greater than zero. The RL represents the concentration of an analyte that can be routinely measured in the sampled matrix within stated limits and with confidence in both identification and quantitation. For this program, RLs must be verifiable by having the lowest non-zero calibration standard or calibration check sample concentration at or less than the RL. RLs have been established in this CCWTMP QAPP 56 August 15,2007 Revision 1 QAPP based on the verifiable levels and general measurement capabilities demonstrated for each method. These RLs should be considered as maximum allowable reporting limits to be used for laboratory data reporting. Note that samples diluted for analysis may have sample-specific RLs that exceed these RLs. This will be unavoidable on occasion. However, if samples are consistently diluted to overcome matrix interferences, the analytical laboratory will be required to notify the Project Manager how the sample preparation or test procedure in question will be modified to reduce matrix interferences so that project RLs can be met consistently. Method Detection Limit Studies Any laboratory performing analyses under this program must routinely conduct MDL studies to document that the MDLs are less than or equal to the project-specified RLs. If any analytes have MDLs that do not meet the project RLs, the following steps must be taken: • Perform a new MDL study using concentrations sufficient to prove analyte quantitation at concentrations less than or equal to the project-specified RLs per the procedure for the Determination of the Method Detection Limit presented in Revision 1.1, 40 Code of Federal Regulations (CFR) 136, 1984. • No samples may be analyzed until the issue has been resolved. MDL study results must be available for review during audits, data review, or as requested. Current MDL study results must be reported for review and inclusion in project files. An MDL is developed from seven aliquots of a standard containing all analytes of interest spiked at five times the expected MDL. These aliquots are processed and analyzed in the same manner as environmental samples The results are then used to calculate the MDL. If the calculated MDL is less than 0.33 times the spiked concentration, another MDL study should be performed using lower spiked concentrations. Project Reporting Limits Laboratories generally establish RLs that are reported with the analytical results—these may be called reporting limits, detection limits, reporting detection limits, or several other terms by the reporting laboratory. These laboratory limits must be less than or equal to the project RLs listed in Table 12. Wherever possible, project RLs are lower than the relevant numeric criteria or toxicity thresholds. Laboratories performing analyses for this project must have documentation to support quantitation at the required levels. Laboratory Standards and Reagents All stock standards and reagents used for standard solutions and extractions must be tracked through the laboratory. The preparation and use of all working standards must be documented according to procedures outlined in each laboratory's Quality Assurance Manual; standards must be traceable according to U.S. EPA,A2LA or National Institute for Standards and Technology (NIST) criteria. Records must have sufficient detail to allow determination of the identity, concentration, and viability of the standards, including any dilutions performed to obtain the working standard. Date of preparation, analyte or mixture, concentration, name of preparer, lot or cylinder number, and expiration date, if applicable, must be recorded on each working standard. CCWTMP QAPP 57 August 15,2007 Revision 1 Alternate Laboratories In the event that the laboratories selected to perform analyses for the CCWTMP are unable to fulfill data quality requirements outlined herein (e.g., due to instrument malfunction), alternate laboratories will be selected based on their ability to meet ELAP and/or NELAP certifications and data quality requirements specified in this QAPP. The original laboratory selected may recommend a qualified laboratory to act as a substitute. However, the final decision regarding alternate laboratory selection rests with the Project Manager and Project QA Manager. 14. Quality Control Quality control procedures for the field and laboratory activities are summarized in Table 14 and discussed in more detail below. There are no SWAMP requirements for quality control for field analysis of general parameters (e.g., temperature, pH, conductivity, dissolved oxygen, and pH). However, field crews will be required to calibrate equipment as outlined in Element 11 (Sampling Methods). Table 14 presents the QA parameter addressed by each QA requirement as well as the appropriate corrective action if the acceptance limit is exceeded. CCWTMP QAPP 58 August 15,2007 Revision 1 Table 14. Quality Control Requirements Quality Control QA Parameter Frequency' Acceptance Limits Corrective Action Sample Type Quality Control Requirements—Field Once per Identify contamination source, re- Equipment Blanks Contamination equipment batch <MDL clean equipment,and re-run cleaned 2 equipment blank. 5%of all <MDL Examine field log. Field Blank Contamination samples Identify contamination source. Qualify data as needed. 5%of all RPD<25%if Reanalyze both samples if possible. Field Duplicate Precision samples IDifferencel>RL Identify variability source. Qualify data as needed. Quality Control Requirements—Laboratory Identify contamination source. Method Blank Contamination 1 per analytical <MDL Reanalyze method blank and all batch samples in batch. Qualify data as needed. Lab Duplicate Precision 1 per analytical RPD<25%if Recalibrate and reanalyze. batch IDifferencel>RL 80-120% Recovery for Check LCS/SRM recovery. Matrix Spike Accuracy 1 per analytical GWQC Attempt to correct matrix problem batch 50-150%Recovery for and reanalyze samples. Pesticides[31 Qualify data as needed. Check lab duplicate RPD. Matrix Spike Duplicate Precision 1 per analytical RPD<25%if Attempt to correct matrix problem batch IDifferencel>RL and reanalyze samples. Qualify data as needed. Laboratory Control Accuracy 1 per analytical 80-120%Recovery Recalibrate and reanalyze LCS/ Sample(or SRM) batch SRM and samples. Each Check surrogate recovery in LCS. Surrogate Spike Accuracy environmental 30-150%Recovery3 Attempt to correct matrix problem and (Organics Only) and lab QC reanalyze sample. sample Qualify data as needed. MDL=Method Detection Limit RL=Reporting Limit RPD=Relative Percent Difference LCS=Laboratory Control Sample/Standard SRM=Standard/Certified Reference Material GWQC=General Water Quality Constituents 1 "Analytical batch"refers to a number of samples(not to exceed 20 environmental samples plus the associated quality control samples)that are similar in matrix type and processed/prepared together under the same conditions and same reagents(equivalent to preparation batch). 2 Equipment blanks will be collected by the analytical laboratory responsible for cleaning equipment,before returning equipment to the field crew for use. 3 Or control limits set at+3 standard deviations based on actual laboratory data. Comparability Comparability of the data can be defined as the similarity of data generated by different monitoring programs. For this monitoring program, this objective will be ensured mainly through use of standardized procedures for field measurements, sample collection, sample preparation, laboratory analysis, and site selection; adherence to quality assurance protocols and holding times; and reporting in standard units. Additionally, comparability of analytical data will be addressed through the use of standard operating procedures and extensive analyst training at the analyzing laboratory. CCWTMP QAPP 59 August 15,2007 Revision 1 Representativeness Representativeness can be defined as the degree to which the environmental data generated by the monitoring program accurately and precisely represent actual environmental conditions. For the CCWTMP, this objective will be addressed by the overall design of the program. Representativeness is attained through the selection of sampling locations, methods, and frequencies for each parameter of interest, and by maintaining the integrity of each sample after collection. Sampling locations were chosen that are representative of various areas within the watershed and discharges from urban and agricultural lands, which will allow for the characterization of the watershed and impacts discharges may have on water quality. Completeness Data completeness is a measure of the amount of successfully collected and validated data relative to the amount of data planned to be collected for the project. It is usually expressed as a percentage value. A project objective for percent completeness is typically based on the percentage of the data needed for the program or study to reach valid conclusions. Because the CCWTMP is intended to be a long term monitoring program, data that are not successfully collected during a specific sample event will not be recollected at a later date. Rather subsequent events conducted over the course of the monitoring will provide robust data sets to appropriately characterize conditions at individual sampling sites and the watershed in general. For this reason, most of the data planned for collection cannot be considered absolutely critical, and it is difficult to set a meaningful objective for data completeness. However, some reasonable objectives for data are desirable, if only to measure the effectiveness of the program when conditions allow for the collection of samples (i.e., flow is present). The program goals for data completeness shown in Table 15 are based on the planned sampling frequency, SWAMP recommendations, and a subjective determination of the relative importance of the monitoring element within the CCWTMP. If, however, sampling sites do not allow for the collection of enough samples to provide representative data due to conditions(i.e., no flow) alternate sites will be considered. Data completeness will be evaluated on a four year basis to allow for consideration of two Mugu Lagoon sediment and tissue collection events. Grain size fraction analysis, embryo toxicity testing, and macrobenthic community analysis in Mugu Lagoon are optional monitoring elements and are not required to meet the requirements of the TMDL monitoring. As such, these components of the CCWTMP may be discontinued at any time by Management Committee per the process outlined in the Optional Monitoring Elements section of the Project Description (Element 6) and are not assigned completeness objectives. Table 15. Required Data Completeness Monitoring Element Completeness Objective Field Measurements 90% Conventional Parameters 90% Organic Constituents 90% Metals 90% Toxicity' 90% 1 Does not including sediment toxicity testing on embryos. CCWTMP QAPP 60 August 15,2007 Revision 1 Field Procedures For basic water quality analyses, quality control samples to be prepared in the field will consist of equipment blanks, field blanks and field duplicates. Equipment Blanks The purpose of analyzing equipment blanks is to demonstrate that sampling equipment is free from contamination. Equipment blanks will be collected by the analytical laboratory responsible for cleaning equipment and analyzed for pesticides, PCBs, and metals identified in Table 2 before sending the equipment to the field crew. Equipment blanks will consist of laboratory-prepared blank water(certified to be contaminant-free by the laboratory) processed through the sampling equipment that will be used to collect environmental samples. The blanks will be analyzed using the same analytical methods specified for environmental samples. If any analytes of interest are detected at levels greater than the MDL, the source(s)of contamination will be identified and eliminated (if possible), the affected batch of equipment will be re-cleaned, and new equipment blanks will be prepared and analyzed before the equipment is returned to the field crew for use. Field Blanks The purpose of analyzing field blanks is to demonstrate that sampling procedures do not result in contamination of the environmental samples. Per the Quality Assurance Management Plan for the State of California's Surface Water Ambient Monitoring Program (SWRCB, 2002)field blanks are to be collected as follows: • At a frequency of 5% of samples collected for the following constituents: trace metals in water(including mercury), VOA samples in water and sediment, DOC samples in water, and bacteria samples. • Field blanks for other media and analytes should be conducted upon initiation of sampling, and if field blank performance is acceptable (as described in Table 14), further collection and analysis of field blanks for these other media and analytes need only be performed on an as-needed basis, or during field performance audits. An as-needed basis for the CCW TMDL QAPP will be annually. Blanks will consist of laboratory-prepared blank water(certified to be contaminant-free by the laboratory) processed through the sampling equipment using the same procedures used for environmental samples. If any analytes of interest are detected at levels greater than the MDL, the source(s) of contamination should be identified and eliminated, if possible. The sampling crew should be notified so that the source of contamination can be identified (if possible) and corrective measures taken prior to the next sampling event. Field Duplicates The purpose of analyzing field duplicates is to demonstrate the precision of sampling and analytical processes. Field duplicates will be prepared at the rate of 5% of all samples, and analyzed along with the associated environmental samples. Field duplicates will consist of two grab samples CCWTMP QAPP 61 August 15,2007 Revision 1 collected simultaneously, to the extent practicable. If the Relative Percent Difference(RPD) of field duplicate results is greater than 25% and the absolute difference is greater than the RL, both samples should be reanalyzed, if possible. The sampling crew should be notified so that the source of sampling variability can be identified (if possible)and corrective measures taken prior to the next sampling event. Laboratory Analyses Quality control samples prepared in the laboratory will consist of method blanks, laboratory duplicates, matrix spikes/duplicates, laboratory control samples (standard reference materials), and toxicity quality controls. Method Blanks The purpose of analyzing method blanks is to demonstrate that sample preparation and analytical procedures do not result in sample contamination. Method blanks will be prepared and analyzed by the contract laboratory at a rate of at least one for each analytical batch. Method blanks will consist of laboratory-prepared blank water processed along with the batch of environmental samples. If the result for a single method blank is greater than the MDL, or if the average blank concentration plus two standard deviations of three or more blanks is greater than the RL, the source(s)of contamination should be corrected, and the associated samples should be reanalyzed. Laboratory Duplicates The purpose of analyzing laboratory duplicates is to demonstrate the precision of the sample preparation and analytical methods. Laboratory duplicates will be analyzed at the rate of one pair per sample batch. Laboratory duplicates will consist of duplicate laboratory fortified method blanks. If the Relative Percent Difference (RPD)for any analyte is greater than 25% and the absolute difference between duplicates is greater than the RL, the analytical process is not being performed adequately for that analyte. In this case, the sample batch should be prepared again, and laboratory duplicates should be reanalyzed. Matrix Spikes and Matrix Spike Duplicates The purpose of analyzing matrix spikes and matrix spike duplicates is to demonstrate the performance of the sample preparation and analytical methods in a particular sample matrix. Matrix spikes and matrix spike duplicates will be analyzed at the rate of one pair per sample batch. Each matrix spike and matrix spike duplicate will consist of an aliquot of laboratory-fortified environmental sample. Spike concentrations should be added at five to ten times the reporting limit for the analyte of interest. If the matrix spike recovery of any analyte is outside the acceptable range, the results for that analyte have failed to meet acceptance criteria. If recovery of laboratory control samples is acceptable, the analytical process is being performed adequately for that analyte, and the problem is attributable to the sample matrix. An attempt will be made to correct the problem (e.g., by dilution, concentration, etc.), and the samples and matrix spikes will be re-analyzed. If the matrix spike duplicate RPD for any analyte is outside the acceptable range, the results for that analyte have failed to meet acceptance criteria. If the RPD for laboratory duplicates is acceptable, the analytical process is being performed adequately for that analyte, and the problem is attributable to the sample matrix. An attempt will be made to correct the problem (e.g., by CCWTMP QAPP 62 August 15,2007 Revision 1 dilution, concentration, etc.), and the samples and matrix spikes will be re-analyzed. Laboratory Control Samples The purpose of analyzing laboratory control samples (or a standard reference material) is to demonstrate the accuracy of the sample preparation and analytical methods. Laboratory control samples will be analyzed at the rate of one per sample batch. Laboratory control samples will consist of laboratory fortified method blanks or a standard reference material. If recovery of any analyte is outside the acceptable range, the analytical process is not being performed adequately for that analyte. In this case, the sample batch should be prepared again, and the laboratory control sample should be reanalyzed. Surrogate Spikes Surrogate recovery results are used to evaluate the accuracy of analytical measurements for organics analyses on a sample-specific basis. A surrogate is a compound (or compounds) added by the laboratory to method blanks, samples, matrix spikes, and matrix spike duplicates prior to sample preparation, as specified in the analytical methodology. Surrogates are generally brominated, fluorinated or isotopically labeled compounds that are not usually present in environmental media. Results are expressed as percent recovery of the surrogate spike. Surrogate spikes are applicable for analysis of PCBs and pesticides. Toxicity Quality Control For aquatic toxicity tests, the acceptability of test results is determined primarily by performance- based criteria for test organisms, culture and test conditions, and the results of control bioassays. Control bioassays include monthly reference toxicant testing. Test acceptability requirements are documented in the method documents for each bioassay method and are included in Appendix D. 15. Instrument/Equipment Testing, Inspection and Maintenance Sample Equipment Cleaning Procedures Equipment used for sample collection (i.e., peristaltic pump tubing, sample containers and caps) will be cleaned by the analytical laboratory prior to each sample event, according to procedures documented for each analytical method. After cleaning, sample containers will be stored with lids secured, and additional clean caps will be stored in clean re-sealable bags. Cleaned tubing will be stored in clean polyethylene bags. Each batch of cleaned equipment will be used to generate an equipment blank as discussed in Element 14 (Quality Control). Field Measurement Equipment Each field crew will be responsible for testing, inspecting, and maintaining their field measurement equipment in accordance with the manufacturer's specifications. This includes battery checks, routine replacement of membranes, and cleaning of probes and electrodes. Analytical Equipment Testing Procedures and Corrective Actions Testing, inspection, maintenance of analytical equipment used by the contract laboratory and corrective actions are documented in the QA Manual for each analyzing laboratory. Laboratory QA Manuals are available for review at the analyzing laboratory. CCWTMP QAPP 63 August 15,2007 Revision 1 16. Instrument/Equipment Calibration and Frequency Laboratory Analytical Equipment Frequencies and procedures for calibration of analytical equipment used by each contract laboratory are documented in the QA Manual for each contract laboratory. Any deficiencies in analytical equipment calibration should be managed in accordance with the QA Manual for each contract laboratory. Any deficiencies that affect analysis of samples submitted through this program must be reported to the Project Manager, or designee. Laboratory QA Manuals are available for review at the analyzing laboratory. Field Measurement Equipment Calibration of field measurement equipment is performed as described in the owner's manuals for each individual instrument. Each individual field crew will be responsible for calibrating their field measurement equipment. Field monitoring equipment must meet the requirements outlined in Table 5 and be calibrated before field events based on manufacturer guidance, but at a minimum prior to each event. Each calibration will be document on each event's calibration log sheet (presented in Figure 11). If calibration results do not meet manufacturer specifications, the field crew should first try to recalibrate using fresh aliquots of calibration solution. If recalibration is unsuccessful, new calibration solution should be used and/or maintenance should be performed. Each attempt should be recorded on the equipment calibration log. If the calibration results cannot meet manufacturer's specifications, the field crew should use a spare field measuring device that can be successfully calibrated. Additionally, the Project Manager should be notified. Calibration should be verified using at least one calibration fluid within the expected range of field measurements, both immediately following calibration and at the end of each monitoring day. Individual parameters should be recalibrated if the field meters do not measure a calibration fluid within the range of accuracy presented in Table 5. Calibration verification documentation will be retained in the event's calibration verification log (presented in Figure 12). Table 16 outlines the typical field instrument calibration procedures for each piece of equipment requiring calibration. Results of calibration checks will be recorded on the calibration log sheet(presented in Figure 11). CCWTMP QAPP 64 August 15,2007 Revision 1 Table 16. Calibration of Field Measurement Equipment Frequency of Equipment/ Calibration and Verification Description Frequency of Calibration Responsible Instrument Calibration Verification Party Calibration for pH measurement is accomplished pH Probe using standard buffer solutions. Analysis of a mid-range buffer will be performed to verify successful calibration. Temperature Temperature calibration is factory-set and requires no subsequent calibration. Calibration for dissolved oxygen measurements is accomplished using a water saturated air environment. Dissolved oxygen (D.O.) Day prior to 15t After each day's Individual Dissolved measurement of water-saturated air will be day or 15t day calibration and at Sampling Oxygen Probe performed and compared to a standard table of of sampling the end of the Crews D.O.concentrations in water as a function of event sampling day temperature and barometric pressure to verify successful calibration. Conductivity calibration will follow manufacturer's Conductivity specifications. A mid-range conductivity standard will be analyzed to verify successful calibration. Turbidity calibration will follow manufacturer's Turbidity specifications. A mid-range turbidity standard will be analyzed to verify successful calibration. CCWTMP QAPP 65 August 15,2007 Revision 1 Field Measurement Equipment Calibration Log Date: Calibration Post-Cal Calibration Valid Time j Parameter Meter ID Standard Measurement if: 24-hour Initials m /L D.O. reads within D.0. mmHg g 10%of value from (water-sat'd air) D.O.tables Conductivity 500 uS/cm u _ Conductivity 10,000 us/cm uS/cm EC reads w/in 5%of (mid-range std.) expected value pH 7.0 e N ' I Units PH 8 reads within pH 10.0 ±0.2 Units(or w/in (pH=8.0) manufs specs) Turbidity 0 NTU "b' 3f2 . f J 4 rc.o `.$t f Turbidity 100 NTU NTU reads withinfl j Turbidity 1000 NTU (100 NTU) NTU 10%of expected value t Turbidity 3000 NTU �" Notes: Figure 11. Example Field Measurement Equipment Calibration Log Sheet Field Measurement Equipment Calibration Verification Log Date: Verification Calibration Valid Time Parameter Meter ID Standard Measurement if: 24-hour Initials D.O.reads within D.0. mmHg mg/L 10%of value from (water-sat'd air) D.O.tables Conductivity us/cm uS/cm EC reads w/in 5%of (mid-range std.) expected value Units pH 8 reads within pH Units ±0.2 Units(or w/in (pH=8.0) manufs specs) NTU reads within Turbidity NTU (100 NTU) NTU 10%of expected value Notes: Figure 12. Example Field Measurement Equipment Calibration Verification Log Sheet CCWTMP QAPP 66 August 15,2007 Revision 1 17. Inspection/Acceptance of Supplies and Consumables Inspection of gloves, sample containers, and any other consumable equipment used for sampling will be the responsibility of each individual sampling crew. Inspection should be conducted immediately upon receipt of equipment; equipment should be rejected/returned if any obvious signs of contamination (torn packages, etc.) are observed. Inspection protocols and acceptance criteria for laboratory analytical reagents and other consumables are documented in the QA Manual for each laboratory. 18. Non-Direct Measurements Water quality data collected through other monitoring programs (NPDES POTW and Stormwater monitoring and the VCAILG program) in the watershed will be incorporated to the extent practicable. The extent practicable will be dictated by the cost of gathering and compiling information from outside programs. It is not the intent or purpose of the CCWTMP to compile and analyze all available data. Data reported by these entities will be evaluated for suitability for inclusion in the CCWTMP database. If the data are deemed to be suitable they will be included in the database described in the following element. Data from other programs will be used to supplement land use data to evaluate loading to the receiving water as well as to evaluate receiving water quality. It is the responsibility of the Project QA Manager(or designee)to acquire, validate, and compile the necessary data from these programs. The data will be reviewed against the data quality objectives stated in Element 7 (Quality Objectives and Criteria for Measurement Data), if possible. 19. Data Management Event Summary Reports and Analytical Data Reports (described in Element 9)will be sent to and kept by the Project Manager. Each type of report will be stored separately and ordered chronologically. The field crew shall retain the original field logs. The contract laboratory shall retain original COC forms. The contract laboratory will retain copies of the preliminary and final data reports. Concentrations of all parameters will be calculated as described in the laboratory SOPs or referenced method document for each analyte or parameter. The various data and information generated from CCWTMP will be stored and maintained as described in Element 9 (Documents and Records). The field log and analytical data generated will be converted to a standard database format maintained on personal computers. After data entry or data transfer procedures are completed for each sample event, data will be validated as described in Element D (Data Validation and Usability). After the final quality assurance checks for errors are completed, the data will be added to the final database. The database consists of a MicrosoftTm Access database developed for the program and administered by Larry Walker Associates or designee. The version of MicrosoftTM Access database used to manage data will be upgraded as necessary to meet the requirements of the program. Program data will be submitted electronically with the Annual Monitoring Report in either Microsoft CCWTMP QAPP 67 August 15,2007 Revision 1 Access®or Microsoft Excel®file format. Tabular data summaries included in the annual report will be generated from this data file ("database"). Additionally, those data collected by the CCWTMP will be formatted to comply with SWAMP database requirements. C. ASSESSMENT AND OVERSIGHT 20. Assessments and Response Actions Data will be evaluated and documented after each monitoring event to determine whether project quality assurance objectives have been met, to quantitatively assess data quality, and to identify potential limitations on data use. The following assessments of compliance with quality control procedures will be performed during the data collection phase of the project: • Performance assessments of sampling procedures will be performed by the field sampling crews. Corrective actions shall be carried out by the field sampling crew and reported to the Project Manager, or designee. • Field crews will be audited annually by the Project Manager or designee. The initial audit will occur during the first monitoring event. Additional audits will occur as necessary to observe corrective actions taken to resolve errors identified during a previous audit. • The laboratory is responsible for following established SOPs, including those for proper instrument calibration and maintenance and laboratory QC sample analyses at the required frequency(i.e., method blanks, laboratory control samples, etc.)Associated QC sample results are reported with all sample results so that project staff can evaluate the analytical process performance. • Assessment of laboratory QC results and implementation of corrective actions will be the responsibility of the QA Officer at each laboratory and shall be reported to the Project QA Manager, or designee, as part of any data reports. • Assessment of field QC results and implementation of corrective actions shall be the responsibility of the Project QA Manager, or designee. All project data must be reviewed as part of the data assessment. Review is conducted on a preparation batch basis by assessing QC samples and all associated environmental sample results. Project data review established for this project includes the following steps: • Initial review of analytical and field data for complete and accurate documentation, chain- of-custody procedures, compliance with required holding times, and required frequency of field and laboratory QC samples; • Evaluation of analytical and field blank results to identify random and systematic contamination; • Comparison of all spike and duplicate results with data quality objectives for precision and accuracy; • Assigning data qualifier flags to the data as necessary to reflect data use limitations identified by the assessment process; and, • Calculating completeness by analyte. CCWTMP QAPP 68 August 15,2007 Revision 1 The Project QA Manager, or designee, is responsible for conducting the data assessment and for ensuring that data qualifier flags are assigned, as needed, based on the established quality control criteria. If an assessment or audit discovers any discrepancy, the Project QA Manager, or designee, will address the observed discrepancy with the appropriate person responsible for the activity. Discussion points will include whether the information collected is accurate, identifying the cause(s) leading to the deviation, how the deviation might impact data quality, and what corrective actions might be considered. The Project QA Manager, or designee, will maintain a QA Log of all communications and any specified corrective actions, and will make the QA Log available to the Project Manager upon request. Routine procedures to assess the success of the data collection effort are discussed in the Section D (Data Validation and Usability). Routine procedures for corrective actions are summarized in Table 14. 21. Reports to Management In addition to the information provided in Element 9 (Documents and Records), the following reports will be generated: Documents and records for the CCWTMP include: Event Summary Reports, Analytical Data Reports,Annual Reports, and the QAPP. These documents are described in detail in Element 9 (Documents and Records). Table 17 outlines the schedule of when the aforementioned reports will be submitted to management. Table 17. Reports to Management Schedule Person/Organization Type of Report Frequency Delivery Date Responsible for Report Recipients Preparation Every third month at a meeting of CCW Management Quarterly Update Quarterly Management Committee Project Manager Plan Members Event Summary With in one week of the completion Project Manager and Reports Approximately of each sampling event Field Crew Project QA Manager six times per Analytical Data year Within 30 days of sample delivery Contract Laboratories Project QA Manager Reports Annual Report and Electronic Database Four months after receipt of the CCW Management Annually final analytical data report to be Project Manager Plan Members Revised QAPP included in Annual Report Quarterly Updates Quarterly updates will be provided by the Project Manager at a quarterly meeting of the Management Committee participating in the QAPP. The update will include a brief summary of activities completed in the previous quarter, but will not include data. CCWTMP QAPP 69 August 15,2007 Revision 1 i Annual Watershed Monitoring Report A Watershed Monitoring Report will be completed annually by the Project Manager to provide an overview of the conditions in the CCW and to meet TMDL requirements. The Watershed Monitoring Report will be submitted within four months of receipt of the final analytical data report for the sampling year. Appropriate statistical methods will be employed for interpretive analysis of the data. Data will be presented through the use of summary tables, descriptive statistics, and graphical representations (e.g., time series, frequency histograms, mapping, etc.). The Watershed Monitoring Report will provide, at minimum, a comprehensive analysis of the following: • Monitoring objectives; • Monitoring site descriptions including GPS coordinates for each site and a location map of all sites; • Tabulated results of field laboratory data, including sampling and analytical methods used; • Copies of chain-of-custody forms; • Associated field and laboratory quality control sample results, including a summary of accuracy and precision; • Comparison of data to TMDL allocations and applicable criteria; • Trends in water, sediment, and fish tissue data; • Analysis of sources of constituents of concern; and, • Conclusions and recommendations. An adaptive management approach to the CCWTMP will be adopted as it may be necessary to modify aspects of the CCWTMP. Results of sampling carried out through the CCWTMP and other programs within the CCW may be used to modify this plan, as appropriate. Proposed modifications will be brought to the Management Committee for discussion. Any agreed upon modifications will be summarized in the annual report and incorporated into the QAPP. Possible modifications could include, but are not limited to the, following: • The inclusion of additional land use stations to accurately characterize loadings; • The removal of land use stations if it is determined they are duplicative(i.e., a land use site in one subwatershed accurately characterize the land use in other subwatersheds); • The inclusion of additional in-stream sampling stations; • The addition of analysis for constituents identified as contributing to toxicity; and, • The elimination of certain analysis for constituents based on the attainment of allocations or being no longer identified in land use and/or in-stream samples. If a coordinated and comprehensive monitoring plan that addresses multiple regulatory requirements (i.e., TMDL, NPDES, Ag Waiver, etc.) is developed and meets the goals of this monitoring plan, that plan should be considered as a replacement for the CCWTMP. Any such plan would require the approval of the Executive Officer. An electronic database will be submitted as an attachment to the Annual Report and will include the results of all field and laboratory data, as well as copies of all field documentation and laboratory original data reports in PDF format. Data submitted electronically will be made available for inclusion in the SWAMP database. CCWTMP QAPP 70 August 15,2007 Revision 1 • D. DATA VALIDATION AND USABILITY 22. Data Review, Verification and Validation Requirements The acceptability of data is determined through data verification and data validation. Both processes are discussed in detail below. In addition to the data quality objectives presented in Table 14, the standard data validation procedures documented in the contract laboratory's QA Manual will be used to accept, reject, or qualify the data generated by the laboratory. Each laboratory's QA Officer will be responsible for validating data generated by the laboratory. Once analytical results are received from the analyzing laboratory, the Project QA Officer will perform an independent review and validation of analytical results. Appendix G provides equations that are used to calculate precision, accuracy, and completeness of the data. Decisions to reject or qualify data will be made by the Project QA Manager, or designee, based on the evaluation of field and laboratory quality control data, according to procedures outlined in Section 13 of Caltrans document No. CTSW-RT-00-005, Guidance Manual: Stormwater Monitoring Protocols, 2nd Edition (LWA, July 2000). Section 13 of the Caltrans Guidance Manual is included as Appendix H. 23. Data Verification Data verification involves verifying that required methods and procedures have been followed at all stages of the data collection process, including sample collection, sample receipt, sample preparation, sample analysis, and documentation review for completeness. Verified data have been checked for a variety of factors, including transcription errors, correct application of dilution factors, appropriate reporting of dry weight versus wet weight results, and correct application of conversion factors. Verification of data may also include laboratory qualifiers, if assigned. Data verification should occur in the field and the laboratory at each level (i.e., all personnel should verify their own work) and as information is passed from one level to the next(i.e., supervisors should verify the information produced by their staff). Records commonly examined during the verification process include field and sample collection logs, chain-of-custody forms, sample preparation logs, instrument logs, raw data, and calculation worksheets. In addition, laboratory personnel will verify that the measurement process was"in control" (i.e., all specified data quality objectives were met or acceptable deviations explained)for each batch of samples before proceeding with the analysis of a subsequent batch. Each laboratory will also establish a system for detecting and reducing transcription and/or calculation errors prior to reporting data. 24. Data Validation In general, data validation involves identifying project requirements, obtaining the documents and records produced during data verification, evaluating the quality of the data generated, and determining whether project requirements were met. The main focus of data validation is determining data quality in terms of accomplishment of measurement quality objectives (i.e., meeting QC acceptance criteria). Data quality indicators, such as precision, accuracy, sensitivity, CCWTMP QAPP 71 August 15,2007 Revision 1 representativeness, and completeness, are typically used as expressions of data quality. The Project QA Manager, or designee, will review verified sample results for the data set as a whole, including laboratory qualifiers, summarize data and QC deficiencies and evaluate the impact on overall data quality, assign data validation qualifiers as necessary, and prepare an analytical data validation report. The validation process applies to both field and laboratory data. In addition to the data quality objectives presented in Table 14, the standard data validation procedures documented in the analyzing laboratory's QA Manual will be used to accept, reject or qualify the data generated. The laboratory will submit only data that have met data quality objectives, or data that have acceptable deviations explained. When QC requirements have not been met, the samples will be reanalyzed when possible, and only the results of the reanalysis will be submitted, provided that they are acceptable. Each laboratory's QA Officer is responsible for validating the data it generates. E. AMENDMENTS TO QAPP The intent of this section is to provide a place within the QAPP to document significant additions, deletions and revisions to the approved QAPP and to provide the rationale for changes. Revision 1: August 15, 2007 Major revisions include: • Revised Program Management structure to reflect MOA. • Changes based on the April 24, 2007 comment letter from the Los Angeles Regional Water Quality Control Board identified in the Response to Comments matrix(Appendix 1). • Included a Nutrient Investigation component. • Updated Project Schedule and Year 1 project deliverable schedule presented in Table 4. • Updated sediment toxicity identification evaluation (TIE)discussion to reflect recent advancements on whole sediment TIE procedures. CCWTMP QAPP 72 August 15,2007 Revision 1 F. REFERENCES Anderson, T. D. and Lydy, M. J. 2002. Increased toxicity to invertebrates associated with a mixture of atrazine and organophosphate insecticides. Environ. Tox. and Chem. V21, No. 7, 1507-1514. Bailey, H.C., DiGiorgio, C., Kroll, K., Miller, J.L., Hinton, D.E., Starrett, G. 1996. Development of Procedures for Identifying Pesticide Toxicity in Ambient Waters: Carbofuran, Diazinon, Chlorpyrifos. Environ. Tox. and Chem. V15, No. 6, 837-845. California Department of Fish and Game (CDFG). 2000. Standard Operating Procedures for Fish Tissue Sample Collection and Preparation: Sampling and Processing Trace Metal and Synthetic Organic Samples of Marine and Freshwater Fish. Method 102. CDFG Marine Pollution Studies Laboratory. July 2000. Larry Walker Associates (LWA). 2000. Guidance Manual: Stormwater Monitoring Protocols, 2nd Edition. Caltrans document No. CTSW-RT-00-005. Larry Walker Associates (LWA). 2006. Ventura County Agricultural Irrigated Lands Group (VCAILG) Quality Assurance Project Plan. August 3, 2006 [Revision 1]. Resource Management Associates, Inc. (RMA). 2003. FINAL REPORT Mugu Lagoon Numerical Model Development. Prepared for: U.S. Army Corps of Engineers Los Angeles District under subcontract to Coastal Frontiers Corporation. May 2003. State Water Resources Control Board (SWRCB). 1998. Sediment Chemistry, Toxicity, and Benthic Community Conditions in Selected Water Bodies of the Los Angeles Region - Final Report.. August 1998. State Water Resources Control Board (SWRCB). 2004a. Surface Water Ambient Monitoring Program, SWAMP-Compatible Quality Assurance Project Plans. March 2004. State Water Resources Control Board (SWRCB). 2004b. Surface Water Ambient Monitoring Program, Checklist. April 2004. United States Environmental Protection Agency(USEPA). 1991. Methods for Aquatic Toxicity Identification Evaluations: Phase 1 Toxicity Characterization Procedures (Second Edition). EPA- 600/6-91/003. USEPA, Environmental Research Laboratory, Duluth, MN. United States Environmental Protection Agency(USEPA). 1992. Toxicity Identification Evaluation: Characterization of Chronically Toxic Effluents Phase I. EPA-600/6-91/005. USEPA, Office of Research and Development, Washington, D.C. CCWTMP QAPP 73 August 15,2007 Revision 1 • United States Environmental Protection Agency(USEPA). 1993a. Methods for Measuring the Acute Toxicity of Effluents and Receiving Waters to Freshwater and Marine Organisms, Fourth Edition. EPA/600/4-90/027F. USEPA, Office of Research and Development, Washington, D.C. United States Environmental Protection Agency(USEPA). 1993b. Methods for Aquatic Toxicity Identification Evaluations: Phase II Toxicity Identification Procedures for Samples Exhibiting Acute and Chronic Toxicity. EPA/600/R-92/080. USEPA, Office of Research and Development, Washington, D.C. United States Environmental Protection Agency(USEPA). 1991. Sediment Toxicity Identification Evaluation: Phase I (Characterization), Phase II (Identification) and Phase III (Confirmation) Modifications of Effluent Procedures. EPA/600/6-91-007. USEPA, Environmental Research Laboratory, Duluth, MN. United States Environmental Protection Agency(USEPA). 1996. Marine Toxicity Identification Evaluation. Phase I Guidance Document EPA/600/R-96/054. USEPA, Office of Research and Development, Washington, D.C. United States Environmental Protection Agency(USEPA). 2000. Guidance for Assessing Chemical Contamination Data for Use in Fish Advisories, Volume 1, Fish Sampling and Analysis, Third Edition. EPA 823-B-00-007. USEPA Office of Water, Washington, D.C. November. United States Geological Survey(USGS). 1994. Guidelines for Collecting and Processing Samples of Stream Bed Sediment for Analysis of Trace Elements and Organic Contaminants for the National Water Quality Assessment Program. Weston, D.P., You, J.C., Lydy, M.J.. Distribution and Toxicity of Sediment-Associated Pesticides in Agriculture-Dominated Water Bodies of California's Central Valley. accepted for publication in Environ. Sci. &Technology. CCWTMP QAPP 74 August 15,2007 Revision 1 JUNE 18, 2007 APPENDICES DRAFT (REVISION 1 ) Calleguas Creek Watershed Management Plan Quality Assurance Project Plan (QAPP) Monitoring and Reporting Program Plan for the Nitrogen , OC and PCBs, and Toxicity Total Maximum Daily Loads submitted to Los Angeles Regional Water Quality Control Board prepared by LARRY WALKER ASSOCIATES on behalf of the CALLEGUAS CREEK WATERSHED MANAGEMENT PLAN WATER QUALITY/WATER RESOURCES SUBCOMMITTEE Appendix A Sampling Site Descriptions GPS Coordinates Thomas Guide Reach Site ID Site Type Lat Lon Site Description Driving Directions Pages 9 Mugu Lagoon Subwatershed From US 101 in Camarillo,exit Las Posas Rd. Turn left onto Las Posas 1 01_RR_BR RW 34.1090 -119.0916 Ronald Reagan Street Bridge and follow until Naval Base Ventura County-Point Mugu. Upon entering 583-H4 the base through the furthest gate south;turn left at Ronald Reagan Street. Access lagoon from bridge. 1 01 BPT 3 RW The QAPP presents a figure with Located near marsh area at the opening to the the approximate location for eastern arm of the lagoon 1 01 BPT 6 RW sample collection. Because of Located eastern portion of the western arm of the shifting shoals and sand bars in lagoon From western portion of the western arm of the From US 101 in Camarillo,exit Las Poses Rd. Turn left onto Las Posas 1 01_BPT_14 RW the lagoon,sediment samples will and follow until Naval Base Ventura County-Point Mugu. Enter base 583-H4 lagoon be collected from the deepest part Located in channel between estuary and mouth of the through the gate furthest south and meet with Navy staff to position 1 01_BPT_15 RW of the channel in the sampling equipment for sample collection. zones instead of reoccupying lagoon. 1 01 SG RW Located in the western portion of central lagoon. 1 Central Lagoon RW stations based only on GPS Central Lagoon 1 Western Arm RW Western Western Arm of the Lagoon From US 101 in Camarillo,exit Los Poses Rd.and head south. Turn 1 01T_ODD2_DCH Ag 34.1395 -119.1183 Duck Pond/Mugu/Oxnard Drain#2 S.of Hueneme Rd right onto Hueneme Rd. Just past the Hwy 1 interchange,turn left onto 553-E7 the 2nd ranch road on the left(Nauman Rd is too far).The site is located at the bridge crossing. Revolon Subwatershed From US 101 in Camarillo,exit Las Posas. Turn left onto Las Posas; 4 04 WOOD RW 34.1703 -119.0953 Revolon Slough-East Side Of Wood Road turn right onto Pleasant Valley Road;turn left onto Wood Road and 553-H3 continue until Wood Road crosses Revolon Slough. Access slough on east side of Wood Rd through a locked VCWPD gate. From US 101 in Camarillo,exit Las Posas. Turn left onto Las Posas; 4 04D WOOD Ag 34.1707 -119.0960 Agricultural Drain On East Side Of Wood Rd North Of turn right onto Pleasant Valley Road;turn left onto Wood Road and turn 553-H3 Revolon left onto flood control access road immediately before Wood Road crosses Revolon Slough. From US 101 in Camarillo,exit Las Posas Rd and head south. Turn left Camarillo Hills Drain at Ventura Blvd and Las Posas onto Ventura Blvd and follow the road until the first opportunity to 4 04D_VENTURA Urban 34.2161 -119.0675 Rd at VCWPD Gage 835 complete a legal U-tum. Head back towards Las Posas Rd and turn into 524-B3 flood control channel on right side of road. Access channel through gate next to VCWPD gage 835. From US 101 in Camarillo,head north on Central Ave to Beardsley Rd. 5 05_CENTR Ag 34.2300 -119.1128 Beardsley Wash At Central Avenue Pass Beardsley Road and take immediate right on to flood control 523-F1 access road. Pass through county gate and access channel at ladder next county gage. From US 101 in Camarillo,exit Central Ave and head north to Beardsley Santa Clara Drain at VCWPD Gaging Station 781 Rd. Pass Beardsley Road and take immediate right on to flood control 5 05D_SANT_VCWPD Ag 34.2425 -119.1114 prior To Confluence With Beardsley Channel access road. Pass through county gate and drive until Beardsley splits 493-F7 into 3 channels. Follow the channel heading northwest(Santa Clara Drain)until reaching County gaging station 781. GPS Coordinates Thomas Guide Reach Site ID Site Type Lat Lon Site Description Driving Directions Pages 9 Calleguas Subwatershed Calleguas Creek Lower Main Stem-Northeastern From Oxnard,heading south on Hwy 1,turn left,across northbound Hwy 2 02_PCH RW 34.1119 -119.0818 Side Of Highway 1 1 traffic,just south of Las Posas Rd intersection,onto Deer Path. Make 583-J4 way north to Calleguas Creek. From the southern end of Camarillo,exit Hwy 101 at Lewis Rd and head south. At the Potrero Rd.intersection,turn left onto the flood control 2 02D_BROOM Ag 34.1434 -119.0711 Discharge to Calleguas Creek at Broome Ranch Rd, levee and go through the VCWPD locked gate. Drive south along the 554-86 eastern Calleguas Creek levee until the first dirt road intersection (Broome Ranch Rd.)and park. The site is a discharge pipe located on the Creek side of the levy. Calleguas Creek Upper Main Stem-At University From US 101 in Camarillo,exit Lewis Rd and head south. From Lewis 3 03_UNIV RW 34.1798 -119.0441 Drive Rd take University Dr.(previously Camarillo Dr.)southeast to Calleguas 554-E1 Creek. Sample just upstream of bridge From US 101 in Camarillo,exit Lewis Rd and head south. From Lewis 3 03D_CAMR POTW 34.1679 -119.0530 Camrosa Water Reclamation Plant Rd turn east into the treatment plant approximately 1000 feet before 554-C3 Lewis Rd splits into Hueneme and Potrero. Conejo Creek At Howard Road Bridge-Below From US 101 in Camarillo exit Pleasant Valley Rd,and head south to 9A 9A_HOWAR RW 34.1931 -119.0025 Camarillo Wastewater Treatment Plant Poncho Rd. Turn left(south)on Poncho Rd. Turn left(east)on Howard 524-J7 Rd. Sample upstream of Howard Road Bridge. From US 101 in Camarillo exit Pleasant Valley Rd and head south. Turn 9A 9AD_CAMA POTW 34.1938 -119.0017 Camarillo Water Reclamation Plant south on Poncho Rd,left on Howard Rd and follow straight until reaching 524-J6 the plant gate. Conejo Creek Subwatershed From US 101 in Camarillo head north on Santa Rosa Rd Turn right 9B 9B_ADOLF RW 34.2125 -118.9894 Conejo Creek-At The End Of Adolfo Road (east)on Adolfo Rd and continue to the end. Pass through a locked VCWPD gate at the end of Adolfo. 525-84 9B 9BD_GERRY Ag 34.2369 -118.9473 Drainage Ditch Crossing Santa Rosa Rd At Gerry Rd From US 101 in Camarillo exit Santa Rosa Rd and head northeast.Turn left onto Gerry Rd,and park. 525-G1 From US 101 in Camarillo exit Santa Rosa Rd and head northeast.Turn 9B 9BD_ADOLF Urban 34.2148 -118.9951 Urban Storm Drain Passing Under North Side Of right(east)on Adolfo Rd and continue to end of the road,turn around Adolfo Rd Approximately 300 Meters From Reach 91b and head back to Santa Rosa Rd and park next to storm drain passing under the on north side of Adolfo Rd. 525-A3 From US 101 exit Santa Rosa Rd and head north. Take a right on Hill 10 10 GATE RW 34.2178 -118.9281 Conejo Creek Hill Canyon Below North Fork Of Canyon Rd, Access creek through gate which is located before the last 525-J3 Conejo Creek bend in the road before reaching Hill Canyon Wastewater Treatment Facility. Contact facility staff for access though gate. 10 10D_HILL POTW 34.2131 -118.9250 Hill Canyon Wastewater Treatment Plant From US 101 exit Santa Rosa Rd and head north. Take a right on Hill 526-A4 Canyon Rd and follow all the way to the treatment plant. From US 101 exit Santa Rosa Rd and head north. Take a right on Hill 12 12—PARK RW 34.2144 -118.9150 Conejo Creek North Fork Above Hill Canyon Canyon Rd. Access to creek is to the west of the operations building 526-A4 through a gate at the back of the plant. Proceed through gate until reaching a park area.Collect samples at park crossing. GPS Coordinates Thomas Guide Reach Site ID Site Type Lat Lon Site Description Driving Directions Pages 9 Conejo Creek South Fork Behind Hill Canyon Belt From Santa Rosa Rd head south on Hill Canyon Rd. Access creek 13 13—BELT RW 34.2078 -118.9194 press Building behind belt press building at Hill Canyon Wastewater Treatment Facility. 526-A4 Contact facility staff for access. South Branch Arroyo Conejo On South Side Of W From US 101 in Thousand Oaks exit Ventu Park Rd and head north. 13 13_SB_HILL Urban 34.1852 -118.9074 Hillcrest Turn right on W Hillcrest and turn right into first flood control channel 526-B7 immediately past office buildings. Las Posas Subwatershed From Somis Rd turn east onto road at Hagel Tree Farm,between Ag Rx 6 06_SOMIS RW 34.2540 -118.9927 Arroyo Las Posas Off Of Somis Road and Paty's Farm stand. Cross railroad tracks and follow road until you 495-A5 reach Arroyo Las Posas. 6 06D MOOR POTW 34.2690 -118.9330 Ventura County Wastewater Treatment Plant From Highway 118 turn south into treatment plant. 495-H3 From US 101 in Camarillo,exit Lewis-Souris Rd(Hwy 34)and head 6 06T_FC_BR Ag 34.2646 -119.0115 Fox Canyon At Bradley Rd-Just North Of Hwy 118 north.Turn left onto Hwy 118 and turn right onto Bradley Rd.Pull off 494-H4 Bradley Rd.to the right just past the Fox Canyon bridge.Site access is down the north bank of the channel,on the east side of Bradley Rd. Arroyo Simi Subwatershed 7 07 HITCH RW 34.2717 -118.9228 Arroyo Simi East Of Hitch Boulevard From Highway 118 turn south on Hitch Blvd to intersection of Arroyo Simi 495-J3 and turn left on north side of intersection. 2°d Corrugated Pipe Discharging On North Side Of From Highway 118 turn south on Hitch Blvd to intersection of Arroyo Simi 7 07D_HITCH_LEVEE-2 Ag 34.2714 -118.9205 Arroyo Simi Flood Control Levee Off Of Hitch Blvd and turn left on north side of intersection. 495-134 Just Beyond 15`Power Pole. 7 07_MADER RW 34.2778 -118.7958 Arroyo Simi At Madera Avenue From Highway 118 in Simi Valley exit Madera Rd and head south to 497-F1 intersection of Arroyo Simi. Turn into flood control access road. From Highway 118 in Simi Valley exit Collins Dr head south to with Los 7 07D_SIMI POTW 34.2814 -118.8150 Simi Valley Water Quality Control Plant Angeles Ave and turn east(left). Follow Los Angeles Ave until reaching 477-D7 plant entrance on south side of road. Flood control channel running through Country Trail Follow Tierra Rejada Rd south from Highway 118 and turn west on 7 07D_CTP Urban 34.2646 -118.9072 park. Mountain Trail St. Follow Mountain Trail St to Country Trail Park. 496-83 Sample from the flood control channel on north side of park. From Highway 118 in Simi Valley exit Tapo Canyon Rd and head south- 7 07T_DC_H Urban 34.2682 -118.7599 Dry Canyon At Heywood Street turn west at Los Angeles Ave. Turn south on Erringer Rd and east on 498-A3 Heywood St. Turn right into urban flood control channel on south side of Heywood St. From Highway 118 in Simi Valley exit Stearns St and head north. Turn 7 07T_LL_RC Open Space 34.3005 -118.6806 Las Llajas at Road Crossing left at Alamo St,right at Texas Ave,which becomes Las Llajas Canyon 479-A5 Rd. Turn onto fire road and follow until you see Las Llajas on your left behind VCWPD gate. Appendix B Basin Plan Amendments Appendix B Attachment 1 : Nitrogen Compounds and Related Effects in Calleguas Creek Basin Plan Amendment Attachment A to Resolution No. 02-017 Proposed Amendment to the Water Quality Control Plan—Los Angeles Region to Incorporate the Calleguas Creek Nitrogen Compounds and Related Effects TMDL Adopted by the California Regional Water Quality Control Board, Los Angeles Region on October 24, 2002. Amendments Table of Contents Add: Chapter 7. Total Maximum Daily Loads (TMDLs) 7-7 Calleguas Creek Nitrogen Compounds and Related Effects TMDL List of Figures,Tables, and Inserts Add: Chapter 7. Total Maximum Daily Loads (TMDLs) Tables 7-7 Calleguas Creek Nitrogen Compounds and Related Effects TMDL 7-7.1. Calleguas Creek Nitrogen Compounds and Related Effects TMDL: Elements 7-7.2. Calleguas Creek Nitrogen Compounds and Related Effects TMDL: Implementation Schedule Chapter 7. Total Maximum Daily Loads (TMDLs) Calleguas Creek Nitrogen Compounds and Related Effects TMDL This TMDL was adopted by: The Regional Water Quality Control Board on October 24, 2002. This TMDL was approved by: The State Water Resources Control Board on March 19, 2003. The Office of Administrative Law on June 5, 2003. The U.S. Environmental Protection Agency on June 20, 2003. August 30, 2002 Revised: October 24, 2002 Resolution No. 02-017 Page 2 Table 7-7.1. Calleguas Creek Nitrogen Compounds and Related Effects TMDL: Elements Element Calleguas Creek Nitrogen Compound and Related Effects Problem Elevated nitrogen concentrations (ammonia, nitrite and nitrate) are Statement causing impairments of the warm water fish and wildlife habitat, and groundwater recharge beneficial uses of Calleguas Creek. Nitrite and nitrate contribute to eutrophic effects such as low dissolved oxygen and algae growth. Ammonia contributes to toxicity. Numeric Target Numeric targets for this TMDL are listed as follows: (Interpretation of the numeric 1. Total Ammonia as Nitrogen (NH3-N) water quality NH3-N concentration(mg/L) objective, used One-hour Thirty-day to calculate the Reach average average load * Mugu Lagoon 8.1 2.9 allocations) * Calleguas Creek,South 5.5 2.4 * Calleguas Creek,North 8.4 3.0 * Revlon Slough 5.7 2.9 * Beardsley Channel 5.7 2.9 * Arroyo Las Posas 8.1 2.6 * Arroyo Simi 4.7 2.4 * Tapo Canyon 3.9 1.9 * Conejo Creek(Confluence with Calleguas 9.5 3.5 Creek to Santa Rosa Rd.) * Conejo Creek(Santa Rosa Road 8.4 3.4 to Thousand Oaks City Limit) * Conejo Creek,Hill Canyon Reach 8.4 3.1 * Conejo Creek,North Fork 3.2 1.7 * Arroyo Conejo(South Fork Conejo Creek) 5.1 3.4 * Arroyo Santa Rosa 5.7 2.4 2. Nitrate and nitrite as nitrogen (NO3-N and NO2-N) Constituent Concentration(mg/L) • NO3-N 10 • NO2-N 1 • NO3-N+NO2-N 10 Numeric targets to address narrative objectives required to protect warm freshwater and wildlife habitat are intended to implement the narrative objectives and may be revised based on the results of monitoring and special studies conducted pursuant to the implementation plan. August 30, 2002 Revised: October 24, 2002 Resolution No. 02-017 Page 3 Source Analysis The principal sources of nitrogen into Calleguas Creek are discharges from the POTWs in the watershed and runoff from agricultural activities in the watershed. Linkage Linkage between nitrogen sources and the in-stream water quality was Analysis established through a mass continuity model based on an evaluation of recent hydrodynamic and water quality data. Waste Load The waste load allocations (WLAs) are as follows: Allocations (for Concentration(mg/L) point sources) NHj-N NO3-N NO2-N NO3-N+NO2-N MDELI AMEL2 Daily WLA POTWS (mg/L) (lb/day) (mg/L) • Hill Canyon WTP3 5.6 3.1 254 9.0 0.9 9.0 • Simi Valley WQCF4 3.3 2.4 220 9.0 0.9 9.0 • Moorpark WTP 6.4 2.6 59 9.0 0.9 9.0 • Camarillo WRP5 7.8 3.5 177 9.0 0.9 9.0 • Camrosa WRF 6 7.2 3.0 33 9.0 0.9 9.0 Load Allocation The source analysis indicates that agricultural discharge is the major non- (for non point point source of oxidized nitrogen to Calleguas Creek and its tributaries. sources) This source is particularly significant in Revolon Slough and other agricultural drains in the lower Calleguas watershed where there are no point sources of ammonia and oxidized nitrogen. Load allocations for non-point sources are: NO3-N+NO2-N Nonpoint Source (mg/L) Agriculture 9.0 Other Nonpoint Source 9.0 Implementation 1. Refer to Table 7-7.2 2. Several of the POTWs in the Calleguas Creek watershed will require additional time to meet the nitrogen (NO3-N, NO2-N, and NO3-N + NO2-N) waste load allocations. To allow time to meet the nitrogen waste load allocations, interim limits will be allowed for a period of four years from the effective date of the TMDL during which the POTWs will be required to meet the effluent limit for NO3-N +NO2- N only. Effluent limits for the individual compounds NO3-N and I MDEL:Maximum daily effluent limitation 2 AMEL: Average monthly effluent limitation 3 WTP:Wastewater Treatment Plant 4 WQCF:Water Quality Control Facility 5 WRP:Water Reclamation Plant 6 WRF:Water Reclamation Facility August 30, 2002 Revised: October 24, 2002 Resolution No. 02-017 Page 4 NO2-N are not required during the interim period. Interim Limits for NO3-N+NO2-N Monthly Average Daily Maximum POTWs (mg/L) (mg/L) • Hill Canyon WTP 36.03 38.32 • Simi Valley WQCF 31.60 32.17 • Moorpark WTP 31.5 32.01 • Camarillo WRP 36.23 37.75 *The monthly average and daily maximum interim limits are based on the 95th and 991h percentiles of effluent performance data reported in the Calleguas Creek Characterization Study 3. The waste load allocations for ammonia will be applicable on the effective date of the TMDL. Interim limits for ammonia will be applicable for no more than 2 years starting from October 24, 2002 for POTWs that are not able to achieve immediate compliance with the assigned waste load allocations. The interim limits for ammonia may be established at the discretion of the Regional Board when a POTW's NPDES permit is reissued. Margin of An implicit margin of safety is incorporated through conservative model Safety assumptions and statistical analysis. In addition, an explicit margin of safety is incorporated by reserving 10% of the load, calculated on a concentration basis, from allocation to POTW effluent sources. Seasonal A low flow critical condition is identified for this TMDL based on a Variations and review of flow data for the past twenty years. This flow condition was Critical identified because less assimilative capacity is available to dilute effluent Conditions discharge. August 30, 2002 Revised: October 24, 2002 Resolution No. 02-017 Page 5 Table 7-7.2. Implementation Schedule IMPLEMENTATION TASKS,MILESTONES AND COMPLETION DATE' PROVISIONS- 1. WLA for ammonia apply to POTWs. Effective Date of TMDL 2. Interim Limits for NO3-N+NO2-N apply to POTWs. 3. Formation of Nonpoint Source BMP Evaluation Committee. 4. Submittal of Non point Source Monitoring 1 year after Effective Date Workplan by Calleguas Creek Watershed of TMDL Management Plan — Water Resources/Water Quality(CCWMP) Subcommittee. This monitoring is to evaluate nutrient loadings associated with agricultural drainage and other nonpoint sources. The monitoring program will include both dry and wet weather discharges from agricultural, urban and open space sources. In addition, groundwater discharge to Calleguas Creek will also be analyzed for nutrients to determine the magnitude of these loading and the need for load allocations. A key objective of these special studies will be to determine the effectiveness of agricultural BMPs in reducing nutrient loadings. Consequently, flow and analytical data for nutrients will be required to estimate loadings from nonpoint sources. 5. Submittal of Watershed Monitoring Workplan by CCWMP Subcommittee. In addition to the analytical parameters and flow data requirements, the watershed monitoring program will establish sampling locations from which representative samples can be obtained, including all listed tributaries. Monitoring results will be compared to the numeric instream targets identified in this TMDL to determine the effectiveness of the TMDL. Data on the extent and distribution of algal mats, scum and odors will be included in the watershed monitoring program. The data will be The CCWMP Subcommittee has offered to complete tasks 4 through 9 and 11. In the event the CCWMP Subcommittee fails to timely complete these tasks,the Regional Board will consider whether to amend this Implementation Plan to assign tasks to responsible dischargers in the regulatory approach. The Regional Board also reserves its right to take any other appropriate actions including,but not limited to,exercising its authorities under Water Code section 13267. August 30, 2002 Revised: October 24, 2002 Resolution No. 02-017 Page 6 IMPLEMENTATION TASKS,MILESTONES AND COMPLETION DATE "PROVISIONS* used to provide further verification of the model and refine the TMDL to address nutrient effects as appropriate. 6. Submittal of Special Studies Workplan by CCWMP Subcommittee. These special studies include: Monitoring of minor point sources for nutrients to confirm assumptions that the loadings from these sources are minor; Monitoring of greenhouse discharges and runoff to assess loadings from these sources; Monitoring of groundwater extraction and discharges in the Arroyo Santa Rosa subwatershed and other areas that may add significant nutrient loadings to Calleguas Creek; and Additional studies of the type and extent of algae impairment in Calleguas Creek and Mugu Lagoon. 7. Complete Special Studies for minor sources, 3 years after Effective Date greenhouses, and groundwater loadings. of TMDL 8. Completion of ammonia Water Effect Ratio (WER) studies. 9. Complete planning and preparation for construction of TMDL remedies to reduce non- point source nitrogen loads. 10. Interim Limits for NO3-N+NO2-N expire and 4 years after Effective Date WLAs for NO3-N, NO2-N,NO3-N+NO2-N apply of TMDL to POTWs. 11. Complete Special Studies for algae impairments of 5 years after Effective Date Calleguas Creek, its tributaries and Mugu Lagoon. of TMDL 12. Regional Board consideration of revised water 6 years after Effective Date quality objectives for nitrogen compounds based of TMDL on monitoring data, special studies, and ammonia WER, if appropriate. 13. Final achievement of ammonia and oxidized 7 years after Effective Date nitrogen standards. of TMDL August 30, 2002 Revised: October 24, 2002 Appendix B Attachment 2: Organochlorine (OC) Pesticides, Polychlorinated Biphenyls (PCBs) and Siltation in Calleguas Creek, its Tributaries, and Mugu Lagoon Basin Plan Amendment Attachment A to Resolution No.114-2005-010 Amendment to the Water Quality Control Plan—Los Angeles Region to Incorporate a Total Maximum Daily Loads (TMDLs)for Organochlorine (OC) Pesticides, Polychlorinated Biphenyls (PCBs) and Siltation in Calleguas Creek, Its Tributaries,and Mugu Lagoon Adopted by the California Regional Water Quality Control Board, Los Angeles Region on July 7, 2005. Amendments Table of Contents Add: Chapter 7. Total Maximum Daily Loads (TMDLs) 7- 17 Calleguas Creek Organochlorine Pesticides, Polychlorinated Biphenyls, and Siltation TMDL List of Figures,Tables, and Inserts Add: Chapter 7. Total Maximum Daily Loads (TMDLs) Tables 7-17 Calleguas Creek Organochlorine Pesticides, Polychlorinated Biphenyls, and Siltation TMDL 7-17.1 Calleguas Creek Organochlorine Pesticides, Polychlorinated Biphenyls, and Siltation TMDL: Elements 7-17.2 Calleguas Creek Organochlorine Pesticides, Polychlorinated Biphenyls, and Siltation TMDL: Implementation Schedule Chapter 7. Total Maximum Daily Loads (TMDLs) Calleguas Creek Organochlorine Pesticides,Polychlorinated Biphenyls, and Siltation TMDL Add: This TMDL was adopted by the Regional Water Quality Control Board on July 7, 2005. This TMDL was approved by: The State Water Resources Control Board on September 22, 2005. The Office of Administrative Law on January 20, 2006, The U.S. Environmental Protection Agency on March 14, 2006. The following table includes the elements of the TMDL: July 7, 2005 Attachment A to Resolution No.R4-2005-010 Table 7-17.1. Calleguas Creek Watershed OC Pesticides, PCBs, and Siltation TMDL: Elements TMDL Element Calleguas Creek Watershed OC Pesticide,PCBs,and Siltation TMDL' Problem Eleven of fourteen reaches in the Calleguas Creek Watershed Statement (CCW) were identified on the 2002 303(d) list of water-quality limited segments as impaired due to elevated levels of organochlorine (OC)pesticides and/or polychlorinated biphenyls (PCBs) in water, sediment, and/or fish tissue. Additionally, Mugu Lagoon was listed as impaired for sedimentation/siltation. OC pesticides and PCBs can bioaccumulate in fish tissue and cause toxicity to aquatic life in estuarine and inland waters. Siltation may transport OC Pesticides and PCBs to surface waters and impair a uatic life and wildlife habitats. Numeric The following tables provide the targets for water, fish tissue, and Targets sediment for this TMDL. Water column targets were derived from the California Toxic Rule (CTR) water quality criteria for protection of aquatic life. Chronic criteria(Criteria Continuous Concentration, or CCC) were applied unless otherwise noted in the table below: Water Quality Targets(ng/L)1 Constituent Freshwater Marine 2 Aldrin 300.0 130.0 Chlordane 4.3 4.0 Dacthal 3,500,000.0 (a)3 4,4'-DDD4 (a)3 (a)3 4,4'-DDEs (a)3 (a)3 4,4'-DDT 6 1.0 1.0 Dieldrin 56.0 1.9 Endosulfan I 56.0 8.7 Endosulfan Il 56.0 8.7 Endrin 36.0 2.3 HCH(alpha-BHC') (a)3 (a)3 HCH(beta-BHC) (a)3 (a)3 HCH(delta-BHC) (a)3 (a)3 ng/L:nanogram per litter 2 Marine numeric targets applied to Mugu Lagoon 3 Numeric targets have not been established for these constituents 4 DDD:Dichlorodiphenyldichloroethane 5 DDE:Dichlorodiphenyldichloroethylene 6 DDT:Dichlorodiphenyltrichloroethane BHC:Hexachlorocyclohexane Page 2 July 7, 2005 Attachment A to Resolution No. R4-2005-010 TIMDL Element Calleguas Creek Watershed QC Pesticide,PCBs,and Siltation TMDL HCH(gamma BHC) 950.0 160.0 Heptachlor 3.8 3.6 Heptachlor Epoxide 3.8 3.6 PCBs 140.0' 30.0' Toxaphene 0.2 0.2 Fish tissue targets are derived from CTR human health criteria for consumption of organisms. Fish Tissue Targets(ng/Kg) Constituent Aldrin 50.0 Chlordane 830.0 Dacthal (a)2 4,4'-DDD 45,000.0 4,4'-DDE 32,000.0 4,4'-DDT 32,000.0 Dieldrin 650.0 Endosulfan I 65,000,000.0 Endosulfan Il 65,000,000.0 Endrin 3,200,000.0 HCH(alpha-BHC) 1,700.00 HCH(beta-BHC) 6,000.0 HCH(delta-BHC) (a)' HCH(gamma BHC) 8,200. Heptachlor 2,400.0 Heptachlor Epoxide 1,200.0 PCBs 5,300.03 Toxaphene 9,800.0 Sediment targets were derived from sediment quality guidelines contained in National Oceanographic and Atmospheric Administration (NOAA) Screening Quick Reference Tables (SQuiRT, Buchman, 1999). Sediment Quality Targets(ng/dry Kg) Constituent Freshwater,TEL Marine',ERL' Aldrin (a)' (a)' Chlordane 4,500.0 500.0 Dacthal (a)' (a)' 4,4'-DDD 3,500.0 2,000.0 'Applies to sum of all congener or isomer or homolog or Aroclor analyses 2 Numeric targets have not been established for these constituents 3 Applies to sum of all congener or isomer or homolog or Aroclor analyses °TEL=Threshold Effects Level s Marine numeric targets applied to Mugu Lagoon 'ERL=Effects Range-Low. Page 3 July 7, 2005 Attachment A to Resolution No. R4-2005-010 TMDL Element Calleguas Creek Watershed OC Pesticide,PCBs,and Siltation TMDL 4,4'-DDE 1,400.0 2,200.0 4,4'-DDT (a)' 1,000.0 Dieldrin 2,900.0 20.0 Endosulfan I (a)' (a)' Endosulfan II (a)' (a)' Endrin 2,700.0 (a)' HCH(alpha-BHC) (a)' (a)' HCH(beta-BHC) (a)' (a)' HCH(delta-BHC) (a)' (a)' HCH(gamma BHC) 940.0 (a)' Heptachlor (a)' (a)' Heptachlor Epoxide 600.0 (a)' PCBs 34,000.02 23,000.0 Toxaphene (a)' (a)' Siltation Targets This TMDL includes two numeric targets for siltation reduction and maintenance of existing habitat in Mugu Lagoon which are listed below: • Siltation reduction Annual average reduction in the import of silt of 5,200 tons/year, which will be measured at the US Naval Base total suspended sediment gauge at the entrance to Mugu Lagoon. • Maintenance of existing habitat in Mugu Lagoon Preservation of the existing 1400 acres of aquatic habitat in Mugu Lagoon. Source Analysis Monitoring data from major NPDES discharges and land use runoff were analyzed to estimate the magnitude of OC pesticides and PCBs loads to Calleguas Creek, its tributaries and Mugu Lagoon. The largest source of OC pesticides in the listed waters is agricultural runoff. Most PCB residues are due to past use of PCBs as coolants and lubricants in transformers, capacitors, and other electrical equipment. Atmospheric deposition is also a potential source of PCBs. Urban runoff and POTWs are minor sources of OC pesticides and PCBs. Data analysis suggests that groundwater, atmospheric deposition, and imported water are not significant sources of OC pesticides, PCBs, or sediment. Further evaluation of these sources is set forth in the Implementation Plan. Linkage The linkage analysis is based on a conceptual model for the fate, Analysis transformation, and uptake of OC pesticides and PCBs and a mass- balance model that connects the sources of OC pesticides and PCBs to their fate and transport in Calleguas Creek, its tributaries, and Mu u La oon. The linkage analysis indicates: 1) OC pesticides Page 4 July 7, 2005 Attachment A to Resolution No. R4-2005-010 TMDL Element Calleguas Creek Watershed OC Pesticide,PCBs,and Siltation TMWL' and PCBs concentrations in tissue are proportional to OC pesticides and PCBs concentrations in sediments; 2) OC pesticides and PCBs concentrations in water are a function of OC pesticides and PCBs concentrations in sediment; and 3) OC pesticides and PCBs concentrations in sediment are a function of OC pesticides and PCBs loading and sediment transport. Because sediments store, convey and serve as a source of OC pesticides and PCBs, a reduction of OC pesticides and PCBs concentrations in sediment will result in a reduction of OC pesticides and PCBs concentration in the water column and fish tissue. In this linkage analysis, DDE is used as a representative constituent, because DDE is consistently detected in monitoring and exceeds numeric targets in water, sediment, and tissue samples. Also, other OC Pesticides and PCBs possess similar physical and chemical properties to DDE. Wasteload Allocations 1. Interim and Final WLAs* for Pollutants in Effluent for POTWs. The interim wasteload allocations for POTWs will be re- considered by the Regional Board on a 5-year basis. This re- consideration will be based on sufficient data to calculate Interim Wasteload Allocations in accordance with SIP procedures. a) Interim WLAs (ng/L) Constituent POTW Hill Canyon Simi Valley Moorpark Camarillo Camrosa Daily Daily Daily Daily Daily Chlordane 1.2 100.0 100.0 100.0 100.0 4,4-DDD 20.0 50.0 50.0 6.0 50.0 4,4-DDE 260.0 1.2 1.2 188.0 50.0 4,4-DDT 10.0 10.0 10.0 10.0 10.0 Dieldrin 10.0 10.0 10.0 10.0 10.0 PCBs 500.0 500.0 500.0 31.0 500.0 Toxaphene 500.0 500.0 500.0 500.0 500.0 *WLAs shall be applied to POTWs'effluent b) Final WLAs (ng/L) Constituent POTW Hill Canyon Simi Valley Moorpark Camarillo Camrosa Daily Monthly Daily Monthly Daily Monthly Daily Monthly Daily Monthly Chlordane 1.2 0.59 1.2 0.59 1.2 0.59 1.2 0.59 1.2 0.59 4,4-DDD 1.7 0.84 1.7 0.84 1.7 0.84 1.7 0.84 1.7 0.84 4,4-DDE 1.2 0.59 1.2 0.59 1.2 0.59 1.2 0.59 1.2 0.59 4,4-DDT 1.2 0.59 1.2 0.59 1.2 0.59 1.2 0.59 1.2 0.59 Dieldrin 0.28 0.14 0.28 0.14 0.28 0.14 0.28 0.14 0.28 0.14 Page 5 July 7, 2005 Attachment A to Resolution No. R4-2005-010 TMDL Element Calleguas Creek Watershed OC Pesticide,PCBs,and Siltation TMDL' PCBs 0.34 0.17 0.34 0.17 0.34 0.17 0.34 0.17 0.34 0.17 Toxaphene 0.33 0.16 0.33 0.16 0.33 0.16 0.33 0.16 0.33 0.16 The final WLAs will be included in NPDES permits in accordance with schedule in the implementation plan. The Regional Board may revise final WLAs prior to the dates they are placed into permits and/or prior to the dates of final WLA achievement based on special studies and monitoring of this TMDL. 2. Interim and Final WLAs for Pollutants in Sediment for Stormwater Permittees a) Interim WLAs (ng/g) Constituent Subwatershed Mugu Calleguas Revolon Arroyo Arroyo Conejo Lagoon' Creek Slough Las Posas Simi Creek Chlordane 25.0 17.0 48.0 3.3 3.3 3.4 4,4-DDD 69.0 66.0 400.0 290.0 14.0 5.3 4,4-DDE 300.0 470.0 1,600.0 950.0 170.0 20.0 4,4-DDT 39.0 110.0 690.0 670.0 25.0 2.0 Dieldrin 19.0 3.0 5.7 1.1 1.1 3.0 PCBs 180.0 3,800.0 7,600.0 25,700.0 25,700.0 3,800.0 Toxaphene 22,900.0 260.0 790.0 230.0 230.0 260.0 Compliance with sediment based WLAs is measured as an in- stream annual average at the base of each subwatershed where the discharges are located. b) Final WLAs (ng/g) Constituent Subwatershed Mugu Calleguas Revolon Arroyo Arroyo Conejo Lagoon' Creek Slough Las Posas Simi Creek Chlordane 3.3 3.3 0.9 3.3 3.3 3.3 4,4-DDD 2.0 2.0 2.0 2.0 2.0 2.0 4,4-DDE 2.2 1.4 1.4 1.4 1.4 1.4 4,4-DDT 0.3 0.3 0.3 0.3 0.3 0.3 Dieldrin 4.3 0.2 0.1 0.2 0.2 0.2 PCBs 180.0 120.0 130.0 120.0 120.0 120.0 Toxaphene 360.0 0.6 1.0 0.6 0.6 0.6 'The Mugu Lagoon subwatershed includes Duck Pond/Agricultural Drain/Mugu/Oxnard Drain#2. Compliance with sediment based WLAs is measured as an in- stream annual average at the base of each subwatershed where the discharges are located. 3. Final WLAs for Pollutants in Water Column for Minor Point Sources WLAs for pollutants in water column are allocated below to Page 6 July 7, 2005 Attachment A to Resolution No. 114-2005-010 TMDL Element Calleguas Creek Watershed'4C Pesticide,PCBs,and Siltation TMDL minor point sources enrolled under NPDES permits or WDRs, which discharge to Calleguas Creek. Constituent Daily Maximum(ng/L) Monthly Average(ng/L) Chlordane 1.2 0.59 4,4-DDD 1.7 0.84 4,4-DDE 1.2 0.59 4,4-DDT 1.2 0.59 Dieldrin 0.28 0.14 PCBs 0.34 0.17 Toxaphene 0.33 0.16 4. Siltation WLA for MS4 MS4 dischargers will receive an allocation of 2,496-tons/yr. reduction in sediment yield to Mugu Lagoon. The baseline from which the load reduction will be evaluated will be determined by a special study of this TMDL. The load allocation will apply after the baseline is established, as described in the Implementation Plan. Load Compliance with sediment based LAs listed below is measured as Allocations an in-stream annual average at the base of each subwatershed. 1. Interim and Final Load Allocations a) Interim Sediment LAs (ng/g) Constituent Subwatershed Mugu Calleguas Revolon Arroyo Arroyo Conejo Lagoon Creek Slough Las Posas Simi Creek Chlordane 25.0 17.0 48.0 3.3 3.3 3.4 4,4-DDD 69.0 66.0 400.0 290.0 14.0 5.3 4,4-DDE 300.0 470.0 1,600.0 950.0 170.0 20.0 4,4-DDT 39.0 110.0 690.0 670.0 25.0 2.0 Dieldrin 19.0 3.0 5.7 1.1 1.1 3.0 PCBs 180.0 3,800.0 7,600.0 25,700.0 25,700.0 3,800.0 Toxaphene 22900.0 260.0 790.0 230.0 230.0 260.0 1 The Mugu Lagoon subwatershed includes Duck Pond/Agricultural Drain/Mugu/Oxnard Drain#2. b) Final Sediment LAs (ng/g) Constituent Subwatershed Mugu Calleguas Revolon Arroyo Arroyo Conejo La oonl Creek Slough Las Posas Simi Creek Page 7 July 7, 2005 Attachment A to Resolution No. R4-2005-010 TMDL Element Calleguas Creek Watershed OC Pesticide,PCBs,and Siltation TMDL Chlordane 3.3 3.3 0.9 3.3 3.3 3.3 4,4-DDD 2.0 2.0 2.0 2.0 2.0 2.0 4,4-DDE 2.2 1.4 1.4 1.4 1.4 1.4 4,4-DDT 0.3 0.3 0.3 0.3 0.3 0.3 Dieldrin 4.3 0.2 0.1 0.2 0.2 0.2 PCBs 180.0 120.0 130.0 120.0 120.0 120.0 Toxaphene 360.0 0.6 1.0 0.6 0.6 0.6 1 The Mugu Lagoon subwatershed includes Duck Pond/Agri cultural Drain/Mugu/Oxnard Drain#2. 2.Siltation LAs Agricultural dischargers will receive an allocation of 2,704 tons/yr. Reduction in sediment yield to Mugu Lagoon. The baseline from which the load reduction will be evaluated will be determined by a special study of this TMDL. The load allocation will apply after the baseline is established, as described in the Implementation Plan. Margin of This TMDL relies on an implicit margin of safety,by incorporating Safety conservative assumptions throughout its development, including: �. Basing percent reductions on the historical data set of water and fish tissue concentrations, which does not reflect the effects of attenuation the over the past ten years. • Determining the percent reduction in sediment,by basing it on the greater percent reduction of either water or fish tissue concentrations based on available data. • Reducing the allowable concentration for upstream subwatersheds, to ensure protection of those subwatersheds downstream from upstream inputs. • Choosing Threshold Effects Levels (TELs) and Effects Range Lows (ERLs) as numeric targets for sediment,which are the most protective applicable sediment guidelines. • Selecting the more stringent of the allowable concentration (as calculated by percent reduction methodology) or the numeric target for sediment (TEL or ERL), when available, as the WLA and LA for all reaches with 303(d) listings for sediment. Future Growth Ventura County accounts for slightly more than 2% of the state's residents with a population of 753,197 (US Census Bureau, 2000). GIS analysis of the 2000 census data yields a population estimate of 334,000 for the CCW, which equals about 44% of the county population. According to the Southern California Association of Governments (SLAG), growth in Ventura County averaged about 51% per decade from 1900-2000; with growth exceeding 70% in the 1920s, 1950s, and 1960s. Significant population growth is expected to occur within and near present city limits until at least Page 8 July 7, 2005 Attachment A to Resolution No. R4-2005-010 TMDL Element Calleguas Creek Watershed OC Pesticide, PCBs,and Siltation TMDL' 2020. Since most of the listed OCs and PCBs in the CCW are banned, this growth is not expected to increase current loads. Urban application of those OC pesticides which are still legal (dacthal and endosulfan) may increase,but overall use may decrease because urban expansion tends to reduce total acreage of agricultural land. Population growth may result in greater OC loading to POTW influent from washing food products containing OC residues. This loading may be proportional to the increase in population, if per capita domestic water use and pesticide load per household remain constant. Increased flow from POTWs should not result in impairment of the CCW as long as effluent concentration standards are met for each POTW. As urban development occurs, construction activities may have a range of effects on OC loading to the CCW. Exposure of previously vegetated or deeply buried soil might lead to increased rates of transportation and volatilization. Conversely, urbanization of open space and/or agriculture areas may cover OC pesticides bound to sediments. Future growth in the CCW may result in increased groundwater concentrations of currently used OC pesticides. This is a potential concern for dacthal, which is still used and has been found in groundwater(although current levels of dacthal are significantly lower than all available targets). The effects of future growth upon PCB loads are unknown,but not likely to prove significant, since atmospheric deposition and accidental spills are the primary loading pathways. Any increase in OCs due to population growth may be offset by decreased inputs from banned OCs, as their presence attenuates due to fate and transport processes. Critical The linkage analysis found correlation between concentrations of Conditions OC pesticides and PCBs in water and total suspended solids (TSS), and a potential correlation between OC pesticides and PCBs concentrations in water and seasonality (wet vs. dry season). A similar correlation between sediment loading and wet weather is also noted. OC pesticides and PCB pollutants are of potential concern in the Calleguas Creek Watershed due to possible long-term loading and food chain bioaccumulation effects. There is no evidence of short- term effects. However,pollutant loads and transport within the Page 9 July 7, 2005 Attachment A to Resolution No.114-2005-010 TMDL Element> Calleguas Creek Watershed OC Pesticide,PCBs,and Siltation TMDL' watershed may vary under different flow and runoff conditions. Therefore the TMDLs consider seasonal variations in loads and flows but are established in a manner which accounts for the longer time horizon in which ecological effects may occur. Wet weather events, which may occur at any time of the year, produce extensive sediment redistribution and transport downstream. This would be considered the critical condition for loading. However, the effects of organochlorine compounds are manifested over long time periods in response to bioaccumulation in the food chain. Therefore, short-term loading variations (within the time scale of wet and dry seasons each year) are not likely to cause significant variations in beneficial use effects. Therefore, although seasonal variations in loads and flows were considered, the TMDL was established in a manner which accounts for the longer time horizon in which ecological effects may occur Implementation The final WLAs will be included in NPDES permits in accordance Plan with the compliance schedules provided in Table 7-17.2. The Regional Board may revise these WLAs based on additional information developed through Special Studies and/or Monitoring of this TMDL. WLAs established for the five major POTWs in this TMDL will be implemented through NPDES permit limits. The proposed permit limits will be applied as end-of-pipe concentration-based effluent limits for POTWs. Compliance will be determined through monitoring of final effluent discharge as defined in the NPDES permit. The implementation plan for POTWs focuses on implementation of source control activities. Consideration of annual averaging of compliance data will be evaluated at the time of permit renewal based on available information, Regional Board policies, and US EPA approval. In accordance with current practice, a group concentration-based WLA has been developed for MS4s, including the Caltrans MS4. The grouped allocation will apply to all NPDES-regulated municipal stormwater discharges in the CCW. Other NPDES- regulated stormwater permittees will be assigned a concentration- based WLA consistent with the interim and final WLAs set forth above. Stormwater WLAs will be incorporated into the NPDES permit as receiving water limits measured at the downstream points of each subwatershed and are expected to be achieved through the implementation of BMPs as outlined in the implementation plan. Page 10 July 7, 2005 Attachment A to Resolution No. R4-2005-010 TMDL Element Calleguas Creek Watershed OC Pesticide,PCBs,and Siltation TMDL The Regional Board will need to ensure that permit conditions are consistent with the assumptions of the WLAs. If BMPs are to be used, the Regional Board will need to detail its findings and conclusions supporting the use of BMPs in the NPDES permit fact sheets. Should federal, state, or regional guidance or practice for implementing WI-As into permits be revised,the Regional Board may reevaluated the TMDL to incorporate such guidance. LAs will be implemented through the State's Nonpoint Source Pollution Control Program (NPSPCP). The LARWQCB is developing a Conditional Waiver for Irrigated Lands, which includes monitoring at sites subject to approval by the Executive Officer of the Regional Board. Should adoption of the Conditional Waiver be delayed, monitoring will be required as part of this TMDL. Studies are currently being conducted to assess the effectiveness of BMPs for reduction of pollutants from agricultural operations. Results will be used to develop Agricultural Water Quality Management Plans, including the implementation of agricultural BMPs. Additionally, an agricultural education program will be developed to inform growers of the recommended BMPs and the Management Plan. As shown in Table 7-17.2, implementation actions will be taken by agricultural dischargers located in the CCW. The implementation of agricultural BMPs will be based on a comprehensive approach to address pollutant loads discharged from agricultural operations. The Regional Board may revise these LAs based on the collection of additional information developed through special studies and/or monitoring conducted as part of this TMDL. A number of provisions in this TMDL might provide information that could result in revisions to the TMDL. Additionally, the development of sediment quality criteria and other water quality criteria revisions may require the reevaluation of this TMDL. Finally, the use of OC pesticides in other countries which may be present in imported food products, compounded with the persistence of OC pesticides and PCBs in the environment, indicate that efforts to control sources and transport of OCs to receiving waters may not result in attainment of targets and allocations due to activities that are outside the control of local agencies and agriculture. For these reasons, the Implementation Plan includes this provision for reevaluating the TMDL to consider revised water Page 11 July 7, 2005 Attachment A to Resolution No. R4-2005-010 TMDL Element Calleguas Creek Watershed QC Pesticide,PCBs,and Siltation TMDL' quality objectives and the results of implementation studies, if appropriate. The siltation portion of the TMDL includes wasteload and load allocations set as an annual mass reduction from a baseline value of sediment and silt deposited in Mugu Lagoon. The baseline value of sediment and silt conveyed to Mugu Lagoon is to be determined by a TMDL Special Study and established by the Regional Board through an amendment to the TMDL. The Special Study is eight years in duration to ensure that the full range of current conditions that affect loading of sediment and siltation to Mugu Lagoon are considered. If appropriate, the Special Study may also result in a revision to the mass load reduction. The Special Study will be overseen by a Science Advisory Panel consisting of local, regional, and/or national experts in estuarine habitat biology,hydrology, and engineering. At the conclusion of the special study, the Regional Board will reconsider the TMDL to establish sustainable wasteload and load allocations recommended by the Special Study to support aquatic life and wetland habitat beneficial uses. In implementing this TMDL, staff recognize that dischargers may be implementing management measures and management practices to reduce sediment and Siltation loads through permit and waiver programs during the special studies. Further, since the effective date of the Consent Decree,reaches of Calleguas Creek have been listed due to sediment, and another TMDL may be initiated during the Special Study of this TMDL. Staff's intent is to coordinate the requirements of this TMDL with other programs that reduce sedimentation and siltation. The Special Study can consider sediment and silt load reductions through existing permits and the forthcoming conditional waiver for irrigated lands. Load and wasteload allocations become effective after the Regional Board actions based on the Special Study, nine years after the effective date of the TMDL. Page 12 July 7, 2005 Attachment A to Resolution No. R4-2005-010 Table 7-17.2 Implementation Schedule tip)lemepfationl Ac- t Respon`sibie Party` `<;C©mpletion Date 1 Interim organochlorine pesticide and polychlorinated NPDES Permittees Effective date of the bi hen is wasteload allocations apply. amendment 2 Interim organochlorine pesticide and polychlorinated Agricultural Dischargers Effective date of the biphenyls load allocations apply. amendment Finalize and submit workplan for organochlorine pesticide and polychlorinated biphenyls TMDL monitoring,or finalize and submit a workplan for an Integrated Calleguas Creek Watershed organochlorine pesticide and POTW Permittees,MS4 6 months after effective 3 polychlorinated biphenyls Monitoring Program for approval Permittees,Agricultural date of the amendment by the Executive Officer. The monitoring workplan will Dischargers,US Navy include,but not be limited to,appropriate water,biota,and sediment loading and monitoring to verify attainment of targets and protection of beneficial uses. Initiate Calleguas Creek Watershed organochlorine POTW Permittees,MS4 6 months after Executive 4 Permittees,Agricultural pesticide,polychlorinated biphenyls,and siltation Officer approval of Monitoring Program developed under the Task 3 workplan Dischargers,US Navy Monitoring Program(Task approved b the Executive Officer. 3)workplan Submit a workplan for approval by the Executive Officer to identify urban,industrial and domestic sources of 5 organochlorine pesticides and polychlorinated biphenyls POTW Permittees,MS4 1 year after effective date and control methods and to implement a collection and Permittees,US Navy of the amendment disposal program for organochlorine pesticides and polychlorinated biphenyls. Submit a workplan for approval by the Executive Officer to 6 identify agricultural sources and methods to implement a Agricultural Dischargers 1 year after effective date collection and disposal program for organochlorine of the amendment pesticides and polychlorinated biphenyls. Special Study#1 —Submit a workplan and convene a Science Advisory Panel to quantify sedimentation in Mugu Lagoon and sediment transport throughout the Calleguas Creek Watershed. Evaluate management methods to control siltation and contaminated sediment transport to Calleguas Creek,identify appropriate BMPs to reduce sediment loadings,evaluate numeric targets and wasteload and load allocations for siltation/sedimentation to support POTW Permittees,MS4 1 year after effective date 7 habitat related beneficial uses in Mugu Lagoon, evaluate Permittees,Agricultural of the amendment the effect of sediment on habitat preservation in Mugu Dischargers,and US Navy Lagoon,and evaluate appropriate habitat baseline, effectiveness of sediment and siltation load allocations on a subwatershed basis,and methods to restore habitat for approval by the Executive Officer. Additionally,this special study will evaluate the concentration of organochlorine pesticides and polychlorinated biphenyls in sediments from various sources/land use t es.2 Page 13 July 7, 2005 Attachment A to Resolution No. 114-2005-010 tgm". lmplemeuttt Actiirn y Respansbl k G�tpleon i7aie Develop an Agricultural Water Quality Management Plan in consideration of the forthcoming Conditional Waiver for Irrigated Lands,or,if the Conditional Waiver for Irrigated 9 Lands is not adopted in a timely manner,develop an Agricultural Dischargers 3 years after effective date Agricultural Water Quality Management Plan as part of the of the amendment Calleguas Creek WMP. Implement an educational program on BMPs identified in the Agricultural Water Quality Management Plan. Based on results of the Task 5 workplan approved by 10 Executive Officer,implement a collection and disposal POTW Permittees,MS4 5 years after effective of program for organochlorine pesticides and polychlorinated Permittees,US Navy the amendment bi hen ls. Based on results of the Task 6 workplan approved by 11 Executive Officer implement a collection and disposal Agricultural Dischargers 5 years after effective of program for organochlorine pesticides and polychlorinated the amendment bi hen ls. Re-evaluation of POTW Interim wasteload allocations for 5 years, 10 years and 15 12 organochlorine pesticides and polychlorinated biphenyls Regional Board years after the effective based on State Implementation Plan procedures. date of the amendment Special Study#1—Submit results of Special Study#1, POTW Permittees,MS4 g years after effective date 13 including recommendations for refining the siltation load Permittees,Agricultural of the amendment and wasteload allocations. Dischargers,and US Navy 14 Re-evaluation of siltation and sediment load and wasteload Regional Board 9 years after effective date allocations based on S ecial Stud #1. of the amendment 15 Effective date of siltation load allocation and wasteload Agricultural dischargers, 9 years after effective date allocation. US Navy,MS4 permittees of the amendment Special Study#3—Evaluate natural attenuation rates and POTW Permittees, evaluate methods to accelerate organochlorine pesticide Agricultural Dischargers, 10 years after effective date 16 and polychlorinated biphenyl attenuation and examine the MS4 Permittees,and US of the amendment attainability of wasteload and load allocations in the Calle uas Creek Watershed.2,3 Navy Special Study#4(optional) Examine of the food web and bioconcentration relationships throughout the watershed to 12 years after effective date 17 evaluate assumptions contained in the Linkage Analysis and Interested Parties of the amendment ensure that protection of beneficial uses is achieved.z Based on the results of Implementation Items 1-17,if sediment guidelines are promulgated or water quality criteria are revised,and/or if fish tissue and water column 10 years after effective date 18 targets are achieved without attainment of WLAs or LAs, Regional Board of the amendment the Regional Board will consider revisions to the TMDL targets,allocations, and schedule for expiration of Interim Wasteload and Interim Load Allocations.3 Agricultural Dischargers, 20 years after effective date 19 Achieve Final WLAs and LAs POTW Permittees,and of the amendment MS4 Permittees Page 14 July 7, 2005 Attachment A to Resolution No. R4-2005-010 The Regional Board regulatory programs addressing all discharges in effect at the time an implementation task is due may contain requirements substantially similar to the requirements of an implementation task. If such a requirement is in place in another regulatory program including other TMDLs,the Executive Officer may determine that such other requirements satisfy the requirements of an implementation task of this TMDL and thereby coordinate this TMDL implementation plan with other regulatory programs. V 'Special studies included in the Implementation Plan are based on the TMDL Technical Documents. 3 After completion of this special study,the TMDL will be reopened in order to enable the Regional Board to evaluate whether a shorter time period is appropriate for the achievement of the final WI-As and LAs. Page 15 July 7, 2005 Appendix B Attachment 3 : Toxicity, Chlorpyrifos, and Diazinon in the Calleguas Creek, its Tributaries and Mugu Lagoon Basin Plan Amendment Attachment A to Resolution No. 114-2005-009 Amendment to the Water Quality Control Plan—Los Angeles Region to Incorporate the Total Maximum Daily Load for Toxicity, Chlorpyrifos,and Diazinon in the Calleguas Creek,its Tributaries and Mugu Lagoon Adopted by the California Regional Water Quality Control Board, Los Angeles Region on 7 July, 2005. Amendments Table of Contents Add: Chapter 7. Total Maximum Daily Loads (TMDLs) 7- Calleg as Creek Watershed Toxicity TMDL List of Figures,Tables, and Inserts Add: Chapter 7. Total Maximum Daily Loads (TMDLs) Tables 7-16 Calleguas Creek Watershed Toxicity TMDL 7-16.1. Calleguas Creek Watershed Toxicity TMDL: Elements 7-16.2. Calleguas Creek Watershed Toxicity TMDL: Implementation Schedule Chapter 7. Total Maximum Daily Loads (TMDLs) Calleguas Creek Watershed Toxicity TMDL This TMDL was adopted by: The Regional Water Quality Control Board on July 7, 2005. This TMDL was approved by: The State Water Resources Control Board on September 22, 2005. The Office of Administrative Law on December 22, 2005. The U.S. Environmental Protection Agency on March 14, 2006. July 7, 2005 Resolution No. R4-2005-009 Page 2 Table 7-16.1. Calleguas Creek Watershed Toxicity TMDL: Elements TMIDL Element 'Calleguas Creek Watershed Toxicity TMDL Problem Discharge of wastes containing chlorpyrifos, diazinon, other Statement pesticides and/or other toxicants to Calleguas Creek,its tributaries and Mugu Lagoon cause exceedances of water quality objectives for toxicity established in the Basin Plan. Elevated levels of chlorpyrifos have been found in fish tissue samples collected from a segment of Calleguas Creek. Chlorpyrifos and diazinon are organophosphate pesticides used in both agricultural and urban settings. Excessive chlorpyrifos and diazinon can cause aquatic life toxicity in inland surface and estuarine waters such as Calleguas Creek and Mugu Lagoon. The California 2002 303(d)list of impaired waterbodies includes listings for"water column toxicity," "sediment toxicity," chlorpyrifos in fish tissue," and "organophosphate pesticides in water" for various reaches of Calleguas Creek, its tributaries and Mugu Lagoon. Numeric Targets This TMDL establishes a numeric toxicity target of 1.0 toxicity unit —chronic (1.0 TUc) to address toxicity in reaches where the toxicant has not been identified through a Toxicity Identification Evaluation (TIE) (unknown toxicity). TUB =Toxicity Unit Chronic = 100/NOEC (no observable effects concentration) A sediment toxicity target was defined in the technical report for reaches where the sediment toxicant has not been identified through a TIE. The target is based on the definition of a toxic sediment sample as defined by the September 2004 Water Quality Control Policy For Developing California's Clean Water Act Section 303(d) List(SWRCB). Chlorpyrifos Numeric Targets (ug/L) Chronic Acute (4 day average) (1 hour average) Freshwater 0.014 0.025 Saltwater(Mugu Lagoon) 0.009 0.02 Diazinon Numeric Targets (ug/L) Chronic Acute (4 day average) (1 hour average) Freshwater 0.10 0.10 Saltwater(Mugu Lagoon) 0.40 0.82 July 7, 2005 Resolution No. R4-2005-009 Page 3 TMDL Element Calleguas Creek`Watershed Toxicity TMDL Additionally, the diazinon criteria selected as numeric targets are currently under review by the USEPA. If water quality objectives become available, the Regional Board may reconsider this TMDL and revise the water toxicity numeric target. Source Analysis Source analysis determined that agricultural and urban uses are the largest sources of chlorpyrifos and diazinon in the watershed. Urban use of diazinon and chlorpyrifos is unlikely to be a long-term source to the Calleguas Creek Watershed (CCW) as both of these pesticides have been banned for sale for non-agricultural uses on December 31, 2005 by federal regulation. As a result, the proportion of the loading from urban sources will likely decrease after December 2005. Chlorpyrifos—Sources by Use Dry Weather Wet Weather Agriculture 66% 80% Urban 23% 20% POTW 11% <1% Other <1% <1% Diazinon—Sources by Use Dry Weather Wet Weather Agriculture 30% 1% Urban 13% 62% POTW 57% 37% Other <1% <1% Linkage Analysis Water quality modeling established the linkage of sources of chlorpyrifos and diazinon in the CCW to observed water quality data. The linkage analysis qualitatively describes the connection between water column concentrations and sediment and fish tissue concentrations. The qualitative analysis demonstrates that the water column analysis conducted by laboratories implicitly includes sediment associated diazinon and chlorpyrifos loads transported to receiving waters as almost all water quality data do not differentiate between dissolved and particulate fractions. The linkage analysis assumes a reduction in water column concentrations will result in a reduction in fish tissue as chlorpyrifos in freshwater fish tissue rapidly depurate within several days of removal from exposure. Additionally, as chlorpyrifos preferentially binds to sediment the linkage analysis suggests that sediment concentrations of July 7, 2005 Resolution No. R4-2005-009 Page 4 TMDL Element Calleguas Creek Watershed Toxicity TMDL chlorpyrifos will need to decrease to achieve water quality numeric targets. The modeling approach reflects the uncertainty in current conditions and the potential impacts of watershed planning actions that may affect those conditions. A detailed description of the model is provided in an Attachment to the TMDL Technical Report. Wasteload Ma_ior point sources: Allocations (WLA) A wasteload of 1.0 TU,is allocated to the major point sources (POTWs) discharging to the Calleguas Creek Watershed. Additionally, the following wasteloads for chlorpyrifos and diazinon are established for POTWs. A margin of safety of 5% was included in the targets for chlorpyrifos for discharges to the Calleguas and Revolon subwatersheds. Chlorpyrifos WLAs, ug/L POTW Interim WLA Final WLA (4 day) (4 day) Hill Canyon WWTP 0.030 0.014 Simi Valley WQCP 0.030 0.014 Ventura County (Moorpark)WTP 0.030 0.014 Camarillo WRP 0.030 0.0133 Camrosa WRP 0.030 0.0133 Diazinon WLAs,uWL Interim Interim Final WLA Acute Chronic (Acute or Chronic) (1 hour) (4 day) POTW Hill Canyon WWTP 0.567 0.312 0.10 Simi Valley WQCP 0.567 0.312 0.10 Ventura County (Morepark)WTP 0.567 0.312 0.10 Camarillo WRP 0.567 0.312 0.10 Camrosa WRP 0.567 0.312 0.10 A wasteload of 1.0 TU,is allocated to Urban Stormwater Co- Permittees (MS4) discharges to the Calleguas Creek Watershed. July 7, 2005 Resolution No. R4-2005-009 Page 5 TMDL Element Calle guas Creek Watershed Toxicity TMDL Additionally, the following wasteloads for chlorpyrifos and diazinon are established for MS4 discharges. Chlorpyrifos WLAs, uy,/L Interim WLA Final WLA (4 day) (4 day) 0.45 0.014 Diazinon WLAs,ug/L Interim WLA Interim WLA Final WLA Acute(1 hour) Chronic(4 day) Acute and Chronic 1.73 0.556 0.10 Minor point sources: Minor sources include NPDES permittees other than POTWs and MS4s, discharging to the Calleguas Creek Watershed. A wasteload of 1.0 TU,is allocated to the minor point sources discharging to the Calleguas Creek Watershed. Additionally, the following wasteloads for chlorpyrifos and diazinon are established. Chlorpyrifos WLAs,ug/L Interim WLA Final WLA (4 day) (4 day) 0.45 0.014 Diazinon WLAs,ug/L Interim WLA Interim WLA Final WLA Acute(1 hour) Chronic(4 day) Acute and Chronic 1.73 0.556 0.10 Load Allocations Non Point Source Dischargers: A load of 1.0 TUB is allocated to nonpoint sources discharging to the Calleguas Creek Watershed. July 7, 2005 Resolution No. R4-2005-009 Page 6 TMDL Element Calleguas Creek Watershed Toxicity TMDL Additionally, the following loads for chlorpyrifos and diazinon are established. These loads apply to dischargers in accordance with the subwatershed into which the dischargers discharge. A margin of safety of 5% was included for chlorpyrifos for discharges to the Calleguas and Revolon subwatersheds. Chlorpyrifos Load Allocations,uWL Interim Interim Final Subwatershed Acute(I hour) Chronic(4 day) Acute and Chronic Arroyo Simi 2.57 0.810 0.014 Las Posas 2.57 0.810 0.014 Conejo 2.57 0.810 0.014 Calleguas 2.57 0.810 0.0133 Revolon 2.57 0.810 0.0133 Mugu Lagoon 2.57 0.810 0.014 Diazinon Load Allocations,uWL Interim LA Interim LA Final LA Acute Chronic Acute and Chronic 0.278 0.138 0.10 Margin of Safety In addition to the implicit margin of safety achieved by conservative assumptions and by using a concentration based TMDL, an explicit margin of safety of 5% has been added to the targets for chlorpyrifos in the Calleguas and Revolon subwatersheds to address uncertainty in the linkages between the water column criteria and fish tissue and sediment concentrations. The Calleguas and Revolon subwatersheds include those reaches listed for sediment toxicity and chlorpyrifos in fish tissue. Future Growth Ventura County accounts for slightly more than 2% of the state's residents with a population of 753,197 (US Census Bureau, 2000). GIS analysis of the 2000 census data yields a population estimate of 334,000 for the CCW, which equals about 44% of the county population. According to the Southern California Association of Governments (SCAG), growth in Ventura County averaged about 51% per decade from 1900-2000; with growth exceeding 70% in the 1920s, 1950s, and 1960s. The phase-out of chlorpyrifos and diazinon is expected to reduce loads from urban and POTWs significantly by 2007. Use of diazinon in agriculture has declined considerably between 1998 and 2003. Conversely, chlorpyrifos use July 7, 2005 Resolution No. R4-2005-009 Page 7 TMDL Element Calle uas Creek Watershed Toxicity TMDL in agriculture has remained relatively stable over the same period. The phase out of chlorpyrifos and diazinon as well as population growth will cause an increase in the use of replacement pesticides (e.g. pyrethroids)in the urban environment and may have an impact on water and/or sediment toxicity. Additionally,population growth may affect an increase in the levels of chlorpyrifos and diazinon loading in the CCW from imported products which contain residues of these pesticides. Critical The critical condition in this TMDL is defined as the flowrate at Conditions which the model calculated the greatest in-stream diazinon or chlorpyrifos concentration in comparison to the appropriate criterion. The critical condition for chlorpyrifos was in dry weather based on a chronic numeric target; the critical condition for diazinon was in wet weather based on an acute numeric target except in Mugu Lagoon where it was in dry weather based on the chronic numeric target. Implementation WLAs established for the major points sources, including POTWs Plan in the CCW will be implemented through NPDES permit effluent limits. The final WLAs will be included in NPDES permits in accordance with the compliance schedules provided. The Regional Board may revise these WLAs based on additional information as described in the Special Studies and Monitoring Section of the Technical Report. The toxicity WLAs will be implemented in accordance with US EPA, State Board and Regional Board resolutions, guidance and policy at the time of permit issuance or renewal. Currently, these WLAs would be implemented as a trigger for initiation of the TRE/TIE process as outlined in USEPA's `Understanding and Accounting for Method Variability in Whole Effluent Toxicity Applications Under the National Pollutant Discharge Elimination System Program"(2000) and current NPDES permits held by dischargers to the CCW. Stormwater WLAs will be incorporated into the NPDES permit as receiving water limits measured in-stream at the base of each subwatershed and will be achieved through the implementation of BMPs as outlined below. Evaluation of progress of the TMDL will be determined through the measurement of in-stream water quality and sediment at the base of each of the CCW subwatersheds. The Regional Board may revise these WLAs based on additional information developed through special studies and/or monitoring conducted as part of the TMDL. July 7, 2005 Resolution No. R4-2005-009 Page 8 TMDL Element Calle as Creek Watershed Toxicit',TMDL As shown in the attached table the following implementation actions will be taken by the MS4s discharging to the CCW and POTWs located in the CCW: • Plan, develop, and implement an urban pesticides public education program; • Plan, develop, and implement urban pesticide education and chlorpyrifos and diazinon collection program; • Study diazinon and chlorpyrifos replacement pesticides for use in the urban environment; and, • Conduct environmental monitoring as outlined in the Monitoring Plan and NPDES Permits. LAs for chlorpyrifos and diazinon will be implemented through the State's Nonpoint Source Pollution Control Program(NPSPCP), nonpoint source pollution (i.e. Load Allocations). The LARWQCB is currently developing a Conditional Waiver for Irrigated Lands. Once adopted,the Conditional Waiver Program will implement allocations and attain numeric targets of this TMDL. Compliance with LAs will be measured at the monitoring sites approved by the Executive Officer of the Regional Board through the monitoring program developed as part of the Conditional Waiver, or through a monitoring program that is required by this TMDL. The toxicity LAs will be implemented in accordance with US EPA, State Board and Regional Board resolutions, guidance and policy at the time of permit or waiver issuance or renewal. The following implementation actions will be taken by agriculture dischargers located in the CCW: • Enroll for coverage under a waiver of waste discharge requirements for irrigated lands; • Implement monitoring required by this TMDL and the Conditional Waiver program; 4. Complete studies to determine the most appropriate BMPs given crop type,pesticide, site specific conditions, as well as the critical condition defined in the development of the LAs; and, .� Implement appropriate BMPs and monitor to evaluate effectiveness on in-stream water and sediment quality. The Regional Board may revise this TMDL based on monitoring data and special studies of this TMDL. If the Regional Board revises NPDES permits or the Basin Plan to use other methods of July 7, 2005 Resolution No. R4-2005-009 Page 9 TMDL Element Calle uas Creek Watershed Toxicity TMDL evaluating toxicity or if other information supporting other methods becomes available, the Regional Board may reconsider this TMDL and revise the water toxicity numeric target. Additionally, the development of sediment quality guidelines or criteria and other water quality criteria revisions may call for the reevaluation of the TMDL. The Implementation Plan includes this provision for reevaluating the TMDL to consider sediment quality guidelines or criteria and revised water quality objectives and the results of im lementation studies, if appropriate. July 7, 2005 Resolution No. R4-2005-009 Page 10 Table 7-16.2. Overall Implementation Schedule for Calleguas Creek Watershed Toxicity TMDL Implementation Action Responsible Date Part Interim chlorpyrifos and diazinon waste-load allocations POTW permittees z 1 i and MS4 Effective date apply. Copermittees 2 Interim chlorpyrifos and diazinon load allocations apply.' Agricultural Effective date Dischargers Finalize and submit workplan for integrated Calleguas POTW permittees, 3 Creek Watershed Monitoring Program for approval by MS4 Copermittees, 6 months afterzeffective date the Regional Board Executive Officer.3 and Agricultural of amendment Dischargers POTW permittees, 6 months after E.O. Initiate Calleguas Creek Watershed Toxicity TMDL MS4 Copermittees, 4 Monitoring Program developed under Task 3 workplan. and Agricultural approval of Monitoring Program(task 3)workplan. Dischargers Special Study#1 - Investigate the pesticides that will POTW permittees replace diazinon and chlorpyrifos in the urban 2 5 and MS4 2 years after effective date environment,their potential impact on receiving waters, Copermittees and potential control measures. Special Study#2— Consider results of monitoring of 6 months after completion sediment concentrations by source/land use type through Agricultural of CCW OC Pesticides, special study required in the OC Pesticide,PCB and 3 6 Dischargers and PCBs and Siltation TMDL siltation TMDL Implementation Plan. If the special study MS4 Copermittees sediment concentrations is not completed through the OC Pesticides,PCBs and 2 Siltation TMDL no consideration is necessary 3 special study. Develop and implement collection program for diazinon POTW permittees 7 and chlorpyrifos and an educational program. Collection and MS4 3 years after effective date and education could occur through existing programs Copermittees such as household hazardous waste collection events Develop an Agricultural Water Quality Management Plan in conjunction with the Conditional Waiver for Irrigated Agricultural 2 8 Lands,or(if the Conditional Waiver is not adopted in a Dischargers3 3 years after effective date timely manner)develop an Agricultural Water Quality Management Plan as part of the Calleguas Creek WMP. Identify the most appropriate BMPs given crop type, Agricultural 2 9 pesticide,site specific conditions,as well as the critical Dischargers 3 years after effective date condition defined in the development of the LAs. 10 Implement educational program on BMPs identified in Agricultural I year after E.O. approval of the Agricultural Water Quality Management Plan. Dischar ers Plan(Task 7) Special Study#3 Calculation of sediment transport rates Agricultural 6 months after completion 11 in CCW. Consider findings of transport rates developed Dischargers3 and of CCW OC Pesticides, through the OC Pesticide,PCB and siltation TMDL MS4 Copermittees PCBa and Siltation TMDL 'Interim WLAs and LAs are effective immediately upon TMDL adoption. WLAs will be placed in POTW NPDES permits as effluent limits. WLAs will be placed in stormwater NPDES permits as in-stream limits. LAs will be implemented using applicable regulatory mechanisms. 2 Effective date of this TMDL. 3 The Regional Board regulatory programs addressing all discharges in effect at the time an implementation task is due may contain requirements substantially similar to the requirements of an implementation task. If such a requirement is in place in another regulatory program including other TMDLs,the Executive Officer may determine that such other requirements satisfy the requirements of an implementation task of the TMDL and thereby coordinate this TMDL implementation plan with other regulatory programs. July 7, 2005 Resolution No. R4-2005-009 Page 11 Responsible Implementation Action Party Date Implementation Plan. If the special study is not sediment transport special completed through the OCsTMDL,no consideration is study.2 necessary.3 Agricultural 1 year after E.O. approval of 12 Begin implementation of BMPs. Dischargers 3 Plan(Task 8)' Agricultural 3 years after E.O. approval 13 Evaluate effectiveness of BMPs. Dischargers 3 of Plan(Task 8)2 Based on monitoring data and on the results of Stakeholders and Implementation Actions 1-13 and if sediment guidelines Regional Board are promulgated,or water quality criteria are revised, 2 years after the submittal of 14 and/or if targets are achieved without attainment of information necessary to WLAs or LAS reevaluate the TMDLs,interim or final reevaluate the TMDL WLAs and LAS and implementation schedule,if necessary. POTW permittees 2 years after the effective 15 Achievement of Final WLAs and MS4 date of the TMDL2 Co ermittees 16 Achievement of Final LAS Agricultural 10 years after the effective Dischargers date of the TMDL July 7, 2005 Appendix C Supporting Documents for Field Procedures Appendix C Attachment 1 : Ambient Water Sampling SOP Ambient Water Sampling Standard Operating Procedures Version Date 07/20/06 Monitoring Event Preparation Monitoring event preparation includes preparation of field equipment, placing bottle orders, and contacting the necessary personnel regarding site access and schedule. The following steps shall be completed two weeks prior to each sampling event: 1. Contact laboratories to order bottles and to coordinate sample transportation details. 2. Confirm scheduled monitoring date with field crew(s), and set-up sampling day itinerary including sample drop-off. 3. Prepare equipment(see Table 1). 4. Prepare container labels and apply to containers. 5. Prepare the monitoring event summary and field log sheets to indicate the type of field measurements, field observations and samples to be collected at each of the stations. 6. Verify that field measurement equipment is functioning properly(i.e., check batteries, calibrate, etc.) Table 1 provides a checklist of field equipment to prepare prior to each sampling event. Table 1.Field Equipment Checklist X Project QAPP X Tape Measure X Peristaltic Pump X Sample Containers plus Extras X Paper Towels or Rags in X Extra Pump Batteries with Extra Lids a Box X Pre-Printed and Extra Labels X Safety Equipment X 1 length of Clean Tubing per S ite X Event Summary Sheets X First Aid Kit (including calibration logs) X Field Log Forms X Cellular Telephone X Chain of Custody Forms X Gate Keys X Bubble Wrap X Hip Waders X Coolers w/Ice X Plastic Trash Bags New Powder-Free Nitrile Distilled/DI Wash X Gloves X Bottles X Pens X Blank Water X Watch X Sealable Plastic Bags X Field Measurement Equipment X Grab Pole and Calibration Standards X Camera X Clean Secondary Container(s) Monitoring Event Summary and Post Event Summary A monitoring event summary sheet shall be produced for the sampling crew prior to each sampling event. The event summary sheet shall outline sampling requirements at each monitoring site, including a list of samples to be collected and quality control(QC) sample collection requirements. This summary will act as a guide to help field crews Ambient Water Sampling 1 July 2006 Standard Operating Procedures prepare for and track sample collection during each event. Additionally, the event summary sheet will list required containers and processing and storage requirements. A post monitoring event summary report will be produced by the field crew subsequent to each monitoring event. This summary will serve as a guide for quality assurance personnel to qualify data. The post event summary will contain chain-of-custody (COC) forms submitted with samples and field log sheets. Bottle Order/Preparation Sample container orders will be placed with the appropriate analytical laboratory at least two weeks prior to each sampling event. Containers will be ordered for all water samples, including quality control samples, as well as extra containers in case the need arises for intermediate containers or a replacement. The containers must be the proper type and size and contain preservative as appropriate for the specified laboratory analytical methods. The field crew must inventory sample bottles upon receipt from the laboratory to ensure that adequate bottles have been provided to meet analytical requirements for each monitoring event. After each event, any bottles and tubing used to collect water samples will be cleaned by the laboratory and either picked up by or shipped to the field crew. Sample Bottle Labeling All samples will be pre-labeled before each sampling event to the extent practicable. Pre- labeling sample bottles and jars simplifies field activities, leaving only sample collection time and date and field crew initials to be filled out in the field. Custom labels will be produced using blank water-proof labels. This approach will allow the stations and analytical constituent information to be entered in advance and printed as needed prior to each monitoring event. Labels will be applied to the appropriate sample containers in a dry environment, as labels usually do not adhere to wet bottles. The labels will not be applied to container caps. Field labels shall contain the following information: • Program Name • Date • Analytical Requirements • Station ID • Time • Preservation Requirements • Sample ID • Sampling • Laboratory Conducting Personnel Analysis Sample Collection Sampling Technique Samples will be collected in a manner that minimizes the possibility of sample contamination. These sampling techniques are summarized below: • Samples are collected only into rigorously pre-cleaned sample bottles. • At least two persons,wearing clean powder-free nitrile gloves at all times, are required on a sampling crew. Ambient Water Sampling 2 July 2006 Standard Operating Procedures • Clean, powder-free nitrile gloves are changed whenever something not known to be clean has been touched. • To reduce the potential for contamination, sample collection personnel must adhere to the following rules while collecting samples: 1. No smoking. 2. Never sample near a vehicle, running or otherwise. 3. During wet weather events avoid allowing rain water to drip from rain gear or any other surface into sample bottles. 4. Do not eat or drink during sample collection. 5. Do not breathe, sneeze or cough in the direction of an open sample bottle. Water Sample Collection Grab samples will be collected at approximately mid-stream, mid-depth at the location of greatest flow (where feasible)by direct submersion of the sample container. This is the preferred method for grab sample collection. However, due to sampling station configurations and safety concerns, direct filling of sample containers may not always be feasible, especially during wet events. Monitoring station configuration will dictate grab sample collection technique. Grab samples will be collected directly into the appropriate containers as outlined in the Project QAPP. The grab sample techniques that may be employed are described below. Direct Submersion: Hand Technique Where practical, all grab samples will be collected by direct submersion at mid-stream, mid-depth using the following procedures. 1. Wear clean powder-free nitrile gloves when handling bottles and lids. Change gloves if soiled or if the potential for cross-contamination occurs from handling sampling materials or samples. 2. Use pre-labeled sample containers as described in the Sample Bottle Labeling section. 3. Remove lid, submerge bottle to mid-stream/mid-depth, let bottle fill, and replace lid. 4. Place sample on ice. 5. Collect remaining samples including quality control samples, if needed,using the same protocols described above. 6. Fill out COC form, note sample collection on field form, and deliver to appropriate lab. Intermediate Container Technique Samples for which the introduction of a secondary container is acceptable, and which will be collected from an open channel, may be collected with the use of a specially cleaned intermediate container following the steps listed below. A secondary container could include a container of similar composition to the sample container or a pre-cleaned pitcher of the same material as the sample container. Ambient Water Sampling 3 July 2006 Standard Operating Procedures 1. Wear clean powder-free nitrile gloves when handling bottles and lids. Change gloves if soiled or if the potential for cross-contamination occurs from handling sampling materials or samples. 2. Use pre-labeled sample containers as described in the Sample Bottle Labeling section. 3. Submerge intermediate container to mid-stream/mid-depth, let container fill, and pour off into individual sample bottles. 4. Place sample on ice. 5. Collect remaining samples including quality control samples, if needed, using the same protocols described above. 6. Fill out COC form, note sample collection on field form, and deliver to appropriate lab. Pumping Samples for which the use of a peristaltic pump is acceptable and/or necessary because of sampling station configuration, and which will be collected from an open channel, may be collected with the use of a peristaltic pump and specially cleaned tubing following the steps listed below. Pumping may not be used to collect samples analyzed for ammonia. 1. Wear clean powder-free nitrile gloves when handling bottles, lids, and pump tubing. Change gloves if soiled or if the potential for cross-contamination occurs from handling sampling materials or samples. 2. Use pre-labeled sample containers as described in the Sample Bottle Labeling section. 3. Insert pre-cleaned tubing into the pump using"clean sampling techniques". New clean tubing must be used at each sample location for which the pump is used. 4. Place one end of the tubing below the surface of the water. To the extent possible, avoid placing the tubing near the bottom of the channel so that settled solids are not pumped into the sample container. 5. Hold the other end of the tubing over the opening of the sample container. Be careful not to touch the tubing to the sample container. 6. Pump the necessary sample volume into the sample container. 7. Place sample on ice. 8. Collect remaining samples including quality control samples, if needed, using the same protocols described above. 9. Fill out COC form, note sample collection on field form, and deliver to appropriate lab. Field Measurements and Observations Field measurements required by the Project QAPP will be collected and observations made at each sampling station after a sample is collected. Field measurements typically include flow, pH, temperature, dissolved oxygen, and conductivity. Temperature, pH, dissolved oxygen, and conductivity measurements will be collected at approximately mid-stream, mid-depth at the location of greatest flow(if feasible). Field probes shall be lowered to mid-depth and readings recorded on the field log for that station. All field Ambient Water Sampling 4 July 2006 Standard Operating Procedures measurement results and comments on field observations will be recorded on a field log. Flow measurements will be collected using a velocity meter or estimated at each sampling station after a sample is collected. When a velocity meter is unavailable or flow is not sufficiently deep to use a velocity meter, depth, width, and velocity will be estimated to provide an estimate of flow. Depth will be estimated by using the average of several depth measurements taken along the channel. Width will be measured by extending a tape measure from one side of the bank to the other. Velocity will be estimated by measuring the time it takes a floating object(e.g., stick, orange)to travel a known distance. If at any time the collection of field measurements by wading appears to be unsafe, field crews will not attempt to collect mid-stream, mid-depth measurements. Rather, field measurements will be made either directly from a stable, unobstructed area at the channel edge, or by using a telescoping pole and intermediate container to obtain a sample for field measurements and for filling sample containers. In addition to field measurements, observations shall be made at each sampling station. Observations will include color, odor, floating materials as well as observations of contact and non-contact recreation. All comments on field observations will be recorded on a field log sheet. Field Protocols Field crews (2 persons per crew, minimum)will only be mobilized for sampling when weather conditions and flow conditions are considered to be safe. For safety reasons, sampling will be scheduled to occur during daylight hours,when possible. Sampling events will proceed in the following manner: 1. Before leaving the base of operations, confirm number and type of sample bottles as well as the complete equipment list. 2. Proceed to the first monitoring site. 3. Record the general information on the field log sheet. 4. Collect the samples indicated on the event summary sheet in the manner described in the Project QAPP. Collect additional volume and blank samples for field- initiated Quality Control (QC) samples as necessary. Place filled sample containers in coolers and carefully pack and ice samples as described in the Project QAPP. Using the log sheet, confirm that all appropriate bottles were filled. 5. Collect field measurements and observations, and record on the field log sheet. 6. Repeat the procedures in steps 3, 4, and 5 for each of the remaining monitoring sites. 7. Complete the chain of custody forms using the field log sheets. 8. After sample collection is completed, deliver and/or ship samples to appropriate laboratory on the same day as sample collection. Ambient Water Sampling 5 July 2006 Standard Operating Procedures Appendix C Attachment 2: Freshwater Sediment Sampling SOP Freshwater Sediment Sampling Standard Operating Procedures Version Date 07/20/06 Sampling Event Preparation Sample event preparation includes preparation of field equipment, placing bottle orders, and contacting the necessary personnel regarding site access and schedule. The following steps shall be completed two weeks prior to each sampling event: 1. Contact laboratories to order jars and to coordinate sample transportation details. 2. Confirm scheduled sampling date with field crew, and set-up sampling day itinerary including sample drop-off. 3. Prepare equipment(see Table 1). 4. Prepare sample labels and apply to jars. 5. Prepare the sampling event summary and field log sheet to indicate the type of field measurements, field observations and samples to be taken at each of the stations. 6. Calibrate field measurement equipment. Table 1 provides a checklist of field equipment to prepare prior.to each sampling event. Table 1.Field Equipment Checklist • Project QAPP X Camera X 4-mil Poly Bags • Sample Bottles and Jars w/ X Tape Measure X Stainless Steel Sampling and Pre-Printed and Extra Labels Mixing Spoons • Event Summary Sheets X Paper Towels or Rags in X Stainless Steel Mixing Bowl (including calibration logs) a Box • Field Log Forms X Safety Equipment • Chain of Custody Forms X First Aid Kit • Bubble Wrap X Cellular Telephone • Coolers w/Ice X Gate Keys • New Powder-Free Nitrile X Hip Waders Gloves • Pens X Plastic Trash Bags • Watch X Distilled/DI Wash Bottles X Field Measurement Equipment X Blank Water and Calibration Standards Sampling Event Summary and Post Event Summary A sampling event summary sheet shall be produced for the sampling crew prior to each sampling event. The event summary sheet shall outline sampling requirements at each sampling station, including a list of samples to be collected and QA/QC requirements. This summary will act as a guide to help field crews prepare for and track sample collection during each event. A post sampling event summary will be produced by the sampling crew subsequent to each sampling event. This summary will act as a guide for quality assurance personnel to Ambient Sediment Sampling 1 July 2006 Standard Operating Procedures qualify data. The post event summary will contain: chain-of-custody (COC) forms submitted with samples and field log sheets. Bottle Order/Preparation Sample bottle orders will be placed with the appropriate analytical laboratory at least two weeks prior to each sampling event. Bottles and jars will be ordered for all water and sediment samples, including quality control samples as well as extra bottles in case of a need for intermediate containers or replacement. The bottles must be the proper size and material, and contain preservatives as appropriate for the specified laboratory analytical methods. The field crew must inventory sample bottles upon receipt from the laboratory to assure that adequate bottles have been provided to meet analytical requirements for each sampling event. After each sampling event, any bottles and tubing used to collect water samples and the equipment used for collecting sediment samples shall be cleaned by the laboratory and either picked up by or shipped to the sampling crew. Sample Bottle Labeling All samples will be pre-labeled before each sampling event to the extent practicable. Pre- labeling sample bottles and jars simplifies field activities; leaving only sample collection time and date, and the names of sampling personnel to be filled out in the field. Custom labels will be produced using blank water-proof labels. This approach will allow the stations and analytical constituent information to be entered into the computer program in advance, and printed as needed prior to each sampling event. Labels shall be applied to the appropriate bottles and jars in a dry environment; attempting to apply labels to sample bottles after filling may cause problems, as labels usually do not adhere to wet bottles. The labels shall be applied to bottles and jars rather than to the caps. Field labels shall contain the following information: • Program Name • Date • Analytical Requirements • Station ID • Time • Preservation Requirements • Sample ID • Sampling • Laboratory Conducting Personnel Analysis Sample Collection Sampling Technique Samples will be collected in a manner that minimizes the possibility of sample contamination. These sampling techniques are summarized below: • Samples are collected only into rigorously pre-cleaned sample bottles. • At least two persons, wearing clean powder-free nitrile gloves at all times, are required on a sampling crew. • Clean, powder-free nitrile gloves are changed whenever something not known to be clean has been touched. Ambient Sediment Sampling 2 July 2006 Standard Operating Procedures • To reduce the potential for contamination, sample collection personnel must adhere to the following rules while collecting samples: 1. No smoking. 2. Never sample near a vehicle, running or otherwise. 3. During wet weather events avoid allowing rain water to drip from rain gear or any other surface into sample bottles. 4. Do not eat or drink during sample collection. 5. Do not breathe, sneeze or cough in the direction of an open sample bottle. Sediment Sample Collection Collection of in-stream sediment samples for chemical analysis and toxicity testing shall be conducted according to methods developed by the USGS and outlined in Guidelines for Collecting and Processing Samples of Stream Bed Sediment for Analysis of Trace Elements and Organic Contaminants for the National Water Quality Assessment Program (1994). Sediment sampling stations will encompass a section of the reach approximately 100 meters in length upstream from water-column sampling stations. However,this definition may vary based on conditions at each sampling station. Sediment sampling stations should contain 5 to 10 wadeable depositional zones. Depositional zones are defined as locations in streams where the energy regime is low and fine-grained particles accumulate in the stream bed. Depositional zones include areas on the inside bend of a stream or areas downstream from obstacles such as boulders, islands, sand bars, or simply shallow waters near the shore. The purpose of selecting numerous wadeable depositional zones is to collect a representative sample of each reach. Each depositional zone identified at a sampling station shall be subsampled several times and composited in the field for chemical analysis, or at the lab for toxicity analysis. The number of subsamples collected at each depositional zone shall be based on the size of the zone. If all of the depositional zones within a reasonable distance of the water sampling station have dried, samples should be collected from a partially wetted zone. Wetted zones include areas near the active stream channel. Sediment samples will be collected using pre-cleaned stainless steel trowels from the top two to three centimeters (cm)of sediment. Collection of sediments in the top two to three cm is a common approach to conducting sediment sampling to conduct sediment toxicity testing. This approach was used in sediment toxicity studies conducted by the Southern California Coastal Water Research Project(SCCWRP)Bight Program and the State Water Resources Control Board Bay Protection and Toxic Cleanup Program (BPTCP), which led to the sediment toxicity listing in the lagoon. All sediment samples to be analyzed for organic constituents shall be collected as composite samples as described below. Sediment samples analyzed for toxicity will be composited at the toxicity laboratory. Composite samples shall be collected directly into a clean polyethylene bag, mixed, and then placed into the appropriate jars as outlined in Error! Reference source not found.. Sediment sampling techniques that may be employed are described below. Ambient Sediment Sampling 3 July 2006 Standard Operating Procedures Sediment Sample Collection for Chemical Analysis 1. Wear clean powder-free nitrile gloves when handling bottles and lids. Change gloves if soiled or if the potential for cross-contamination occurs from handling sampling materials or samples; 2. Use pre-labeled sample containers as described in the Sample Bottle Labeling section; 3. Approach first depositional zone from downstream, care should be taken to minimize the disturbance of sediments; 4. Collect a sample of the top layer(3 cm) of sediment carefully with stainless steel trowel. Avoid loosing the fines when lifting the sample; 5. Place sample into a clean polyethylene bag; 6. Repeat collection in the deposition zone 5 times, if feasible; 7. Move to the next depositional zone and repeat collection; 8. Upon gathering sediment at each depositional zone in the reach, mix the composite sample in the polyethylene bag and fill sample containers used for chemical analysis; 9. Place sample on ice; and, 10. Fill out COC form, note sample collection on field form, and deliver to appropriate lab. Sediment Sample Collection for Toxicity Analysis 1. Wear clean powder-free nitrile gloves when handling bottles and lids. Change gloves if soiled or if the potential for cross-contamination occurs from handling sampling materials or samples; 2. Use pre-labeled sample containers as described in the Sample Bottle Labeling Section; 3. Approach first depositional zone from downstream, care should be taken to minimize the disturbance of sediments; 4. Collect a sample of the top layer(3 cm)of sediment carefully with stainless steel trowel. Avoid loosing the fines when lifting the sample; 5. Place sample into a clean polyethylene bag, 6. Collect sample for chemical analysis, as described immediately above; 7. Move to the next depositional zone and repeat collection; 8. Repeat collection with sample spoon in each of the deposition zones until a total volume of 60 L of sample has been collected; 9. Place sample on ice; and, 10. Fill out COC form, note sample collection on field form, and deliver to appropriate lab. Field Measurements and Observations Field measurements will be collected and observations made at each sampling station Ambient Sediment Sampling 4 July 2006 Standard Operating Procedures after a sample is collected. Field measurements typically include flow, pH,temperature, dissolved oxygen, and conductivity. Temperature, pH, dissolved oxygen, and conductivity measurements will be collected at approximately mid-stream, mid-depth at the location of greatest flow(if feasible). Field probes shall be lowered to mid-depth and readings recorded on the field log for that station. All field measurement results and comments on field observations will be recorded on a field log. Flow measurements will be collected using a velocity meter or estimated at each sampling station after a sample is collected. When a velocity meter is unavailable or flow is not sufficiently deep to use a velocity meter, depth, width, and velocity will be estimated to provide an estimate of flow. Depth will be estimated by using the average of several depth measurements taken along the channel. Width will be measured by extending a tape measure from one side of the bank to the other. Velocity will be estimated by measuring the time it takes a floating object(e.g., stick, orange)to travel a known distance. If at any time the collection of field measurements by wading appears unsafe, do not attempt to collect mid-stream, mid-depth measurements. Rather, collect field measurements from a stable, unobstructed area at the reach's edge or use an expandable pole and intermediate container to obtain a sample for field measurements. In addition to field measurements, observations shall be made at each sampling station. Observations will include color, odor, floating materials as well as observations of contact and non-contact recreation. All comments on field observations will be recorded on a field log. Field Protocols Field crews (2 persons per crew, minimum)will only be mobilized for sampling when weather conditions and flow conditions are considered to be safe. For safety reasons, sampling will occur only during daylight hours, when possible. Sampling events should proceed in the following manner: 1. Before leaving the sampling crew base of operations, confirm number and type of sample bottles as well as the complete equipment list. 2. Proceed to the first sampling station. 3. Fill-out the general information on the field log sheet. 4. Collect the samples indicated on the event summary sheet in the manner described in this study plan. Collect additional volume and blank samples for field-initiated QA/QC samples, if necessary. Place bottles and/or jars in the coolers, carefully pack and ice samples. Double check against the log sheet that all appropriate bottles were filled. 5. Collect field measurements and observations, and record on the field log sheet. 6. Repeat the procedures in steps 3, 4, and 5 for each of the remaining sampling stations. 7. Complete the chain of custody forms using the field notes. 8. After sample collection is completed, deliver and/or ship samples to appropriate laboratory on the same day as sample collection. Ambient Sediment Sampling 5 July 2006 Standard Operating Procedures Appendix C Attachment 3 : Mugu Lagoon Sediment Sampling SOP Mugu Lagoon Sediment Sampling Standard Operating Procedures Version Date 08/07/06 Sediment Collection Divers will collect sediments for chemical and toxicity analysis at all stations in situ. This process will eliminate the need for multiple grab sets from the small sampling boat and be more efficient for the amount of sediment needed for analysis. In addition, diver sampling will allow for more precise sediment collection at the station location. In situ sediment samples will be collected directly with the sample storage and transport container, eliminating the potential for metal contamination from grab samplers, and reduce handling and transferring otherwise required after sample collection. Benthic Infauna Collection Benthic samples for infaunal community analysis will be collected in conjunction with the sediment and toxicity sampling throughout Mugu Lagoon. In the central lagoon and eastern arm,benthic sample collection will be accomplished using a 0.1-m2, chain-rigged Van Veen grab deployed from the small sampling boat. One Van Veen grab will be collected at each station in the eastern arm of the lagoon. Once on station,the Van Veen grab will be lowered at a rate not to exceed 1 m/sec to ensure proper deployment. On the bottom,moderate cable tension will be maintained to prevent the sampler from toppling. The grab will be slowly raised until free from the bottom to ensure that an acceptable sample is collected. The grab will continue to be slowly raised until the grabs break the surface and are safely retrieved. In the western arm, or other areas is not accessible to a boat large enough to deploy the Van Veen grab,benthic infauna samples will be collected by divers. At these stations a diver will place a box quadrat with the same surface area as the Van Veen on the bottom and sediments carefully removed, so that no sediments or organisms are lost. Sediments within this quadrat will be excavated to a depth consistent with that collected by Van Veen grab. Upon retrieval,the benthic infaunal samples will examined and a description of the sample recorded on an MBC Sample Collection Form. The sample description will include penetration depth(minimum 10 cm), sediment type, color, general quality of the grab, amount of shell debris, and presence and number of worm tubes. Grab samples will be visually graded as "good," "acceptable," or "poor." A good sample will have an undisturbed sediment surface, an acceptable sample will have a light amount of surface disturbance or slight skewing of the sediments in the grab. A poor sample will be more disturbed or have unacceptable penetration. Poor samples will be discarded and replaced with a new sample. Only grab samples with sediment volumes of at least four liters and which contain a relatively undisturbed sediment surface will be accepted for sample processing. Only good or acceptable samples will be considered for processing. If after three drops with low sample volumes (and no other obvious problems), sample volumes of less than four liters but greater than three liters will be accepted for processing. No samples of less than three liters will be acceptable. Diver collected samples of three liters or more will be accepted. The grab sampler will be thoroughly rinsed with pre-screened seawater between samples. Lagoon Sediment Sampling I August 2006 Standard Operating Procedures Appendix C Attachment 4: Sediment Water Interface Core Sampling SOP Sediment Water Interface Core Sampling Standard Operating Procedures Adapted from Pacific EcoRisk Environmental Consulting and Testing SOP Effective December, 8 2002 Version Date 07/20/06 1.0 GENERAL FIELD SAMPLING EQUIPMENT 1.1 Coring Device—A push core device with a 4-inch diameter removable barrel. A separate pre- cleaned polycarbonate tube is used for each individual core obtained. All tubes are cleaned by approved EPA methods. 1.2 Sediment Water Interface Cores (SWICs)—Polycarbonate tubing, 4-inches in diameter and 8- 10 inches in length. 1.3 SWIC End Caps-High-Density Polyethylene end caps for the 4" diameter SWIC cores (2 caps per core). 1.4 Para-Film—For sealing SWIC cores prior to or after attaching end caps. 1.5 Scissors 1.6 Duct-Tape—For sealing g nd-caps onto SWICs 1.7 Stainless Steel Spatulas—For"slicing" off any extruding sediment prior to sealiong of SWIC. 1.8 Wash Bottle and DI-Water—For rinsing off outside of SWICs 1.9 ZipLoc Bags—For sealing C.O.C. forms within Ice Chests. 1.10 Sample Equipment for Storage and Transport—Samples are stored on ice in large coolers for shipment to laboratory. All samples are shipped, under chain-of-custody, to the testing laboratory via same day or overnight delivery. 1.11 Navigation and Positioning Equipment—Sites will be identified by the use of differential GPS. 2.0 SEDIMENT CORE SAMPLING METHODS The type of sediment collection will depend on the nature of the study to be performed. This description is limited to the collection of"intact" sediment cores (as opposed to SWICs prepared with homogenized sediment). 2.1 Sediment cores are collected in the field and contain the in situ overlying site water. The pre- cleaned empty polycarbonate SWIC is attached to a SWIC coring device. The SWIC coring device is then immersed and pressed into the sediments to the appropriate depth. The core is then Sediment Water Interface Core Sampling July 2006 Standard Operating Procedures carefully pulled out of the sediment and as quickly as possible, an end cap is placed on the bottom of the core to prevent the loss/movement of any sediment within the core. Once the core is securely on the boat, the top end core is placed on the top keeping the in situ overlying water in place (the continued presence of overlying water verifies core integrity). The outside of the core is dried and the bottom wrapped in ParaFilm and then taped to prevent leakage. Each core must be appropriately labeled using a permanent Sharpie marker. If the use of a push-corer is not possible, SWIC cores can be collected from an Eckman sediment dedge. 2.2. At the time of collection of each SWIC, record general observations of core composition (i.e. silt, sand, presence of biota, etc.). Additional sediment core characterization may be required; however the extent and natures of this characterization will be project specific. Record site (and/or sample)ID,time of collection, and analysis-to-be-performed on Chain-of-Custody (COC) form. Samples are stored upright and should immediately be placed on ice (or"blue ice"type product)to bring the temperature to 4°C. 2.3 Between sites, clean all visible sediment from the sampling equipment using site water. The sampling gear is then decontaminated by rinsing with an alconox solution, followed by copious D.I. water rinses. 2.4 Place the C.O.C. inside a sealed plastic bag(e.g., ZipLoc)and enclose within the sample ice chest. The sample should be shipped or transported to the testing laboratory ASAP. 3.0 SAMPLE RECEIPT 3.1 Upon arrival at the laboratory, note condition of custody seal, if present. 3.2 Remove SWIC sample(s) from shipping ice chest/cooler and examine physical condition of each SWIC(s); note any deficiencies (e.g., damaged container, absence of overlying water, leaking, etc.). Cross check each SWIC sample against the C.O.C.; note any deviations and bring to attention to Project Manager. After verifying samples, sign and date C.O.C. 4.0 SEDIMENT SAMPLE CHECK-IN 4.1 Record basic sample description information onto Sample Log-In sheet. Fill out the following information in the Project Log book: project number,test I.D. number, sample I.D. number,test start date, and test description(i.e., species, duration, and client sample ID). 5.0 SAMPLE STORAGE Place sample into the sample storage refrigerator, until needed for test. Samples are stored at 4°C in the dark. SOP 9 Page 2 of 2 Appendix C Attachment 5: Freshwater Tissue Collection SOP Freshwater Tissue Collection SOP for the Calleguas Creek Watershed TMDL Monitoring Program Version Date 07/20/06 Tissue Sample Collection Fish species collected in the past in the CCW include goldfish, fathead minnow,black and brown bullhead, arroyo chub,mosquito fish, and green sunfish. According to USEPA guidance (2000), the target fish species for sample collection should be the largest individual fish captured from both 1)the highest trophic level sampled(e.g., predatory species) and 2) a bottom feeder. The USEPA guidance document lists bass, crappie, walleye, yellow perch, common carp, suckers, catfish, and trout among its recommended target species for inland fresh waters. Other species not listed above may be collected if they are species known to be consumed by people in the CCW, within the size range typically kept for consumption, and are predatory or bottom-feeding species. Total length (longest length from tip of tail fin to tip of nose/mouth) and fork length should be measured and recorded in the field. Scale samples should be collected for aging purposes. For Mugu Lagoon, the Navy has recommend the collection of spotted sand bass (predatory) and diamond turbot(benthic-feeding) (personal communication, Ruane). The diamond turbot was suggested as it is the resident benthic-feeding flatfish in southern California estuarine bays; other benthic feeding flatfishes and croakers are not likely to be resident in Mugu Lagoon. For collection considerations the spotted sand bass can be taken by hook and line whereas the diamond turbot may be caught by seine such as a beach seine. Sampling Protocols Either the California Department of Fish and Game (CDFG) or a local environmental consulting firm with knowledge of resident species will be contracted to perform sample collection. Tissue monitoring will involve the field-collection of fish and the obtaining and storing of fish tissue samples to be analyzed for trace levels of target organics, using protocols detailed in CDFG's (2000) standard operating procedures for fish tissue sample collection and preparation. These protocols are summarized below. Fish(fish, amphibians, invertebrates)will be collected using gear appropriate to the collection site and the species being targeted. Sampling gear may include electrofishing boats, backpack electrofishers, seine nets, gill nets,trap nets, hook and line, or other equipment as required. Specimens are collected as individuals for larger species and as bulk samples (100 gm minimum sample size) for small species requiring whole body tissue analysis. Tissue Collection 1 July 2006 Standard Operating Procedures The preferred species to be collected will be species of the highest trophic level at a given location. Efforts will be made to collect fish of a variety of sizes for each species collected,but all within the typical size range selected by anglers. Efforts also will be made to collect and freeze more samples than the target number to be initially analyzed, thereby providing opportunity to conduct subsequent rounds of tissue analyses, if appropriate. Fish taken for the sample are held alive within a circulating live well (e-boat) or a stainless steel bucket(backpack e-fishing, seine netting, etc.)until they are to be processed. Specimens are counted(when practical), measured/recorded for fork length(FL)/total length(TL) (fin fish only), and packaged (after being humanely dispatched) in extra-heavy duty aluminum foil(dull side against specimen). When possible, individual specimens are labeled to correspond to their physical data on the data sheets. Packaged specimens are then frozen and stored on dry ice for transport. Data sheets include date/time of sampling, site location information, equipment used, effort, specimen data(Spp., FL/TL), additional species captured, and any pertinent field notes. Individual fish will be wrapped in trace metal- and organic-free TeflonTM sheets and frozen for transportation to the laboratory. The tissue samples are prepared in the laboratory using non-contaminating techniques in a clean room environment. For larger species and individual fish, tissue samples for analysis will consist of a 200-g skin-on fillet sample excised from individual fish(except for catfish and other scaleless species, which are usually prepared as skin-off fillets) (USEPA,2000). If multiple fish are required to achieve a 200-g sample, smaller, equal-sized skin-on tissue samples from similar size individuals may be combined for a composite sample of 200 g. However,the preferred method is to collect an adequate size sample from individual fish. Collection,handling and storage of tissue samples will be performed in a manner to assure the collection of representative, uncontaminated tissue chemistry samples. Briefly, the key aspects of quality control associated with fish tissue sample collection are as follows: • Field personnel must be trained in the proper use of sample collection gear and will be able to distinguish acceptable versus unacceptable samples in accordance with pre-established criteria. • Field personnel must be thoroughly trained to recognize and avoid potential sources of sample contamination(e.g., engine exhaust,winch wires, deck surfaces, ice used for cooling). • Samplers and utensils that come in direct contact with the sample will be made of non-contaminating materials (e.g., glass, high-quality stainless steel and/or Teflon TM)and will be thoroughly cleaned between sampling stations. • Sample containers will be pre-cleaned and of the recommended type. In general, sampling protocols are consistent with national guidance developed by USEPA (2000). The minimum number of fish tissue samples to be initially analyzed for each Tissue Collection 2 July 2006 Standard Operating Procedures sampling site is three,but five samples is recommended. These samples may be from the same or different fish species. For any single composite sample of smaller fish,the total length of the smallest fish should be no less than 75%of the total length of the largest fish. If, after expending a reasonable amount of effort,the field crew is unable to catch the required number of fish of an appropriate size at a location, CDFG staff or the sampling contractor will contact the sampling plan manager of the CCWTMP to discuss whether sampling should continue at that location. Tissue Collection 3 July 2006 Standard Operating Procedures Appendix C Attachment 6: Mugu Lagoon Tissue Collection SOP Tissue Collection SOP for Mugu Lagoon for the Calleguas Creek Watershed TMDL Monitoring Program Version Date 08/07/06 Fish Collection Fish for tissue analysis for human and wildlife consumption will be collected in the central portion of Mugu Lagoon by 16-ft otter trawl. An otter trawl is a bottom sampling net that is kept open by wooden doors spread apart by the forward motion of the towing vessel. The otter trawl will be towed by boat in the deepest areas of the central portion of the lagoon during high tide to avoid disturbing harbor seals that haul out on flats in the eastern arm on low tide. The otter trawl will collect both bottom fish such as diamond turbot and halibut, and mid-water species such as bass and schooling species like topsmelt. Tows will be conducted until a sufficient number of fish are caught for analysis purposes. Fish for tissue analysis for wildlife consumption will be collected in the western arm of Mugu Lagoon by seine or trap net. Because of limited access and maneuverability in the western arm it is unlikely that it will be possible to use the otter trawl in the area. Actual collection techniques will be developed in the field based on what works at the time. Fish sampling in this area will be limited to schooling species that provide forage for local bird species. Because of local conditions and abundances, the most abundant prey fish species collected in the western arm may differ from the most abundant species collected in the eastern arm. Mussel Collection Native California or bay mussels will be collected for tissue analysis in two areas of Mugu Lagoon. Mussels will be collected by hand from the pipe overcrossing bridge or from bulkhead walls in the back channel of the Lagoon near the mouth of Calleguas Creek and off the concrete culvert under Lagoon Rd which separates the central and western arms of the lagoon. Mugu Lagoon Tissue Collection 1 August 2006 Standard Operating Procedures Appendix C Attachment 7: Current Measurement (Flow Measurement) SOP Current Measurement (Flow Measurement) Standard Operating Procedures Version Date 07/20/06 If conditions safely permit, current-meter measurements are best made by wading. Measurements are made by recording velocity and depth at increments across the channel. The channel cross section should be defined such that: 1. It is perpendicular to the direction of flow. 2. Velocity and depth measurements should be spaced apart such that no more than 10% of the flow passes through any one cross section. For water depths less than 2.5 ft, velocities are measured at a depth equal to 0.6 times the depth of the water at the measurement location, which is the theoretical depth at which the velocity is equal to the depth-averaged velocity. For water depths greater than 2.5 ft, velocities are measured at 0.2 and 0.8 times the depth, and the average is calculated and assumed to be equal to the depth-averaged velocity. While taking velocity measurements, field personnel should stand in a position that least affects the velocity of the water passing the current meter. That position is usually obtained by facing the bank so that the water flows against the side of the leg. The current meter should be placed ahead of and upstream from the feet. In all cases, the wading rod, to which the current meter is affixed, should be held in a vertical position with the meter parallel to the direction of flow while the velocity is being observed. Personnel should avoid standing in the water if their feet and legs occupy a significantly large percentage of a narrow cross section. In very small streams, measurements should be taken while standing on the bank or an elevated plank or other support, rather than in the water. When the flow is too low for a reliable measurement of discharge by current meter, typically one inch deep,the discharge is determined by use of(1) a volumetric method of measurement or(2)the float method,both of which are described below. VOLUMETRIC MEASUREMENTS Some monitoring locations may be free-flowing,which allows for collection of the entire flowing stream of water into a container of known volume. The time it takes to fill the known volume is measured using a stopwatch and recorded on the field log. The time it takes to fill the container should be measured three times and averaged to ensure that the calculated discharge is representative. For free-flowing outfalls, the estimated flow rate, Q, is calculated by: Q=(Filled-container volume)/(Average time to fill container) Current Meter Measurement 1 July 2006 Standard Operating Procedures FLOAT MEASUREMENTS In cases where flows are too shallow to use a current meter and it is not possible to collect the entire flow into a container, a float and stopwatch may be used. Typically, floats consist of debris collected near the site (e.g. a leaf)or objects that are already floating in the stream of water. The width of the flowing water(not the entire part of the channel that is damp) is measured using a tape measure, along with the depth of the flowing stream in the middle of the channel. The average velocity of the stream is calculated by measuring the time it takes the float to travel a pre-measured distance, normally 10 feet, at least three times and recorded on the field log. For sheet flows, the estimated flow rate, Q, is calculated by: Q =f x(Flowing Width)x(Water Depth)x(Average Velocity) The coefficient f is used to account for friction effects of the channel bottom. The value of f typically ranges from 0.60—0.90. Current Meter Measurement 2 July 2006 Standard Operating Procedures Appendix C Attachment 8: Wet Weather Sample Initiation Procedures L A R R Y W A L K E R Technical 1A Memorandum qgg�.. Dustin Bambic, DATE: June 29, 2006 Project Engineer TO: Chris Minton 250 Lafayette Circle, Suite 200 SUBJECT: Timing of wet weather sampling in Calleguas Lafayette, CA 94549 Creek (925) 962-9700 (925) 962-9701 fax COPY TO: dustinb @Iwa.com PROJECT BACKGROUND Sampling in Calleguas Creek is being conducted for the Calleguas Creek Watershed Total Maximum Daily Load Monitoring Program (CCWTMP). The monitoring goal during wet weather sampling is to collect grab samples from several locations at the peak of the hydrograph of each location. The current criteria to trigger sampling is described in the QAPP, as paraphrased below: Sufficient precipitation is needed to produce runoff, mobilize contaminants, and increase stream flow. The decision to sample a storm event will be made in consultation with weather forecasting information services and after a quantity of precipitation forecast(QPF) has been determined. Wet weather samples will be collected after a targeted storm event, defined as a storm that produces at least 0.5 inches of precipitation. Peak flows shall be targeted, to the extent practicable. Samples are to be collected as instantaneous"grabs", ideally at the peak of the storm hydrograph. Recent experience found a rapid response of runoff at some sampling stations and identified a need to predict more accurately the time of peak discharge. This memo suggests a scheduling process for wet weather sampling events at each monitoring station. SAMPLING STATIONS Table 1 lists each of the receiving water sampling locations. Table 1. CCWTMP Compliance Monitoring Locations Subwatershed Station ID Reach Station Location Mugu Lagoon 01 11 BR 1 11th St Bridge Revolon 04 WOOD 4 Revolon Slough East Side of Wood Road Slough 05 CENTR 5 Beardsley Wash at Central Avenue 02 PCH 2 Calleguas Creek Northeast Side of Hwy 1 Bridge Calleguas 03_CAMAR 3 Calleguas Creek At University Drive 9A_HOWAR 9A Conejo Creek at Howard Road Bridge 9B ADOLF 9B Conelo Creek At Adolfo Road Conejo 10 GATE 10 Conejo Creek Hill Canyon Below North Fork of Conejo Creek 12 PARK 12 Conejo Creek North Fork Above Hill Canyon 13 BELT 13 Conejo Creek South Fork Behind Hill Canyon Belt Press Building Las Posas 06_SOMIS 6 Arroyo Las Posas Off Somis Road 07 HITCH 7 Arroyo Simi East Of Hitch Boulevard Arroyo Simi 07 MADER 7 Arroyo Simi at Madera Avenue 08_WALNU 8 Tapo Canyon At Walnut Street 1 Includes two wet events per site. HYDROLOGIC SETTING The 343-square-mile Calleguas Creek watershed is geographically diverse. Storm systems typically arrive from the west, first providing rain in the lower reaches of the watershed. As the storm moves eastward, the topography rises, causing greater precipitation at higher elevations. The total rainfall per storm has varied little throughout the historical record (1973-present), although the number of storms varies. Generally, 15-20 storm events occur per year. Many Calleguas streams have little or no dry weather flow even during the wet season. Runoff-related discharges are typically 10-100 times greater than base flow. Even during the wet season, most of the dry weather flow in several reaches is attributed to municipal wastewater effluent. Throughout the watershed, runoff is characterized by high flood peaks of short duration. Runoff-related discharges are typically 10-100 times greater than base flow. Runoff generated in the upper basin concentrates quickly into streams, generally peaking within several hours. Most storms affect the watershed from west to east, and therefore flows in Revolon Slough often peak before the other streams.After long period of antecedent dry weather, stream response to rainfall may be minimal even up to 0.5" total rainfall, depending on the rainfall intensity. Spatial variation in rainfall can result in relatively high flows in some streams, and virtually no response in others (e.g. smaller storms often generate runoff in Revolon Slough but not in Tapo Canyon). FORECASTING TOOLS The VCWPD is responsible for flood control in the CCW. VCWPD staff utilize two weather services to forecast rainfall: ■ A contracted forecaster provides geospatially-referenced Quantitative Precipitation Forecasts (QPFs) in 1-hr increments. These forecasts are updated at 8 AM and 3 PM daily. Wet Weather Sample Timing 2 June 29,2006 ■ National Weather Service QPFs are provided in 3-hr and 6-hr increments, which are an unsuitable resolution for the hydrology model. These forecasts are updated at 4 AM and 4 PM daily. If the 1-hr forecasts are drastically different from the contractor's forecast, the 1- hr results are adjusted to account for expected differences. The 1-hr forecast data are input to HEC-1, a hydrologic simulation model simulating rainfall runoff for all of Ventura County. The model divides the CCW into approximately 10 subwatersheds, which are calibrated independently. The model results are storm hydrographs at the outlet of each subwatershed. Many of these locations appear to correspond to our sampling stations. Results are generally available daily at 8 AM and 4:30 PM prior to every upcoming storm event. In addition, when local rain gauge data are reported (i.e., rain begins), these data are input to the hydrology model. The model is then re-run approximately every half hour during storm events to provide updated stream discharge estimates. This hydrology forecasting process occurs in the VCWPD's "flood warning room". Jayme Laber and Scott Holder are the personnel responsible for forecasting. Telephone contact information is as follows: • Flood warning room: 805-654-2666 • Mark Bandurrhea's office: 805-654-2003 • Scott Holder's office: 805-477-7121 VCWPD flood warning summaries are faxed to the county's Office of Emergency Services when storms are pending. The fax sheet contains the most recent QPFs from the two weather forecasting services, observed five-day rainfalls, countywide summary of discharge, critical discharges that trigger flood warning stages, and forecasted peak discharges and time to peak. Re-calibration of the hydrologic model is on-going because of the recent fires, which have upset the normal rainfall-runoff pattern. Model resolution is 15-minutes. Actual peaks have tended to occur later than model predictions, but are typically within 30 minutes. SAMPLING TRIGGER FOR WET WEATHER MONITORING In summary, scheduling sampling should proceed as follows: Step 1.The sampling decision protocol begins when the sampling crew recognizes an approaching storm, through daily monitoring of forecasts. Field staff can estimate that any rainfall prediction for the watershed exceeding 0.5 inches in a 6-hour period (or less)would be sufficient to mobilize for wet season sampling. Step 2. Contact VCWPD's"flood warning room" personnel to notify them that crews will be sampling. Request to receive faxed summary flood warning sheets. Telephone contact information is as follows (given in the appropriate order to try establishing contact): • Flood warning room: 805-654-2666 • Mark Bandurrhea's office: 805-654-2003 Wet Weather Sample Timing 3 June 29,2006 ■ Scott Holder's office: 805-477-7121 Smaller storms, with lower concern for flooding, do not present problems in terms of forecast personnel being in contact with LWA sampling crews. However, forecast personnel may not monitor smaller storms. Conversely, larger storm events are monitored closely by forecast personnel, but they may be less available for updates to LWA sampling crews. When communicating with VCWPD staff, it is important to recall that a"big storm" in terms of water quality monitoring may be a"small storm" in terms of flood control. Step 3. For longer-term scheduling (24-hour), interpolate peak discharge times from hydrology model output to water quality sampling stations as follows: WQ Sample VCWPD Output Point Adjustment in Predicted Time to Station Peak 01_11_BR Calleguas Cr @ CSUCI* +1:10 02_PCH Calleguas Cr @ CSUCI* +1:00 03_CAMAR Calleguas Cr @ CSUCI* <none> 04 WOOD Revolon Slough <none> 05_CENTR Revolon Slough -0:30 06_SOMIS Arroyo Simi @ Madera Rd. -1:15 07 HITCH Arroyo Simi @ Madera Rd. <none> 07_MADER Arroyo Simi @ Madera Rd. <none> 08_WALNU Arroyo Tapo @ Walnut <none> 9A_HOWAR Conejo Cr. US of Hwy.101 -0:15 9B_ADOLF Conejo Cr. US of Hwy.101 <none> 10 GATE Conejo Cr. US of Hwy.101 -0:45 12 PARK Conejo Cr. US of Hwy.101 -1:00 13 BELT Conejo Cr. US of Hwy.101 -1:00 *The peak flow at Calleguas Creek @ CSUCI typically lags the peak at Conejo Creek @ Hwy 101 by three to five hours,depending on the spatial variation in rainfall intensity. Step 4.As a storm approaches(within 12 hours), VCWPD personnel can provide more accurate estimates of time to peak at more locations than presented in the faxed sheets. Communication directly with those personnel would be the most efficient means of obtaining more accurate updates. Alternatively, laptops or cell phones with wireless internet access can by used to access the VCWPD Storm Watch web page and monitor flows real time. Monitoring flows real time is the most reliable means to characterize the response of streams to rainfall. Step 5. Compare actual sample times to actual discharge peaks. Actual sample times are recorded on the field log sheets. VCWPD flood forecasting staff(listed above) can report discharge peaks in real time.As above, monitoring flows real time with a laptop or cell phone is the most accurate method to determine the difference between timing of sampling and peak flow. Step 6. If necessary for final data reporting, corrected, 5-minute-interval discharge data can be obtained from VCWPD flood forecasting staff(listed above). These data are generally not available for a period of one year. Wet Weather Sample Timing 4 June 29,2006 Appendix D Supporting Documents for Toxicity Testing and Benthic Infuana Assessment Appendix D Attachment 1 : Standard Operating Procedure for Chronic Ceriodaphnia dubia Bioassay Pacific EcoRisk Environmental Consulting and Testing Revision#2 (Date last modified: 1/14/05 8:06 PM by Pacific EcoRisk) Effective Date: December 8, 2002 Accepted: Ceriodaphnia dubia (Cerio) Chronic Survival and Reproduction Bioassay Standard Operating Procedures This S.O.P. is based upon the U.S. EPA Guidelines described in Short-Term Methods for Estimating the Chronic Toxicity of Effluents and Receiving Waters to Freshwater Organisms (EPA-821-R-02-013 and EPA-600-4-91-002) 1.0 INTRODUCTION This test is based on a seven-day static-renewal exposure of< 24 hr old(neonate,first instar) Ceriodaphnia dubia to different concentrations of effluents and/or receiving waters. The test endpoints are survival and reproduction. 2.0 TEST PREPARATION 2.1 Equipment and Supplies Needed 1. Food: Selenastrum, YCT and the vitamins Thiamin, Biotin and Blz 2. Control/dilution (80:20)Water: Calistoga spring water and Evian spring water, mixed at a ratio of 80:20,respectively. 3. Meters: D.O.,pH and conductivity/salinity, needed to document test water quality. 4. Thermometer: ASTM certified, for documenting test water temperature. 5. Beakers: (2) 1-L beakers and(4) 250-mL beakers. 6. "Cerio"Test containers: 30-mL plastic cups. Cups must be appropriately-cleaned and rinsed, and then pre-soaked for 24 hrs (overnight) in control water, before use in test. 7. Cerio board: Foam Board containing pre-cut holes to support replicate cups in waterbath. 8. Water quality test cups: 100-mL plastic cups for water quality analysis. 9. De-ionized water: for rinsing of probes, etc. 10. Wash bottles: for rinsing of probes, etc. 11. Volumetric and graduated flasks and pipettes: for making up dilution series and reference toxicant test solutions. 12. Transfer pipettes, wide-bore: for transfer of organisms to and from test containers. 13. Cubitainers may be necessary for the client's collection of effluent. 14. Temperature controlled water bath under cool white fluorescent lighting. 15. ACS reagent CuSO, (copper sulfate), for use as reference toxicant. SOP# Page 1 of 6 Pacific EcoRisk Environmental Consulting and Testing 2.2 Ordering and Holding of Test Organisms 1. Test organisms should be ordered far enough in advance so as to ensure arrival of<24 hrs old animals on test set-up day. Approximately 25-33% more animals should be ordered than are actually needed for the test, so as to allow for some attrition of organisms that are stressed from the shipping, etc. Order cerios from: - Aquatic Research Organisms (603) 926-1650 2. For additional instruction on the receipt and handling of the test organisms, see the "Test Organism Receipt and Handling S.O.P." 3. Alternatively, <24 hour old neonates can be obtained from in-house Stock Cultures (See Ceriodaphnia dubia Culture Maintenance SOP for methods). 2.3 Collection and Holding of Water Samples Grab or composite samples should be collected into appropriately-cleaned glass or plastic container(s) (e.g. cubitainers), and immediately be placed on ice (or"blue ice type product) to bring the temperature to 4°C. The sample should be shipped or transported to the testing laboratory ASAP. Upon receipt of the sample(s) in the laboratory, sample log-in water quality measurements should be taken. For instruction on the log-in of incoming samples, see the"Test Sample(s) Log-In Procedures". The test sample(s) used to start the test must be <36 hrs old (i.e. 36 hrs after collection). No sample >72 hrs old should be used in any test(s). For each test, a minimum of I Liter of sample will be needed each day. 3.0 TEST INITIATION These guidelines may be modified according to specific test conditions required by the NPDES permit of the individual client. Identify these specific requirements prior to test initiation and read the attached"Summary of Test Conditions for Ceriodaphnia dubia". I. Label (1) 1-L beaker for the Control treatment and(1) 1-L beaker for the 100% sample treatment. 2. Fill the Control beaker with 800 mL of Control water and fill the 100% sample beaker with 600 mL of the 100% sample; volume requirements may need to be adjusted for each client. Check the D.O. level of the Control water and the 100% sample and make sure that there is enough oxygen; if not,you must aerate the sample until the D.O. reaches adequate levels. 3. Add food into the 800 mL of Control and 600 mL of sample water: a. Selenastrum (algae) (13 mL/L): 10.4 mL in Control; 7.8 mL in 100% sample b. YCT (7 mL/L): 5.6 mL in Control; 4.2 mL in 100% sample 4. Label (4) 250-mL beakers with the appropriate intermediate test dilutions. See client NPDES permit for specific dilution requirements. 5. Prepare 10 replicate "cerio" test cups for each treatment dilution according to client requirements (e.g.: Control, 6.25%, 12.5%, 25%, 50%, 100%). Label the cups with their treatment and replicate I.D. (i.e. as A-J) using a Sharpie pen. 6. Label (1) water quality test cup (-100-mL size) for each treatment using a Sharpie pen. 7. Using the Control water and the 100% effluent that have been spiked with food,prepare SOP# Chronic Cerio SOP.doc Page 2 of 6 Pacific EcoRisk Environmental Consulting and Testing 200-mL volumes of test solution at each of the intermediate test treatment concentrations. 8. For each treatment, dispense 25-50 mL into a water quality test cup and record the initial water quality (pH, D.O., conductivity, and temperature) onto the data sheets; check to make sure that all parameters, especially the D.O. are within acceptable levels. 9. Place the replicate"cerio"test cups onto a foam support board. Then,beginning with the Control treatment and working up through the concentration series, aliquot 15 mL of test media into each of the 10 replicate cups at each treatment using a clean 60-cc syringe. 10. Use the Sharpie pen and trace the water level line onto each container. Place the foam support board with the dilution containers into the water bath to allow test waters to acclimate to test temperature. 11. Identify 10 adult cerio females from the brood board cultures that have had 8 or more offspring within the past 24 hours. There must not be more than an 8-hour deviation in the ages of the neonates. 12. Using a wide-bore transfer pipette, carefully capture and randomly allocate 1 neonate cerio into each of the test containers. Each of the neonates from one adult will be used to load one replicate (e.g. all A replicates) from each treatment concentration (this is done so that any anomalies, such as a high proportion of males in a particular replicate, can be addressed by omitting that particular replicate from the statistical analysis). a. The organisms are delicate. When transferring, release organisms under the surface of the water. Make sure that each individual is uninjured. Replace injured individuals. b. Be consistent with the volume of stock water used to transfer the organisms. Take care to avoid excessive dilution of the test treatments. 13. Place the foam support board, now containing the test replicate cups, into a temperature controlled water bath at 25°C under cool-white fluorescent lighting on a 16L:8D photoperiod. 14. Place transparent plastic cover sheet over the top of the test replicate cups on the foam support board. 15. Record the water bath temperature onto the test data sheet. 4.0 MAINTAINING THE TEST 4.1 Each day 1. Check the D.O. level of the Control water and the highest concentration of treatment media and make sure that there is enough oxygen (at least 4.0 mg/mL); if not,you must aerate the sample until the D.O. reaches adequate levels. 2. Prepare the appropriate beakers, test cups, and test solutions with the appropriate amounts of food, as above in section 3.0 Test Initiation (steps 1-7). 3. Record the"new" water quality measurements (temperature,pH, D.O. and conductivity) before pouring into new cerio test cups (section 3.0, step 8). 4. Fill each new "cerio"test cup with 15 mL of new test solution using a clean 60-cc syringe SOP# Chronic Cerio SOP.doc Page 3 of 6 Pacific EcoRisk Environmental Consulting and Testing (section 3.0, step 9) and trace the water level onto each container(section 3.0, step 10). 5. Pull the foam support board containing the test replicate cups out of the water bath, and examine each replicate cup. Record observations of dead organisms onto the test data sheets. 6. Using a pipette, carefully transfer each original test organism into its designated new test replicate cup (see section 3.0, step 12). 7. Examine each old test replicate cup to determine the number of neonates (if any) and record the count onto the test data sheet. Discard neonates after counting. Save —25-50 mL of old test solution for each treatment and measure the "old"pH and D.O.,recording the data onto the test data sheets. 8. Place the test organisms within their new test replicate containers onto a foam support board, and return the test replicates to the water bath. Record the water bath temperature onto the test data sheets. 5.0 TEST TERMINATION Test are terminated when 60% or more of the surviving females in the controls have produced their third brood or at the end of 8 days, whichever occurs first. All observations on organisms' survival and number of offspring should be completed within two hours of test termination. 1. Pull the foam support board containing the test replicate cups out of the water bath, and examine each replicate cup. Record observations of dead organisms onto the test data sheets. 2. Examine each old test replicate cup to determine the number of neonates (if any) and record the count onto the test data sheet. Save—25-50 mL of old test solution for each treatment and measure the "old"pH and D.O.,recording the data onto the test data sheets. 3. Count the number of total offspring produced by each individual test organism and record onto the test data sheets. Any animal not producing young should be examined to determine if it is male. 6.0 REFERENCE TOXICANT TESTING To ensure that the organisms being used in the test are responding to chemical stress in a"typical" manner, a reference toxicant test is run side-by-side with the effluent test. The reference toxicant results are then compared with an in-house data base for that reference toxicant to make this determination. Once the various reference toxicant concentrations are prepared, test set-up, maintenance, and termination are identical to those above. Information regarding the Ceriodaphnia reference toxicity test is presented in the"Chronic Ceriodaphnia dubia Reference Toxicity Test SOP". 7.0 DATA ANALYSIS The two endpoint data for each replicate, which are recorded on the appropriate data sheets, are entered into a CETIS" v1.023 data file labeled for identification of the specific test. Statistical analysis are performed in accordance with EPA guidelines for statistical analysis. SOP# Chronic Cerio SOP.doc Page 4 of 6 Pacific EcoRisk Environmental Consulting and Testing 8.0 TEST ACCEPTABILITY CRITERIA Test acceptability criteria for the Ceriodaphnia datbia chronic test includes: 1. 80% or greater control survival 2. Production of three broods of offspring by >60% of surviving control females 3. An average of >_15 offspring per surviving control female. 4. Identified males must be excluded for analysis of the reproduction endpoint,but may be used for the survival endpoint. If 50% or more of the surviving organisms in a replicate block are males,the entire replicate block is excluded from analysis of the reproduction endpoint. 5. The entire test is invalid if fewer than 8 control replicates remain after excluding males. 9.0 QUALITY CONTROL 1. Control water, consisting of a mixture of commercial spring waters for tests and cultures. 2. All equipment is calibrated and operated as described in each applicable equipment SOP. 3. All staff working independently on any test shall have previously demonstrated familiarity and competency with the test, analytical equipment used, and the corresponding SOPs. 10.0 SAFETY The Ceriodaphnia dubia chronic toxicity test poses little risk to those performing it. Care should be taken in the preparation of the reference toxicant spiking solution. Review the MSDS for the reference toxicant. After the ref-tox spiking solution has been used, any remaining solution should be appropriately stored for hazardous waste disposal. SOP# Chronic Cerio SOP.doc Page 5 of 6 Pacific EcoRisk Environmental Consulting and Testing SUMMARY OF TEST CONDITIONS AND TEST ACCEPTABILITY CRITERIA FOR CHRONIC CERIODAPHNIA DUBIA REPRODUCTION AND GROWTH TEST (TEST METHOD 1002.0) 1. Test type Static renewal 2. Temperature 25 ± VC 3. Light quality Ambient laboratory illumination 4. Light intensity 50-100 ft-c (10-20 pE/m'`/s) 5. Photoperiod 16 hours light: 8 hours darkness 6. Test chamber size 30 mL 7. Test solution volume 15 mL 8. Renewal of test solutions Daily 9. Age of test organisms Less than 24 hour old neonates (8 hour release) 10. No. of organisms per test chamber One 11. No. of replicate chambers per Ten concentration 12. No. of organisms per concentration Ten 13. Feeding regime Algae(13mL/L) & YCT (7mL/L) 0.1 mL daily 14. Test chamber cleaning New cups daily. Rinse with deionized water. 15. Test chamber aeration None 16. Dilution water According to NPDES permit. According to NPDES permit. 17. Test Concentrations Effluents: 5 and a control Receiving Waters: 100% and a control. 18. Test duration 7 days or until 60% of the surviving females in the control have 3 broods 19. Test endpoint % survival and reproduction Grab or composite samples must be used to 20. Sampling and holding requirements start test within 36 hours (no sample>72 hours is used in test) 80% control survival, 60% of surviving 21. Test acceptability females in control have three broods, and an average of 15 neonates per surviving control female. Exclude males for repro. 22. Sample volume required 1 Liter per day SOP# Chronic Cerio SOP.doc Page 6 of 6 Appendix D Attachment 2: Standard Operating Procedure Chronic Americamysis Bahia Bioassay Pacific EcoRisk Environmental Consulting and Testing Revision#2 (Date last modified: 1/14/05 3:23 PM by Pacific EcoRisk) Effective Date: December 8, 2002 Accepted: Americamysis Bahia Chronic (7-Day) Survival Growth and Fecundity Bioassay Standard Operating Procedures This S.O.P. is based upon the U.S. EPA Guidelines described in Short-Term Methods for Estimating the Chronic Toxicity of Effluents and Receiving Waters to Marine and Estuarine Organisms,Third Edition (EPA-821-R-02-014). See Addendum, for tests that require the guidelines set forth in previous editions (EPA/600/4-87/028 and EPA-600-4-91-003). 1.0 INTRODUCTION This test is based on a seven-day static-renewal exposure of 7 day old Americamysis bahia to different concentrations of effluents and/or receiving waters during the life period when eggs are produced by the females. The test endpoints are survival, growth (measured as dry weight) and fecundity (measured as the number of mature females with eggs in the oviduct and brood sac). 2.0 TEST PREPARATION 2.1 Equipment and Supplies Needed 1. Food: Brine shrimp nauplii -The test organisms will need to be fed brine shrimp (Artemia) nauplii at least twice per day. These nauplii should be produced with in-house cultures that will require brine shrimp eggs, seawater(natural or artificial), and egg incubation containers. Incubation of the eggs should begin long enough prior to receiving the test organisms so as to assure a ready supply of newly-hatched nauplii as needed. 2. Aeration System: needed for aeration when D.O. drops below acceptable levels. 3. Meters: D.O.,pH and conductivity/salinity, needed to document test water quality. 4. Thermometer: ASTM certified, for documenting test water temperature. 5. Test Containers: 400-mL glass beakers or 200-mL disposable plastic cups. Cups must be appropriately cleaned and rinsed, and then pre-soaked for 24 hrs (overnight) in control water,before use in test. 6. De-Ionized water: for rinsing of probes, etc. 7. Wash Bottles: for rinsing of probes, etc. 8. Volumetric and Graduated Flasks and Pipettes: for making up dilution series and reference toxicant test solutions 9. Wide-bore transfer pipettes or small handheld dip nets: for transfer of organisms to and from test containers. 10. NITEX mesh sieves (150 ycm&500 ysm); for concentrating organisms. 11. Dissecting microscope, for examination of organisms and enumeration of females with brood sacs. SOP# Page 1 of 6 Pacific EcoRisk Environmental Consulting and Testing 12. Depression slide, for microscopic examination of live mysids. 13. Balance: capable of weighing to 0.01 mg. 14. Reference Weights: for calibration of balance. 15. Drying Oven: for drying fish at 105°C at test termination. 16. Desiccator: for holding dried fish. 17. Forceps: for transfer of organisms to weighing pans. 18. Aluminum Foil Weighing Pans: for drying and weighing of fish. 19. Cubitainers: may be necessary for the client's collection of effluent. 20. Artificial Sea Salt(Crystal Seag): for salting up of effluent to acceptable test salinity. 21. ACS Reagent K,Cr04 (Potassium Dichromate), for use as reference toxicant. 2.2 Ordering and Holding of Test Organisms 1. Test organisms should be ordered far enough in advance so as to ensure arrival of 7 day old animals by the day of test set-up. Approximately 25-33% more animals should be ordered than are actually needed for generation of larvae, so as to allow for some attrition of organisms that are stressed from the shipping, etc. Order mysids from: (1) - Aquatic Indicators: (904) 829-2780 (2) - Aquatic Biosystems Inc.: (303) 223-2938 (3)—Aquatox (501)767-9120 2. Order the juvenile mysids to be pre-adapted to the test salinity. This is important as the supplier may be culturing the mysids at a different salinity than the desired test salinity. If the mysids come in at a"non-test" salinity, they must begin acclimation ASAP. Place them in control water at the receiving salinity and immediately begin the adjust the holding salinity towards the test salinity. 3. For additional instruction on the receipt and handling of the test organisms, see the "Test Organism Receipt and Handling SOP". 2.3 Collection and Holding of Water Samples Grab or composite samples should be collected into appropriately-cleaned glass or plastic container(s) (e.g. cubitainers), and immediately be placed on ice (or"blue ice type product) to bring the temperature to 4°C. The sample should be shipped or transported to the testing laboratory ASAP. Upon receipt of the sample(s) in the laboratory, sample log-in water quality measurements should be taken. For instruction on the log-in of incoming samples, see the"Test Sample(s) Log-In Procedures". The test sample(s) used to start the test must be<36 hrs old (i.e. 36 hrs after collection). No sample>72 hrs old should be used in any test(s). For each test, a minimum of 3 Liters of sample will be needed each day. 3.0 TEST INITIATION These guidelines may be modified according to specific test conditions required by the NPDES permit of the individual client. Identify these specific requirements prior to test initiation and read SOP# Chronic Mysid SOP.doc Page 2 of 6 Pacific EcoRisk Environmental Consulting and Testing the attached"Summary of Test Conditions for Americamysis bahia". 1. Mysids should be fed artemia at least two hours prior to the start of the test. 2. Label an appropriate number of 400-mL beakers with the appropriate test treatments for your dilution series (e.g.: control, 5%, 10%, 25%, 50%, and 100%). You will need 8 replicate containers per treatment. Label the beakers with their treatment and replicate I.D. using a Sharpie pen. See client NPDES permit for specific dilution requirements. 3. Label test cups for water quality measurements with treatment and replicate I.D. using a Sharpie pen. 4. Prepare dilutions (as needed) with filtered seawater or appropriately salted receiving water according to client NPDES permit. Always work from low to high concentration and rinse out any glassware 3X with dH2O and one final with seawater prior to use. 5. For each treatment,record the initial water quality (pH, D.O., salinity, conductivity and temperature) onto the data sheets; check to make sure that all parameters, especially the D.O. are within acceptable levels. 6. Then,beginning with the Control treatment and working up through the concentration series,pour 150 mL of sample water into each of the 8 containers. 7. Use the Sharpie pen and trace the water level line onto each container(if using cups). 8. Clean the tank holding the test organisms as much as possible (i.e.,remove uneaten food and any dead mysids) minimizing any disturbance of the live animals. 9. Using a net or sieve,concentrate some of the animals into a corner of the holding tank or into a smaller container of control water. Using a wide-bore transfer pipette, capture and randomly allocate 5 mysids into each of the test containers following the randomization template. a. The organisms are delicate. When transferring,release organisms under the surface of the water. Make sure that each individual is uninjured. Replace injured individuals. b. Be consistent with the volume of water used to transfer the organisms. Take care to avoid excessive dilution of the test treatments. Note any excess dilution of the test solution. 10. Randomly place the test containers within the temperature-controlled water bath (26 ± 1°C) under a 16-hour light, 8-hour dark photoperiod at a light intensity of 50-100 foot- candles. Make sure that all of the necessary data are recorded upon the data sheets. 4.0 MAINTAINING THE TEST 1. The test organisms should be fed newly-hatched brine shrimp nauplii first thing in the morning. 2. At the time of the media renewal,pull the test containers from the water bath and arrange, in replicate#order, and by treatment. From one randomly selected container at each treatment, measure the "old"temperature, pH, D.O. and salinity/conductivity. Check these measurements to make sure that the water quality is within acceptable limits. 3. Remove the uneaten food and any dead animals. This can be accomplished either of two SOP# Chronic Mysid SOP.doc Page 3 of 6 Pacific EcoRisk Environmental Consulting and Testing methods: (1) siphon out the debris and approximately 80% of the "old"test media from each replicate container,being careful not to accidentally siphon any of the live animals; (2) use a transfer pipette to squirt water across the bottom of the replicate container, stirring up debris from the bottom in the process, and then quickly pour approximately 80% of the"old"media out,being careful not to pour out any live animals. 4. Count the number of live animals in each replicate and record the number on the data sheet. 5. Check the D.O. level of the Control water and the highest concentration of treatment media and make sure that there is enough oxygen; if not, you must aerate the sample until the D.O. reaches adequate levels. Carefully (and slowly)pour fresh media back into the replicate containers until the water level is at the 150-mL line. In order not to stress the animals while pouring in this media, tilt the containers and slowly pour in the new media down the side of the tilted container. 6. From one randomly selected replicate container at each treatment (beginning with the Control, and working upward through the concentration series), measure the"new" pH, D.O., and salinity/conductivity. Record these data on the data sheet and randomly place the replicate beakers back in the water bath. Sometime between 3 p.m. and 5 p.m., feed each replicate container with newly-hatched brine shrimp nauplii. 5.0. TEST TERMINATION 1. After 7 days, pull the test containers from the water bath. Measure and record the "old" pH, D.O., and salinity/conductivity. Count and record the number of live animals in each replicate container and remove the dead ones. Siphon or pour out approximately 90% of the old media and replace with control water. 2. Examine the live animals within 12 hours of termination. Using a microscope (240X), determine the number of immature animals, sex of the mature animals, and the presence or absence of eggs in the oviduct or brood sacs for surviving females. Record data on the data sheet. 3. Pour the remaining test solution containing the surviving mysids into a<300 Ym mesh screen submerged in deionized water so as to wash away debris that may alter final weights. 4. Euthanize the organisms from each replicate in an ice-bath with filtered seawater,rinse in de-ionized water and transfer the organisms onto a pre-dried and pre-weighed aluminum drying pan (the pans should be weighed as per the Weighing of Test Organisms S.O.P.). When all of the replicates have been transferred into their respective drying pans,place the pans into the drying oven, and dry at 105°C for at least 6 hrs. 5. After drying, place the aluminum pans into the dessicator and seal. Allow to cool at least 4 hrs, after which each pan must be weighed and the weight data recorded. The weight recorded for the empty pans minus the weight of the pans +dried animals =the pooled dry weight of the organisms for that replicate. Divide this number by the number of organisms in the replicate to obtain the mean dry weight for individual mysids in that replicate. For the control treatment,calculate the mean weight per surviving fish for each replicate to determine if the weights met test acceptability criteria. SOP# Chronic Mysid SOP.doc Page 4 of 6 Pacific EcoRisk Environmental Consulting and Testing 6. At this point, there should be two endpoint data for each replicate: percentage survival and mean dry weight per individual. 7. Notify client immediately if toxicity is observed. 6.0 REFERENCE TOXICANT TESTING To ensure that the organisms being used in the test are responding to chemical stress in a"typical" manner, a reference toxicant test is run side-by-side with the effluent test. The reference toxicant results are then compared with an in-house data base for that reference toxicant to make this determination. Once the various reference toxicant concentrations are prepared, test set-up, maintenence, and termination are identical to those above. Information regarding the Americamysis Bahia reference toxicity test is presented in the "Chronic (7-day)Americamysis Bahia Reference Toxicity Test SOP". 7.0 DATA ANALYSIS The three endpoint data for each replicate, which are recorded on the appropriate data sheets, are entered into a CETIS" v1.023 data file labeled for identification of the specific test. Statistical analyses are performed in accordance with EPA guidelines for statistical analysis. 8.0 TEST ACCEPTABILITY CRITERIA Test acceptability criteria for the Americamysis Bahia chronic test are as follows: (1) 80% or greater survival in the control; (2) average dry weight of 0.20 mg/individual in controls; and (3) fecundity can be used if>50% of females in controls produce eggs. 9.0 QUALITY CONTROL 1. Control water, consisting of deionized water salted up to test salinity with Crystal Seas sea salt, is used. 2. The test mysids shall be maintained in the laboratory 4-7 days prior to use in tests in order to monitor and examine them for health and quality. 3. All equipment is calibrated and operated as described in each applicable equipment SOP. 4. All staff working independently on any test shall have previously demonstrated familiarity and competency with the test, analytical equipment used, and the corresponding SOPs. 10.0 SAFETY The Americamysis Bahia 7-day chronic toxicity test poses little risk to those performing it. Care should be taken in the preparation of the reference toxicant spiking solution. Review the MSDS for the reference toxicant. After the ref tox spiking solution has been used, any remaining solution should be appropriately stored for hazardous waste disposal. SOP# Chronic Mysid SOP.doc Page 5 of 6 Pacific EcoRisk Environmental Consulting and Testing SUMMARY OF TEST CONDITIONS AND TEST ACCEPTABILITY CRITERIA FOR MYSID,AMERICAMYSIS BAHIA, LARVAL SURVIVAL, GROWTH, AND FECUNDITY TEST (TEST METOD 1007.0) 1. Test type Static renewal 2. Test duration 7 days 3. Salinity 20 to 30 ppt± 2 ppt 4. Temperature 26 ± 1°C 5. Light quality Ambient laboratory illumination 6. Light intensity 50-100 ft-c (10-20 ycE/m2/s) 7. Photoperiod 16 hours light: 8 hours darkness 8. Test chamber size 400-mL 9. Test solution volume 150 mL 10. Renewal of test solutions Daily 11. Age of test organisms 7 days old 12. No. of organisms per test chamber Five (5) 13. No. of rep. chambers per concentration Eight (8) 14. No. of organisms per concentration Forty (40) 15. Feeding regime Artemia nauplii twice daily 16. Test chamber cleaning Siphon daily, immediately before test solution renewal 17. Test chamber aeration None,unless DO concentration falls below 4.0 mg/L;rate should not exceed 100 bubbles/min According to NPDES permit. Filtered (I ycm) 18. Dilution water seawater,dH2O salted up with Crystal Seams sea salt. According to NPDES permit. 19. Test concentration Effluents: 5 and a control Receiving Waters: 100% and a control. 20. Dilution factor According to NPDES permit. None, or>0.5 dilution series 21. Test endpoint % survival and growth Grab or composite samples must be used to start 22. Sampling and holding requirements test within 36 hours (no sample >72 hours is used in test) 23. Sample volume required 3 Liters per day 80% or greater average survival in controls; 24. Test acceptability average weight of control animals >_0.2 mg; fecundity may be used if>50% of control females produce eggs. SOP# Chronic Mysid SOP.doc Page 6 of 6 Appendix D Attachment 3 : Standard Operating Procedure for Chronic 10-day Hyalella azteca Bioassay Pacific EcoRisk Environmental Consulting and Testing Revision#2 (Date last modified: 1/14/05 8:05 PM by Pacific EcoRisk) Effective Date: December 8, 2002 Accepted: Hyalella azteca Acute (10-day) Survival & Growth Sediment Toxicity Test Standard Operating Procedures This SOP is based upon the U.S. EPA Guidelines described in Methods for Measuring the Toxicity and Bioaccumulation of Sediment-associated Contaminants with Freshwater Invertebrates, Second Edition (EPA/600/R-99/064). It is also in general accordance with ASTM Standard E1706-95b, Test methods for measuring the toxicity of sediment-associated contaminants with freshwater invertebrates. 1. INTRODUCTION This test is based on a 10 day static-renewal exposure of 7-14 day old Hyalella azteca to sediments. The test endpoints are survival (and an optional endpoint of growth (measured as mean dry weight). 2. TEST PREPARATION 2.1 Equipment and Supplies Needed 1. Sample containers may be necessary for the client's collection of sediment. Containers must be pre-cleaned consistent with EPA guidelines. A minimum volume of 1-L of sediment is necessary (2-1, is preferred) to provide sediment for the bioassay and for the accompanying sediment porewater characterization. Additional volume will be necessary for further characterization of sediment (e.g., grain size characteristics, contaminant concentrations). 2. Stainless steel bowls and spatulas (or spoons) to homogenize sediments prior to placement in replicate containers. 3. Test containers, consisting of 300-mL tall-form glass beakers,modified as follows: a. The flared lip of the beakers should be cut off, and the upper rim flame-polished. This service can be provided by Orca Glassworks in Benicia. The prepared beakers must be appropriately cleaned before further use. b. Cut a 2.5 cm-wide band of 120-lim Nitexo, approximately 25 cm in length. Using aquarium-safe silicon sealant, attach the band of Nitex around the upper lip of the beaker, such that —two-thirds of the width of the Nitex band is above the glass. Make sure to completely seal the Nitex such that there are no openings or seams into which the test organisms might become entrapped. Allow the silicon sealant to cure for a minimum of 24 hrs. The resulting test containers must be appropriately cleaned and rinsed, and then pre-soaked for 48 hrs in reverse- osmosis, de-ionized(RO/DI) water, before use in testing. 4. Modified Zumwalt-type water delivery system, consisting of lower plastic tub to hold replicate containers in position, and upper plastic tub, plumbed with 75 mL syringes for delivery of water to replicate containers. 4OP # Pane 1 of 9 Pacific EcoRisk Environmental Consulting and Testing 5. Synthetic Test Water, consisting of synthetic freshwater, prepared as per EPA guidelines (see Section 7.1.3.4 of guidelines): a. Transfer —75 L of reverse-osmosis, de-ionized (RO/DI) water into an appropriately-cleaned 120-L HDPE tank. b. Add 5-gm of CaSO4 and 5 gm of CaCl2 to a 2-L aliquot of RO/DI water and mix on magnetic stir plate for 30 min or until the salts completely dissolve. c. Add 3 gm of MgSO4, 9.6 gm of NaHCO3, and 0.4 gm of KCl to a second 2-L aliquot of RO/DI water, and mix on a magnetic stir plate for 30 min. d. While vigorously stirring, pour each of the 2-L aliquots of salt solutions into the 75-L of RO/DI water, and fill to a total volume of 100-L with RO/DI water. e. Vigorously aerate the water for at least 24 hrs prior to use. f. The water quality should be: i. Hardness, 90-100 mg/L as CaCO3 ii. Alkalinity, 50-70 mg/L as CaCO3 iii. Conductivity, 330-360 mS/cm iv. pH, 7.8-8.2 6. Water quality (pH, DO, and conductivity/salinity) meters, calibrated and used as per the appropriate SOPS. 7. Glass or electronic thermometer, calibrated and used as per the appropriate SOP. 8. Pipets, disposable plastic Pasteur pipets, for the collection and transfer of test organisms. 9. Fine-tip Forceps, for use in collecting individual organisms from culture material at test initiation. 10. Glass dishes, for the sorting and collection of test organisms at test initiation and at test termination. 11. Light boxes, for the sorting and collection of test organisms at test initiation and at test termination. 12. Aeration System, in case needed to aerate should D.O. drops below acceptable levels. 13. Test Food, consisting of YCT. 14. Sieves, #25, #40, and#50, for collection of organisms at test termination. 15. Aluminum Foil Weighing Pans, for drying and weighing of Hyalella at end of test. 16. Drying Oven, at 105°C for drying larval amphipods at test termination. 17. Desiccators, for holding dried organisms. 18. Balance, capable of weighing to 0.01 mg. Calibrate and use as per the appropriate SOP 2.2 Ordering and Holding of Test Organisms 2.2.1 Ordering and Holding of Test Organisms from Commercial Supplier 1. Test organisms should be ordered far enough in advance so as to ensure arrival of 13-day old animals 24 hrs prior to Day 0. Approximately 25-33% more animals should be SOP # 10-D HyalellaAcuteSedTest.doc Page 2 of 9 Pacific EcoRisk Environmental Consulting and Testing ordered than are actually needed for the test, so as to allow for some attrition of organisms that are stressed from the shipping, etc. 2. Order Hyalella azteca from: a. Aquatic Biosystems Inc. b. Aquatic Research Organisms 3. Upon receipt, the test organism culture should be transferred into 4-L HDPE tanks containing test water at 23°C; the culture should be gently aerated, and should be fed slurried ground flake fish food and YCT. 2.2.2 Organisms from In-Lab Culture 1. Test organisms must be isolated from the In-Lab culture at least 13 days before the test is to begin in order to have 14 day-old animals on Day 0 . Adults from each of the culture tanks should be collected and transferred to the top of the sieve bowls in the three neonate collection bowls. Add a few conditioned leaves to each of the sieve bowls as well, and provide gentle aeration. Allow to sit undisturbed overnight. 2. The following day, carefully remove the leaves, shaking to dislodge any clinging adults. Gently shake the top sieve bowl and lift out of the bowl assembly, carefully transferring the retained adults into a temporary holding container (make sure the transferred adults are not trapped at the water surface!). The remaining control water in the bowl assembly contains all of the neonates released. These should be transferred into a new culture tank containing a few conditioned leaves. During this transfer, the neonates should be counted. There should be at least 150% of the number needed for the test. If not, repeat this process with the adults and collect a second day's batch of neonates, which will be combined with the first days. After enough neonates are collected, the adults can be returned to their culture tanks. 3. The collected neonates should be fed a suspension of ground Tetra-Min, YCT, and powdered Spirulina. Change the water at 7 days and at 11 days, inspecting the animals to ensure adequate abundance, health and quality. 2.3 Collection and Holding of Sediment Samples Grab or composite samples should be collected into appropriately-cleaned glass or plastic container(s), and immediately be placed on ice (or "blue ice" type product) to bring the temperature to 4°C. The sample should be shipped or transported to the testing laboratory ASAP. Upon receipt of the sample(s) in the laboratory, each sample should be logged in, and then placed in the sample refrigerator at 4°C. For instruction on the log-in of incoming samples, see the "Test Sample(s) Log-In Procedures". The test sample(s)used to start the test should be <2 weeks old. For each site tested, a minimum of 16 L of sample will be needed for the bioaccumulation testing. Chemistry analyses will require additional samples. The total organic carbon content of each sediment type should be determined before starting test in order to validate the organism loading rate. 3.0 TEST INITIATION Before test initiation begins be aware of any client-specific testing requirements and read the attached"Summary of Test Conditions for Hyalella azteca. " SOP # 10-D HyalellaAcuteSeffest.doc Page 3 of 9 Pacific EcoRisk Environmental Consulting and Testing 3.1 On the Day Before Test Initiation (Day—1): 1. Remove the test replicate containers from soaking in the tank of R/DI water and shake excess water off. Each test treatment, including each Control, will require 8 test replicate containers. Label the test containers with their treatment and replicate ID code (Replicates "A" through "H") using an indelible black ink(Sharpie®)pen. 2. Remove the sediment from the sample storage refrigerator and allow to come to room temperature. Using a stainless steel spoon and bowl,re-homogenize the sediment along with any overlying water that has developed. 3. For each sediment sample, use a stainless steel spoon or spatula to transfer approximately 100 mL of homogenized sediment into each of the 8 replicates, carefully"tamping" down the sediments. Carefully pour approximately 175 mL of control water into each beaker, taking care to minimize disturbance of the sediment. 4. Place the test replicates into the water bath, with the temperature controlled at 23°C, under cool-white fluorescent lighting on a 16L:8D photoperiod. 3.2 Pre-Test Sediment Porewater Characterization (Day—1, or before): 1. Place approximately 500 mL of each homogenized sediment into a 750-mL centrifuge bottle, and centrifuge at 2500 g for 30 min. 2. Decant supernatant (= sediment porewater), and measure routine water quality characteristics of the porewater (pH, DO, conductivity, and total ammonia). Record the water quality data into the Sediment Porewater Data Log Book. 3.3 Immediately Prior to Test Initiation (Day 0): 1. Using the Zumwalt water delivery system,renew the overlying water in each of the replicate containers. 2. After the water is renewed, collect—25 mL of test water from 1-2 cm above the sediment in each test replicate using a disposable 25 ml glass pipet; composite the replicate water samples for each test treatment to provide a total volume of—200 mL. 3. Measure the initial water quality conditions (temperature, pH, DO, conductivity, hardness, alkalinity, and total ammonia). Record the water quality data onto the Sediment Toxicity Test Water Quality Data Sheet. 4. If the DO levels fall below 2.5 mg/L, implement gentle aeration of each test replicate. 5. Isolation and Collection of Individual Test Organisms: a. Immediately prior to test initiation, transfer small portion of test organism culture and test water into shallow glass dish placed on top of light box. b. Using plastic pipet, agitate the culture material. This disturbance will cause the Hyalella to disengage from the substratate and swim around in the water, facilitating their capture. 3.4 Initiate the Test(Day 0): 1. Gently draw individual Hyalella into the pipet and transfer organisms directly into test replicate containers, gently expelling organism from pipet below the water surface. SOP # 10-D HyalellaAcuteSedTest.doc Page 4 of 9 Pacific EcoRisk Environmental Consulting and Testing Alternatively, transfer organisms into a small transfer dish (e.g., plastic weigh boats) containing small aliquot of test water, continuing process until there are 10 organisms in the transfer dish, that can subsequently be poured into the test replicates, again making sure that organisms are below the water surface. Note—this process must take place quickly, as extended period in the transfer dish will stress the organisms. 2. Allocate 10 randomly-selected 7-14 day old Hyalella azteca into each replicate beaker. Load test replicates following a randomized block approach. Load all "A" replicate containers first, with the order of test treatments being randomized. Repeat process for the "B" replicates, with the order of test treatments being re-randomized. Continue until all test replicates are loaded. 3. Immediately re-examine the replicates, replacing any dead or injured animals. Due to surface tension, some organisms may be "trapped" on the water surface. Examine each replicate to ensure that all test organisms are below the water surface. Using a plastic pipet, organisms that are at the water surface should be moved into the water by gently squirting the organisms with test water. 4. Randomly place the replicate containers into the temperature-controlled waterbath at 23°C, under cool-white fluorescent lighting on a 16L:8D photoperiod. 5. Feed each replicate 1.0 mL of YCT. 4.0 TEST MAINTENANCE (DAYS 1-9) 1. Examine each replicate container. Any dead organisms should be removed via pipet, and the number of mortalities recorded onto the test data sheet. 2. Each day, measure the temperature in the test water in one randomly-selected replicate for each treatment and record data onto test data sheet. 3. Using a disposable 25 mL pipet, collect"old" test water from 1-2 cm above the sediment for each replicate, compositing the replicate water samples for each test treatment to provide a total volume of—200 mL. Measure the"old" DO and record data onto test data sheet. If the DO levels fall below 2.5 mg/L, implement gentle aeration of each test replicate. 4. Renew the overlying water using the Zumwalt water delivery system to deliver 2 replicate water volumes to each replicate container. 5. Collect —25 mL of"new" test water from from each replicate, compositing the replicate water samples for each test treatment to provide a total volume of—200 mL. Measure the "new" DO and record data onto test data sheet. 6. Return the test replicates to the test waterbath, and feed each replicate 1.0 mL of YCT. 5.0 TEST TERMINANTION 1. Measure the temperature in the test water in one randomly-selected replicate for each treatment and record data onto test data sheet. SOP # 10-D HyalellaAcuteSeffest.doc Page 5 of 9 Pacific EcoRisk Environmental Consulting and Testing 2. Collect —25 mL of test water from 1-2 cm above the sediment in each test replicate using a disposable 25-mL glass pipet; composite the replicate water samples for each test treatment to provide a total volume of—200 mL. 3. Measure the remaining final water quality conditions (pH, DO, conductivity, hardness, alkalinity, and total ammonia). Record the water quality data onto the Sediment Toxicity Test Water Quality Data Sheet. 4. Working one treatment and one replicate at a time, examine each replicate, noting and recording the number of any pupae, pupal exuvia, and/or adults, and recording this data onto the test weight data sheet. 5. Using a pipet or a squirt bottle containing clean test water, vigorously squirt water onto the top of the sediment so as to disturb the surficial layer — this will often result in the emergence of many of the Hyalella, facilitating their collection. Using a pipet and/or forceps, collect and transfer any emerging larvae into a glass sorting dish atop a light box. Using a squirt bottle, rinse the organisms with clean test water to remove any sediment or other clinging material. Using the forceps, transfer the individual larvae into a pre- labeled, -dried, and—weighed aluminum foil drying pan. 6. Carefully wash the sediment from the same replicate container through a #40 stainless steel sieve, washing the retained materials into the glass sorting dish. Using a pipet and/or forceps, collect and transfer any emerging larvae into a glass sorting dish. Using a squirt bottle, rinse the organisms with clean test water to remove any sediment or other clinging material. Using the forceps, transfer the individual larvae into the same pre-labeled, - dried (via muffle furnace), and—weighed aluminum foil drying pan that was used for the organisms collected in the earlier step (Step 6.5, above). 7. Record the number of live larvae collected from that replicate onto the test weight data sheet. 8. Repeat steps 6.4 through 6.7 for each test replicate. 9. When all of the replicate organisms have been transferred into their respective drying pans, place the pans into the drying oven, and dry at 105°C for 48 hrs. 10. After drying, place the aluminum pans into the desiccator and seal. Allow to cool at least 4 hrs, after which each pan must be weighed and the weight data recorded onto the test weight data sheet. 6.0 REFERENCE TOXICANT TESTING (OPTIONAL) To ensure that the organisms being used in the test are responding to chemical stress in a "typical" manner, a reference toxicant test is run side-by-side with the effluent test. The reference toxicant results are then compared with an in-house database to make this determination. Information regarding the reference toxicity test is presented in the "Hyalella Reference Toxicity Test SOP". SOP # 10-D HyalellaAcuteSeffest.doe Page 6 of 9 Pacific EcoRisk Environmental Consulting and Testing 7.0 DATA ANALYSIS 1. For each sediment, sum up the total number of live organisms that were counted at test termination and record total number of live organisms at test termination onto the toxicity test data sheet. 2. On the test weight data sheet, subtract the weight of the pans + dried animals from the tare weight (the weight recorded for the empty pans) to determine the pooled dry weight of the larval organisms for that replicate. Divide this number by the number of larval organisms for that replicate to obtain the mean dry weight for individual organisms in that replicate. 3. Using the CETIS® statistical software, input the survival and relevant weight data for the Control treatment and for a given test sediment into a linked-file specific for that test sediment. 4. Analyze the test data, as per the EPA guidelines statistical flowchart procedures, comparing the test responses of the test sediment against the Control treatment to determine whether the test sediment exposure resulted in statistically significant reductions in survival or growth (as dry-ash weight) of the larval amphipods. 8.0 TEST ACCEPTABILITY CRITERIA 1. Age of H. azteca at the start of the test must be between 7- to 14-d old. The 10-d test should start with a narrow range in size or age of H. azteca (i.e., 1- to 2-d range in age) to reduce potential variability in growth at the end of a 10-d test. 2. Average survival of H. azteca in the control sediment must be greater than or equal to 80% at the end of the test. Growth of test organisms should be measurable in the control sediment at the end of the 10-d test (i.e., relative to organisms at the start of the test). 3. Hardness, alkalinity, and ammonia in the overlying water typically should not vary by more than 50% during the test, and dissolved oxygen should be maintained above 2.5 mg/L in the overlying water. 9.0 QUALITY CONTROL 1. All measured water quality should be within the limits established by the US EPA guidelines; any deviations must be noted in lab notebook and explained. 2. All equipment is calibrated and operated as described in each applicable equipment SOP. 3. All staff working independently on any test shall have previously demonstrated familiarity and competency with the test, analytical equipment used, and the corresponding SOPs. 10.0 SAFETY The Hyalella survival and growth toxicity test poses little risk to those performing it. Sediments can contain pathogenic organisms and appropriate precautions should be observed when handling this material. After the test is complete, the sediments should be disposed of in an appropriate fashion. SOP # 10-D HyalellaAcuteSedTest.doc Page 7 of 9 Pacific EcoRisk Environmental Consulting and Testing SUMMARY OF TEST CONDITIONS AND TEST ACCEPTABILITY CRITERIA FOR CONDUCTING THE 10-DAY HYALELLA AZTECA SURVIVAL AND GROWTH SEDIMENT TOXICITY TEST (TEST METHOD 100.1) 1. Test type Whole-sediment toxicity test with renewal of overlying water 2. Test duration 10 days 3. Temperature 23 ± 1°C 4. Light quality Wide-spectrum fluorescent lights 5. Light intensity About 100 to 1000 lux 6. Photoperiod 16L:8D 7. Test chamber size 300-mL high-form lipless beaker 8. Test sediment volume 100 mL USEPA MH Culture water, well water, 9. Overlying water surface water, site water, or reconstituted water 10. Overlying water volume 175 mL Temperature and D.O. daily. 11. Overlying water quality Hardness, alkalinity, conductivity, pH, and ammonia at beginning and end of test. 12. Overlying water renewal 2 volume additions/d @ one volume addition every 12 h 13. Age of test organisms 7- to 14-d old at the start of the test (1- to 2-d range in age) 14. No. of organisms per test chamber 10 15. No. of rep. chambers/concentration 8 but depends on the objective of the test. 16. Feeding regime YCT food, fed 1.0 mL daily (1800 mg/L stock) to each test chamber. 17. Test chamber cleaning If screens become clogged during the test, gently brush the outside of the screen 18. Test solution aeration None, unless DO in overlying water drops below 2.5 mg/L 19. Endpoints Survival and growth 20. Sample and sample holding requirements Grab or composite samples should be stored at 4°C. 21. Sample volume required 16 Liter Minimum mean control survival of 80% 22. Test acceptability criteria and measurable growth of test organisms in the control sediment. SOP # 10-D HyalellaAcuteSedTest.doc Page 8 Of 9 Pacific EcoRisk Environmental Consulting and Testing /< 1st Antenna _ r X A 3rd Uropod ,2nd Antenn 1st Uropod Figure 11.1 Hyalalda affeca. (Ali denotes the uropods; (B) denotes the base of the first antennae; (C) denotes the gnathopDd used for grasping females. l enurement of length is made from base of the 3r° uropod (A) to (B). Females are recognized by the presence of egg cases or the absence of an enlarged gnathopod. (Reprinted from Cole and Watkins, 1997 with kind permission from Kluwer Academic Publishers.) SOP # 10-D HyalellaAcuteSedTest.doc Page 9 of 9 Appendix D Attachment 4: Standard Operating Procedure for Chronic 10-day Eohaustorius estuarius Bioassay Pacific EcoRisk Environmental Consulting and Testing Revision#3 Effective Date: 7/20/06 2:56 PM Accepted: Eohaustorius estuarius 10 Day Amphipod Whole Sediment Toxicity Test Standard Operating Procedures 1.0 INTRODUCTION This test is based on a ten day exposure of young adult Eohaustorius estuarius to whole sediments. The test endpoint is percent survival. Methods outlined in this standard operating procedure (SOP) are based on ASTM 1367-99, Standard Guide for Conducting 10-day Static Sediment Tests with Marine and Estuarine Amphipods (1999) and EPA's Methods for Assessing the Toxicity of Sediment-associated Contaminants with Estuarine and Marine Amphipods (EPA/600/R-94/025). 2.0 TEST PREPARATION 2.1 Equipment and Supplies Needed 1. Spatula for homogenization of sediment 2. Analytical balance capable of weighing to 0.01 mg. 3. Reference Weights, for calibration of balance. 4. Aeration System 5. pH, D.O., and conductivity/salinity meter, needed to document test water quality. 6. NIST certified Thermometer, for documenting test water temperature. 7. Test Containers, 1000 mL glass beakers or wide-mouth glass jars. 8. De-Ionized water, for rinsing of probes, etc. 9. Wash Bottles, for rinsing of probes, etc. 10. Volumetric and Graduated Flasks and Pipettes, for making up reference toxicant test solutions. 11. Transfer Pipettes, for transfer of amphipods to test containers. 12. Sieves (1.0 mm), for concentrating organisms. 13. Sieves (0.1 and 0.2 mm), for removing excess debris and indigenous organisms. 14. 2-4 liter jars for the client's collection of sediment. 15. ACS Reagent CdCl, (cadmium chloride), for use as reference toxicant. 16. Centrifugation system, for extraction of sediment porewater. 17. Equipment and supplies for Total Ammonia analysis. SOP#C030-1 Page 1 of 8 Pacific EcoRisk Environmental Consulting and Testing 2.2 Ordering and Holding of Test Organisms 1. Young adult test organisms (3-5 mm) should be ordered far enough in advance of testing so as to ensure proper acclimation to test salinity prior to the test set-up: Order amphipods from: (1) - John Brezena and Associates (707)878-2853 Note - be sure to order"home" sediment for use as a control in the testing. 2. Order the amphipods to be pre-adapted to the test salinity if possible. If the amphipods come in at a"non-test" salinity, they must begin acclimation ASAP. 3. Place them in `Home' sediment at the receiving salinity and immediately begin to adjust the holding salinity towards the test salinity at a rate not to exceed 5 ppt per 24 hours. 2.3 Collection and Holding of Sediment Samples Sediment samples should be collected into appropriately-cleaned glass or plastic container(s), and immediately be placed on ice (or"blue ice type product)to bring the temperature to 4°C. The sample should be shipped or transported to the testing laboratory ASAP. Upon receipt of the sample(s) in the laboratory, sample log-in measurements should be taken. For instruction on the log-in of incoming samples, see the "Test Sample(s) Log-In Procedures". The test sample(s) used to start the test should be<2 weeks old. For each test, a minimum of 2 Liters of sediment will be needed to be collected. 3.0 TEST INITIATION Before test initiation begins, read the attached"Summary of Test Conditions for Eohaustorius estuarius." 3.1 Sediment Preparation (Day-1) 1. Homogenize the sediment, removing large debris (rocks, sticks, etc.). 2. Remove an aliquot from the center interior and examine with a probe for indigenous organisms. If found,press-sieve through a 1 or 2 mm mesh screen and remove any macrobenthic organisms found in the sediment during sieving. 3. Hold the sediment at 4°C until loaded into bioassay chambers. 4. Sieve Control sediment through a 0.5 mm screen to remove indigenous Eohaustorius. 3.2 Loading of Sediment into Test Chambers(Day-1) 1. Pre-label the bioassay beakers for all treatments including the control and add an aliquot of homogenized sediment(approximately 175 mL) into each of the five replicate chambers. Each chamber should be filled to about 2 cm depth. 2. Settle each sediment in the chambers by gently tapping the glass or by smoothing the sediment surface with a polyethylene spatula. 3. Add overlying water(at desired test salinity) to fill the beaker to 750-mL being careful not to disturb the sediment. 4. Place test replicates in a water bath at 15 t 1°C under a continuous light photoperiod. SOP#C030-1 10-D Eohaustorius Sed Test SOP Page 2 of 8 Pacific EcoRisk Environmental Consulting and Testing Gently aerate each chamber overnight. The tip of the aeration pipette should be 2-3 cm above the surface of the sediment. 5. Centrifuge a separate aliquot of sediment at 2500 G for 30 minutes. Measure the pH, sulfide, salinity and total ammonia of the porewater. 3.3 Introduction of Organisms to Test Chambers (Day 0) 1. Measure the temperature, salinity, pH and DO in each replicate. Collect one sub-sample from each control, reference or test site for measuring ammonia. 2. Sieve Eohaustorius from home sediment holding containers using a 1.0 mm sieve. Enough organisms are sieved to provide approximately one third more amphipods than are needed. Transfer organisms to a holding tray and remove any unhealthy organisms. For sieving, use seawater of the same temperature and salinity as the test water. 3. Using a pipette with a 6 mm opening, transfer 20 organisms into loading dishes containing an aliquot(-150 mL) of test water each at the holding temperature and salinity. Avoid mature individuals particularly females with visible embryos in the brood pouch or oviduct. 4. Recount the amphipods to verify that 20 have been collected. Gently pour the organisms into each test chamber, and bring the water level up to 950 mL. 5. After 5-10 minutes, examine each replicate and replace any organisms that may have been injured or stressed during the isolation, counting, or addition process. Healthy animals will burrow into sediment. Animals that are repeatedly burrowing into the sediment and emerging in an apparent avoidance response are not replaced. The number of amphipods that are removed must be recorded. 6. Cover the test chamber, continue aeration, and set up a continuously recording thermometer in the test water bath. 4.0 DAILY MEASUREMENTS AND OBSERVATIONS 1. Temperature, salinity, dissolved oxygen and pH of the overlying water is measured daily in at least one replicate from each treatment. 2. Each test chamber is examined daily to ensure.air flow to the overlying sea water. Any amphipods trapped in the air water interface should be gently pushed down into the water using a pipette. Make general observations (yes/no) of apparently dead organisms and emergent amphipods swimming around in the water column. 3. Measure ammonia in the overlying water at Day 2 and Day 8 of the test. 5.0 TEST TERMINATION 1. After ten days, measure and record temperature, salinity, dissolved oxygen and pH in each test replicate. Collect one subsample per site for measuring ammonia. 2. Remove any surviving amphipods in the water column and rinse (with test water) the remaining contents of each exposure chamber through a 0.5 mm sieve. 3. Wash material that has been retained on the sieve into a sorting tray and carefully examine SOP#C030-1 10-D Eohaustorius Sed Test SOP Page 3 of 8 Pacific EcoRisk Environmental Consulting and Testing for the presence of amphipods. Remove amphipods into 150 mL of clean sea water. The sieve should be forcefully slapped against the surface of the water to ensure that all amphipods are dislodged. 4. Record the number of live, missing and dead amphipods for each test chamber. 6.0 REFERENCE TOXICANT TESTING To ensure that the organisms being used in the test are responding to chemical stress in a "typical" manner, a reference toxicant test can be performed concurrently with the effluent test. The reference toxicant results are then compared with an in-house data base to make this determination. Information regarding the reference toxicity test is presented in the "Eohaustorius Reference Toxicity Test SOP". 7.0 DATA ANALYSIS The endpoint data for each replicate, which are recorded on the appropriate data sheets, are entered into a CETIS TM v1.023 data file labeled for identification of the specific test. Statistical analyses are performed in accordance with EPA guidelines for statistical analysis. 8.0 TEST ACCEPTABILITY CRITERIA 1. Average survival of amphipods in control sediment must be>_ 90% at the end of the test. 2. Salinity,pH and ammonia in the overlying water and sediment grain size are within tolerance limits of test species. 9.0 QUALITY CONTROL 1. Control water, consisting of deionized water salted up to test salinity with Crystal Sea' sea salt, is used. 2. Test organisms shall be maintained in the laboratory 4-7 days prior to use in tests in order to monitor and examine them for health and quality. 3. Home sediment is used as quality controls for this test. 4. All equipment is calibrated and operated as described in each applicable equipment SOP. 5. All staff working independently on any test shall have previously demonstrated familiarity and competency with the test, analytical equipment used, and the corresponding SOPs. A trainee will initially conduct the test with supervision. The test can be conducted independently after a trainee has demonstrated appropriate competence in the following areas: familiarity with test procedures, use of analytical equipment required for test, and ability to retrieve animals from test replicates consistent with experienced staff. 10.0 SAFETY The Eohaustorius estuarius ten day sediment test poses little risk to those performing it. Sediments can contain pathogenic organisms and appropriate precautions should be observed when handling this material. Care should be taken in the preparation of the reference toxicant cadmium chloride. Review the MSDS for the reference toxicant. After the ref tox spiking solution has been used, any remaining solution should be appropriately stored for hazardous waste SOP#C030-1 10-D Eohaustorius Sed Test SOP Page 4 of 8 Pacific EcoRisk Environmental Consulting and Testing disposal. SOP#C030-1 10-D Eohaustorius Sed Test SOP Page 5 of 8 Pacific EcoRisk Environmental Consulting and Testing Summary of Test Conditions and Test Acceptability Criteria for the 10-Day Sediment Test Using the Amphipod, Eohaustorius estuarius (Test Method 100.4) 1. Test type Static whole sediment 2. Test duration 10 day 3. Temperature 15°C ±2°C 4. Salinity 20 ± 2 ppt 5. Light quality Ambient laboratory illumination 6. Light intensity 10-20 ycE/m2/s (50-100 ft-c) 7. Photoperiod Continuous, 24L:OD 8. Test chamber size 1000 ML 9. Seawater Volume 800 ml- 10. Sediment depth 2 cm (175 ml-) 11. Renewal of seawater None 12. Size of test organisms Juveniles, 3-5 mm 13. No. of organisms per test chamber 20 14. No. of rep. chambers per treatment 5 15. No. of organisms per sediment type 100 16. Feeding regime None 17. Test chamber cleaning Standard EPA wash procedures, none during test. 18. Test chamber aeration Rate of 100 bubbles/min 19. Overlying water Filtered (1 o m) seawater, dHZO salted up with Crystal Sea sea salt. 20. Test Materials Test sites,reference and control 21. Dilutions series None 22. Test Endpoint Mortality 23. Sampling and holding requirements < 8 weeks 24. Sample volume required 2.5 Liters 25. Test acceptability 90% or greater survival in controls SOP#C030-1 10-D Eohaustorius Sed Test SOP Page 6 of 8 Pacific EcoRisk Environmental Consulting and Testing Supplemental SOP Language Definitions: ACS: American Chemical Society ASAP : As soon as possible ASTM : American Society for Testing Materials °C : degrees Celsius dH20 : distilled water D.O.: dissolved oxygen ECx: Effective concentration in X% of the population. hrs : hours ICx: Inhibitory concentration in X% of the population. LCx: Lethal concentration in X% of the population. LOEC: Lowest Observed Effect Concentration mg : milligram mg/L : milligram per liter mL : milliliter NOEL: No Observed Effect Concentration NPDES : National Pollutant Discharge Elimination System S.O.P.: Standard Operation Procedure TIE: Toxicity Identification Evaluation U.S. EPA : United States Environmental Protection Agency Interferences: In an effort to eliminate interferences, SOPS have been established for every procedure involved in conducting a successful bioassay test. Additionally, a rigorous daily QA/QC inspection is designed to identify potential sources of interference. Prior to the initiation of toxicity tests every effort is made to identify and eliminate potential sources of interference that could compromise test results. These can include but are not limited to the following: clean and functional facilities, equipment and test chambers; sample storage and handling; test organism and food quality; laboratory water quality. Pollution Prevention As a pollution prevention measure, wastes generates during toxicity testing must be properly handled and disposed of in an appropriate manner. Care should be taken not to generate excessive wastes when preparing solutions for testing. All materials identified as hazardous should be labeled and appropriately stored for hazardous waste disposal. Data Assessment Bioassay and water quality data are assessed each day during the course of testing for accuracy and compliance with established criteria. At test termination,the data for each replicate, which are recorded on the appropriate data sheets, are entered into a CETIST" data file labeled for identification of the specific test. Statistical analyses are performed in accordance with EPA guidelines for statistical analysis. Control data for all endpoints are evaluated for compliance with SOP#C030-1 10-D Eohaustorius Sed Test SOP Page 7 of 8 Pacific EcoRisk Environmental Consulting and Testing established test acceptability criteria. Water Quality data are assessed for compliance with specifications outlined in the appropriate USEPA testing manuals. Corrective Actions and Contingencies for Out-of-Control Data If control performance is not met, a project manager should be notified immediately and, upon approval, the test is to be repeated. The potential cause(s) of poor control performance will be documented by scientific staff and evaluated and assessed by a project manager. Corrective actions will be determined on a case-by-case basis. The results of all tests will be summarized in reports for the regulatory authorities with an explanation of the results. SOP#C030-1 10-D Eohaustorius Sed Test SOP Page 8 of 8 Appendix D Attachment 5: Standard Operating Procedure for 48-Hour Bivalve Sediment Water Interface Paciflc EcoRisk Environmental Consulting and Testing Revision#2 Effective Date: December 8, 2002 Accepted: Mytilus edulis and Crassostrea Qigas Sediment-water Interface Bioassay with Bivalve Embryos Standard Operating Procedures This S.O.P. is based upon the Guidelines described in Anderson, B.S., J.W. Hunt, M. Hester, and B.M. Phillips. 1996. "Assessment of Sediment Toxicity at the Sediment-Water Interface, Chapter 3." Techniques in Aquatic Toxiclolgy. G.K. Ostrander, Ed. CRC Lewis Publishers. New York, New York and Short-Term Methods for Estimating the Chronic Toxicity of Effluents and Receiving Waters to West Coast Marine and Estuarine Organisms (EPA/600/R-95/136). This SOP also meets the requirements of ASTM Method E 724-89. 1.0 INTRODUCTION This test is based on a 48 hour exposure of Mytilus spp. or Crassostrea gigas embryos to sediments at the sediment-water interface. The test endpoints that are evaluated are% development. % survival is determined in the control treatment to assess test acceptability. This test can be applied to intact cores, composited sediments or formulated sediments. 2.0 TEST PREPARATION 2.1 Equipment and Supplies Needed Sediment Cores (10-cm id polycarbonate tubing),plastic core caps and exposure tubes (7.5-cm id polycarbonate tubing) Clean seawater(filtered Bodega Bay water is recommended) 8-12 "ripe" oysters or mussels 8-12 1 L beakers 9" X 13" glass spawning dish Hot plate-magnetic stirrer+ stirbar Thermometer Large volume erlenmeyer flask (4 or 6 L volume) 150 mL graduated cylinder Air pump, air hose, +pipet(for aeration) Microscope Hemacytometer+ Sedgewick-Rafter counting chamber Plunger+beaker for egg/embryo suspension and homogenization Pipettes or auto-pipettor 20 ml, glass or HD-polyethylene scintillation vials w/caps 5%glutaraldehyde solution(20 ml, of 25%glutaraldehyde + 80 ml, seawater) SOP# Page 1 of 6 Pacific EcoRisk Environmental Consulting and Testing ACS Reagent CUSO4 (Copper Sulfate), for use as reference toxicant. 2.2 Ordering and Holding of Test Organisms 1. Test organisms should be ordered far enough in advance so as to ensure arrival organisms on the day of test initiation Approximately 30-50 animals should be ordered, so as to allow for some attrition of organisms that are stressed from the shipping, etc. Order oysters/or mussels from: (1)- Tomalas Bay Oyster Co. (415) 663-1242 (2) - Carlsbad Aquafarms. (619)438-2444 2. For additional instruction on the receipt and handling of the test organisms, see the "Test Organism Receipt and Handling S.O.P." 2.3 Collection and Holding of Sediment Samples The type of sediment collection will depend on the nature of the study to be performed. In general, sediments samples are collected as intact cores or by using an Eckman dredge or similar sediment sampling device. This description is limited to a general description for the collection of intact sediment cores. Intact sediment cores are taken to eliminate any potential artifacts that may occur from the manipulation of sediment samples. Sediment cores are collected in the field and capped with site overlying water. The depth of the sediment core will be study dependent, however, at least a 4" depth is the standard that we use, resulting in at least 2" sediment depth remaining in the test exposure chamber; 4 replicates are typically collected from each site. The core is pressed into the sediments to the appropriate depth with an acrylic disc placed under the bottom of the core to prevent the loss of sediment or interstitial water when the sample is brought to the surface. Immediately upon removal from the sediment, the core is capped on the top and bottom with the overlying water maintained(the presence of overlying water verifies core integrity). The outside of the core is dried and the bottom wrapped in parafilm to prevent leakage. Samples are stored upright and immediately be placed on ice (or"blue ice"type product)to bring the temperature to 4 C. The sample should be shipped or transported to the testing laboratory ASAP. Upon receipt of the sample(s) in the laboratory, sample log-in measurements should be taken. For instruction on the log-in of incoming samples, see the "Sample Receipt/Control and Storage". 3.0 TEST INITIATION 3.1 Spawning and Fertilization 1. Obtain 8-12 "ripe" Crassostrea gigas or Mytilus from a commercial supplier. These organisms should be cleaned of any detritus or fouling organisms. Bivalves should be obtained no more than 24 hrs before start of test and should be maintained at a constant temperature (i.e. in an ice chest with blue ice) on top of seawater-soaked burlap or towels. 2. Place 3-3.5 L of seawater in large volume erlenmeyer flask and heat on the magnetic stirrer SOP # Page 2 of 6 Pacific EcoRisk Environmental Consulting and Testing until temperature reaches 30°C (20°C for mussels). 3. Place oysters or mussels in glass spawning dish and fill with the heated seawater until the bivlaves are submerged. 4. Monitor the seawater temperature in the spawning dish. When temperature falls below 27 C (20 C for mussels), replace with freshly heated seawater. 5. Monitor the bivalves for spawning activity. This is typically characterized by an active pumping of water, an increase in valve "clapping", and finally by the appearance of a whitish stream of gametes emerging from the animals. 6. As an oyster begins to spawn, the non-spawners should be removed from the dish,rinsed off, and placed in a fresh spawning dish with freshly heated seawater. Alternately, carefully transfer the spawner to a 1 L beaker of freshly heated seawater;this latter approach may be more desirable to ensure collection of unfertilized gametes. 7. The gametes of the early-spawning animals should be examined under the microscope. If the gametes are sperm, then aliquots of the sperm-seawater mix should be pipetted into the incurrent flow of the non-spawning oysters;the presence of this sperm often stimulates spawning in these remaining animals. 8. Steps 4-7 should be repeated until an adequate quantity of both sperm and eggs are made available. Gametes should be inspected under the microscope for sperm motility and egg development(this is especially important if the gametes were obtained by strip spawning, as described below). Eggs should be tear-shaped to somewhat roundish; sperm should be active. 9. Eggs and seawater should be transferred to the 250 mL graduated cylinder containing 20C seawater and aerated for 60-90 minutes for final egg maturation(this is not required for Mytilus eggs). 10. If the above steps are not successful in inducing spawning by the oysters, it will be necessary to strip the desired gametes (not performed for Mytilus), described in the following steps: a. Open the oysters with shucking knife and examine for gonadal material. b. With the jagged edge of a broken pipette (disposable variety), make several incisions into the gonad. With a clean pipette, wash the incised area with seawater and collect the released gametes. 3.2. Gamete Fertilization and Embryo Production 1. Examine and quantify the gametes. The sperm density is determined using a hemacytometer. The eggs are thoroughly mixed in suspension using the plunger-beaker apparatus and are then quantified using a Sedgewick-Rafter counting chamber. SOP# Page 3 of 6 Pacific EcoRisk Environmental Consulting and Testing 2. Add an appropriate amount of sperm to the eggs within the plunger-beaker apparatus so as to provide 5-10 sperm per egg. Every five minutes, mix the gametes-embryos with the plunger. Temperature should be maintained at 20°C during this time. 3. After 30 minutes, examine and quantify the embryos in a Sedgewick-Rafter counting chamber to determine % fertilization. Fertilized embryos are distinguished by the presence of polar bodies. A fertilization rate of approximately 75% is necessary to proceed with the experiment. If the fertilization rate is near 75%, then allow the embryo suspension an additional 30 minutes (with mixing, as before) and reexamine. If the fertilization rate does not meet the 75% requirement, start over. If it is decided that either the eggs or sperm are just not viable, it may be necessary to obtain gametes from different oysters. 3.3 Preparation of Test Chambers 1. Approximately 24 hours prior to initiation of toxicity tests, prepare each site replicate core by gently siphoning off the overlying water, leaving about 0.5-cm to minimize disturbance of the sediment surface. 2. Replace the overlying water with 500 ml, of fresh 0.22 µm filtered 32 ppt seawater(salinity can vary from 30-32 ppt depending on application of the test). Water is introduced to the core using and acrylic disk to minimize sample disturbance. 3. The following day, screen tubes are gently added to the cores and water quality for each replicate record. 4. For each replicate, record the initial water quality(pH, D.O., salinity, and temperature) onto the data sheets; check to make sure that all parameters, especially the D.O. are within acceptable levels. Test temperature is 20oC+ 1°C (18°C± 1°C for mussels) 3.4 Test Inoculation 1. A precise volume of the homogeneously mixed embryo suspension should be transferred(in a random order) into each test chamber to a concentration of 300 embryos/chamber in a random order. 2. Place the inoculated test cores into a temperature chamber at 20'C (18°C for mussels) for 48 hours. 4.0 MAINTAINING THE TEST 1. Hydrogen sulfide,total ammonia, dissolve oxygen(D.O.), pH, salinity are measured at the beginning and end of the test at the sediment water interface. 2. Dissolve Oxygen(D.O.), pH, salinity and temperature are measured daily in one replicate test SOP# Page 4 of 6 Pacific EcoRisk Environmental Consulting and Testing chamber in the overlying water. Temperature is also continuously measured in the waterbath. Any replicate were aeration is being performed and has been interrupted must have the D.O. levels measured immediately and recorded. 5.0. TEST TERMINATION After 48 hours (+6 hours), the embryos are gently washed from the SWIC apparatus into a 20 mL scintillation vial and are preserved by the addition of 1 mL of the 5% solution of glutaraldehyde. The vials can now be stored for later analysis. 6.0 TEST ENUMERATION 1. After fixation, the embryos should have settled to the bottom of the vial;this "concentration" makes it easy to collect an adequate number of embryos for counting. When ready to examine the embryos, carefully remove (by pipette)the top 3 mL of solution from the vial. With a I mL pipette, gently scrape the bottom of the vial while slowly filling the pipette. 2. Transfer the collected 1 mL to a Sedgewick-Rafter counting chamber and place on the microscope stand. 3. A count of both completely developed("D" shell) embryos and non-developed embryos is made while examining the counting chamber(as described in the next step). The control treatment vials should be examined first. 4. Examine the contents of the counting chamber. The search pattern should be to start at the upper left hand corner of the chamber, examining from left to right till the right side is reached. Then move the examination field down to the adjacent unexamined row field and proceed to the opposite side. Repeat this procedure until the entire chamber has been counted. This may require collecting and examining additional 1 mL samples from the vial. 5. Record the number of"normal" and "abnormal" embryos on the appropriate data sheets. 6. Dispose of the vial and any remaining contents. 7. If the percentage of"normal" embryos in the control treatment is <90%, the test is invalid and must be repeated. 7.0 DATA ANALYSIS Data are recorded on a standardized Bivalve Enumeration Data Sheet. Normal development in each treatment is compared to the appropriate reference control treatment. Statistical comparisons are made using the CETIS statistical package. SOP 4 Page 5 of 6 Pacific EcoRisk Environmental Consulting and Testing 8.0 REFERENCE TOXICANT TESTING To ensure that the organisms being used in the test are responding to chemical stress in a"typical" manner, a reference toxicant test is run side-by-side with the sediment water interface test. The reference toxicant results are then compared with an in-house/or existing database for that reference toxicant to make this determination. Once the various reference toxicant concentrations are prepared, test set-up, maintenance, and termination are identical to those above. See the reference Toxicant SOP 9.0 QUALITY CONTROL 1. Control water, consisting of 0.22 µm-filtered seawater, is used. 2. A clean sediment"positive control" or reference sediment can be used. A"negative" control can be performed using copper sulfate 3. All equipment is calibrated and operated as described in each applicable equipment SOP. 4. All staff working independently on any test shall have previously demonstrated familiarity and competency with the test, analytical equipment used, and the corresponding SOPs. 10.0 SAFETY The bivalve sediment-water interface toxicity test poses little risk to those performing it. Care should be taken in the preparation of the reference toxicant spiking solution. After the ref tox spiking solution has been used, any remaining solution should be appropriately stored for hazardous waste disposal. SOP# Page 6 of 6 Appendix D Attachment 6: Standard Operating Procedure for Benthic Infuana Assessment Benthic Infauna Community Analysis Standard Operating Procedures Version Date 08/07/06 If a benthic grab sample is accepted,the contents will be released into a sample tray and any sediments retained in the sampler will be rinsed into the tray using gentle hose spray. The sample will be placed in the sieve array, then slowly and carefully washed with pre- screened seawater to minimize damage to the specimens or contamination from benthopelagic organisms potentially entrained in the wash water. The samples will be screened through a 1.0-mm sieve screen. The retained material from each screen will be condensed and placed in separate containers each with a preprinted label identifying the station number of the sample. The screen mesh will be carefully examined and any organisms retained on the mesh will be carefully removed with forceps and placed in the sample containers. Sample containers will not be filled more than halfway with sample material to ensure proper fixation. The samples will be preserved with sufficient 37% buffered formalin to yield a 10% formalin in seawater solution. The sample containers will be gently rotated/inverted after fixation to ensure adequate fixative penetration throughout the sample sediment. All sample containers will be double-labeled inside and outside, logged on an MBC Chain-of-Custody Form, and safely stored in a plastic bucket or crate to avoid breakage. The samples will be transported to the MBC laboratory at the completion of the sampling effort and stored in a secure area until the samples are logged-in. The field team leader will relinquish the chain of custody form and the samples to the sorting supervisor and all associated sample-tracking forms will be placed in a fireproof file to await further processing. Upon return to the laboratory, the benthic samples will be logged-in on an MBC Sample Log and sample container labels verified with the MBC Chain-of-Custody Form relinquished by the MBC field team leader. The samples will be gently rotated/inverted during the log-in procedure to ensure adequate fixative penetration throughout the sample. The samples will be held in the buffered 10% formalin-seawater preservative for 48 to 72 hours and stored in a sample storage area. Utilizing MBC's Formalin Transfer Procedures, each sample will be re-screened on a 0.5-mm screen,the retained material transferred into 70% isopropyl alcohol, and returned to the storage area for sample processing. All samples will be processed. All biological organisms and fragments will be removed from the samples collected during the field surveys. These organisms will be gently transferred with forceps into pre-labeled vials containing 70% isopropyl alcohol and sorted into five phylogenetic classifications; crustaceans, echinoderms, mollusks, polychaetes, and minor phyla. Preprinted sample labels for each classification will be compared with the field labels and will include survey, date, station location, replicate, and organism type. The sorter will Benthic Infauna August 2006 Standard Operating Procedures initial the label to ensure label verification has been completed and for internal QA/QC for each sample. Any remaining sediment, shell or algal debris will be retained in a labeled container for internal QA/QC processing by MBC. A minimum 10% internal QA/QC resort will be performed on each sample by the sorting supervisor. All organisms sorted will be identified to the lowest practical taxonomic level, counted, and listed on a preprinted MBC Identification Lab Data Sheet. Each preprinted lab data sheet will include all sample identification data, which will be compared with the sample vial label for accuracy. Each lab data sheet will have the species identifications confirmed and the data sheet initialed by the lead taxonomist for each phyla prior to submitting the sheet to the data reduction staff. Taxonomic standardization QA/QC procedures include active participation of MBC taxonomic personnel in the Southern California Association of Marine Invertebrate Taxonomists (SCAMIT). SCAMIT maintains and regularly updates a list of standardized taxonomic names for infaunal species of the Southern California Bight,which is utilized by all regional taxonomists. In addition, MBC taxonomists maintain regular periodic contact with other SCAMIT members and are able to confer on species or species complexes that may be difficult to identify. Internal infaunal taxonomic QA/QC will consist of comparison of questionable species by MBC taxonomists with MBC's in-house voucher museum collection. MBC maintains an on-site, in-house voucher collection. Specimens contained in the collection undergo stringent scrutiny, verification by outside taxonomic experts, and must be consistent with the SCAMIT accepted name prior to inclusion in the MBC voucher collection. MBC's in- house voucher collection is more diverse and extensive than even the SCAMIT taxonomic listing. This is because MBC's biological work over the past 30 years has not been limited to only soft bottom, southern California, or 60 to 600-foot depths. After infaunal identifications have been completed, wet weight biomass for each of the five phylogenetic classifications will be determined for each replicate sample and recorded on a MBC Biomass Data Sheet. Each fraction will be placed into a tared weigh container with a 0.2-mm mesh screen bottom. The samples will be placed on blotter paper for five minutes to remove excess alcohol, and then weighed to the nearest 0.001 gram on an analytical balance. The weight of the tared container will be subtracted, and the wet weight of each fraction recorded. The biomass data sheets will be reviewed and initialed by the laboratory manager, and the data sheets submitted to the data reduction staff. Benthic infaunal field observations and laboratory data will be entered from MBC Lab Data Sheets and MBC Biomass Data Sheets into MS EXCEL spreadsheets. Each spreadsheet will include a description of the data including: sample number, location, date, filename, and the date that the data were entered. After data entry QC review, 100% of the data will be verified against the original field observation forms and laboratory data forms. Benthic Infauna August 2006 Standard Operating Procedures Appendix E Supporting Documents for Chemical Analysis Appendix E Attachment 1 : Standard Operating Procedure for Method 625 by GCMS CRG MARINE LABORATORIES 2020 Del Amo Blvd.,Suite 200,Torrance,CA 90501 (310)533-5190 SEPARATORY FUNNEL LIQUID-LIQUID EXTRACTION AND ANALYSIS BY GAS CHROMATOGRAPHY/MASS SPECTROMETRY Approved by: Rhonda Moeller, QA Officer Date Richard Gossett, Laboratory Manager Date Laboratory Operating Procedure Method 625, Revision E Page 1 of 18 METHOD 625: SEPARATORY FUNNEL LIQUID-LIQUID EXTRACTION AND ANALYSIS BY GAS CHROMATOGRAPHY/MASS SPECTROMETRY REFERENCES: U.S. EPA 40CFR Part 136 1.0 SCOPE AND APPLICATION 1.1 This method covers the extraction and concentration procedures required for the determination of chlorinated pesticides and PCBs and semi-volatile base/neutral and acid-extractable compounds in Laboratory Operating Procedure Methods (LOPM) 625. It is applicable to liquid samples. 1.2 The glassware cleaning procedure for extraction glassware is listed in this method. Table 1. Target Com ound List COMPOUND RETENTION METHOD TIME DETECTION DB-5 COLUMN LIMIT (pg/kg) D5-Phenol 8.00 (Recovery Surrogate) Naphthalene-d8 (Recovery 13.34 Surrogate) 2-Fluorophenol 15.00 (Recovery Surrogate) Acenaphthene-d10 (Recovery 21.49 Surrogate) 2,4,5,6-Tetrachloro-m-xylene 26.45 (Recovery Surrogate) 2,4,6-Tribromophenol 27.17 (Recovery Surrogate) PCB030 31.66 (Recovery Surrogate) Phenanthrene-d10 (Recovery 32.29 Surrogate) Anthracene-d10 32.84 Internal Standard PCB112 46.29 (Recovery Surrogate) 2,2'-5,5'-Tetrabromobiphenyl 52.07 Internal Standard Laboratory Operating Procedure Method 625, Revision E Page 2 of 18 Chrysene-d12 56.25 (Recovery Surrogate) PCB198 60.57 (Recovery Surrogate) Perylene-d12 68.49 (Recovery Surrogate) a Phenol 8.21 100 2-Chloro henol 10.56 50 Aniline 11.37 100 2,4-Di meth I phenol 11.11 100 bis 2-Chloroetho methane 11.44 50 1,3-Dichlorobenzene 11.98 10 1,4-Dichlorobenzene 12.13 10 1,2-Dichlorobenzene 12.39 10 Benz I Alcohol 12.23 100 2-Nitro phenol 12.41 100 bis 2-Chloroiso ro I ethane 12.61 50 2,4-Dichloro henol 12.83 50 N-nitrosodi-n- ro lamine 12.95 50 N-nitrosodimeth lamine 12.97 50 Hexachloroethane 13.15 50 Nitrobenzene 13.32 50 Naphthalene 13.39 1.0 Iso horone 13.99 50 Dichlorvos 14.52 10 bis 2-Chloroeth I ether 14.59 50 1,2,4-Trichlorobenzene 14.81 10 Benzidine 15.31 50 4-Ch loro-3-meth I phenol 15.59 100 4-Chloroaniline 15.74 50 2-Meth Ina hthalene 15.98 1.0 Hexachlorobutadiene 16.24 50 1-Meth Inaphthalene 16.39 1.0 2,4,6-Trichloro henol 17.42 50 Benzoic Acid 17.70 100 Biphenyl 18.30 1.0 2,6-Di methyl naphthalene 19.05 1.0 Mevin hos 19.55 10 Hexachloroc clo entadiene 19.83 50 Acena hth lene 20.47 1.0 Dimeth I Phthalate 20.56 5 Acena hthene 21.74 1.0 4-Nitroaniline 21.82 50 Laboratory Operating Procedure Method 625, Revision E Page 3 of 18 2,4-Dinitro henol 22.27 100 4-Nitro phenol 23.30 100 2,3,5-Tri methy Ina phtha lene 24.42 1.0 3-Nitroaniline 24.57 50 Fluorene 25.18 1.0 Diethyl Phthalate 25.45 5 2,6-Dinitrotoluene 25.89 50 2-Meth I-4,6-dinitro henol 26.04 100 Dibenzofuran 26.12 50 Demeton 26.21 10 2,4-Dinitrotoluene 26.55 10 Ethoprop 26.83 10 4-Chloro hen I phenyl ether 28.97 50 2-Nitroaniline 29.13 50 Phorate 29.17 10 N-nitrosodi hen famine 30.04 50 Azobenzene 30.21 50 Dimethoate 30.60 5 Pentachloro henol 31.70 50' Phenanthrene 32.67 1.0 4-Bromo hen I phenyl ether 32.96 50 Anthracene 32.96 1.0 al ha-BHC 33.26 1.0 Diazinon 33.48 5 Disulfoton 33.65 10 Hexachlorobenzene 33.90 1.0 beta-BHC 35.29 1.0 gamma-BHC 35.79 1.0 Methyl Parathion 36.69 10 delta-BHC 37.56 1.0 Fenchloro hos 37.91 10 1-Meth I henanthrene 38.01 1.0 Dibut I Phthalate 39.46 5 Marathion 39.91 5 Fenthion 40.38 10 Chlorpyrifos 40.53 5 Heptachlor 41.36 1.0 Trichloronate 41.44 10 Fluoranthene 42.98 1.0 Aldrin 43.99 1.0 P rene 44.85 1.0 Tetrachlorvin hos 45.61 10 Tokuthion 46.91 10 Heptachlor Epoxide 47.00 1.0 Laboratory Operating Procedure Method 625, Revision E Page 4 of 18 Bolstar 47.40 10 gamma-Chlordane 48.77 1.0 2,4'-DDE 49.18 1.0 Endosulfan 1 49.69 1.0 alpha-Chlordane 49.91 1.0 Fensulfothion 50.10 10 trans-Nonachlor 50.29 1.0 4,4'-DDE 51.50 1.0 Mer hos 51.55 10 Dieldrin 51.61 1.0 2,4'-DDD 52.11 1.0 But Ibenz I Phthalate 53.13 5 Endrin 53.19 1.0 Endosulfan II 53.84 1.0 4,4'-DDD 54.53 1.0 2,4'-DDT 54.79 1.0 Endrin Aldehyde 55.20 1.0 Benz a anthracene 56.25 1.0 Chrysene 56.52 1.0 Endosulfan Sulfate 56.93 1.0 4,4'-DDT 57.24 1.0 bis- 2-eth the I Phthalate 59.24 5 Endrin Ketone 60.23 1.0 Guthion 60.47 10 Couma hos 60.52 10 Methox chlor 61.36 1.0 M i rex 64.27 1.0 Di-n-oct I Phthalate 64.71 5 Benzo b fluoranthene 65.47 1.0 Benzo k fluoranthene 65.87 1.0 Benzo e rene 67.71 1.0 Benzo a rene 68.07 1.0 Perylene 68.77 1.0 3,3'-Dichlorobenzidine 72.45 50 Indeno 1,2,3-c,d rene 76.29 1.0 Dibenz a,h anthracene 76.68 1.0 Benzo[g,hj]perylene 77.87 1.0 PCBs By Congener 1 PCBs By Aroclor 10 Laboratory Operating Procedure Method 625, Revision E Page 5 of 18 2.0 SUMMARY OF METHOD A measured volume of sample, usually 2 liters, is serially extracted with methylene chloride at pH >11 and again at pH <2 using a separatory funnel. The methylene chloride extract is concentrated in preparation for instrumental analysis. Samples are to be stored at 4 °C, extracted within 7 days of collection, and analyzed within 40 days of extraction. A 1-3 pL sample is injected into a gas chromatograph (GC) equipped with a mass selective detector. The GC is temperature programmed to separate the compounds and confirmation is achieved for the single component peaks using ions specific to each target compound. Compounds eluting from the GC are identified by matching the retention times of the unknown peaks with those from a known calibration standard and the concentration of each identified component is measured by comparison of the responses. 3.0 PREVENTION OF INTERFERENCES 3.1 Solvents, glassware, and other processing apparatus are to be free of any interferences. A procedural blank is be analyzed with each sample batch to demonstrate the absence of any method interferences. 3.2 High purity solvents are to be used to minimize interferences. 3.3 Phthalate esters and PCBs are contaminants found in many types of products commonly used in the laboratory. Care should be taken to avoid or eliminate the use of plastic products during sample processing and handling. 3.4 Impurities in the carrier and makeup gases may be avoided by using Ultra-High purity gases and/or gas purifying cartridges. See the instrument manufacturer for guidelines. 3.5 Contamination by carryover may occur whenever high level and low- level samples are sequentially analyzed. To reduce carryover, the syringe used for sample injection shall be rinsed a minimum of 5 times between samples using n-hexane. Whenever possible, samples shall be analyzed from low to high concentrations. 3.6 A procedural blank shall be analyzed with each batch of 20 or less samples to check for contamination during sample processing. 4.0 SAFETY Laboratory Operating Procedure Method 625, Revision E Page 6 of 18 4.1 It is mandatory to wear a laboratory coat, closed-toe shoes and safety glasses in the laboratory. Gloves are to be worn when working with samples. 4.2 All glassware cleaning and extraction procedures involving any solvent exposure shall take place in a fume hood. Use of a respirator and appropriate safety gloves are recommended for working with solvents. 4.3 Material Safety Data Sheets (MSDS) are on file in the laboratory and are available to all personnel involved in the use of hazardous materials during any procedure. 4.4 Extreme caution and the proper use of safety equipment are required during the handling of any hazardous material. If the analyst has any questions regarding safety, he or she should contact a supervisor or the laboratory director prior to the start of this procedure. 5.0 APPARATUS AND MATERIALS 5.1 Glassware A. Separatory funnel: 2 L, with Teflon stopcock B. Round-bottom flasks: 250 mL C. Pear-shaped flasks: 25 mL D. Graduated cylinder: 100 mL E. Erlenmeyer flask: 1 L F. Glass filter funnel G. Pasteur pipettes H. Gastight volumetric syringes: 100, 500 µL I. Autosampler vials with Teflon-lined screw caps: 2 mL 5.2 Glass wool 5.3 pH indicator paper: pH 0-6 5.4 Graduated cylinder: 2 L Laboratory Operating Procedure Method 625, Revision E Page 7 of 18 5.5 Heavy duty aluminum foil 5.6 Roto-evaporator system with aspirator pump and water bath set at 30 ± 5°C 5.7 Chiller unit set at 10 ± 5°C or cool tap water 5.8 High-temperature oven set at 1000 ± 50 OF 5.9 Non-ionic detergent 5.10 Shimadzu GC2010 GC equipped with a Mass Selective Detector, an AOC 20i Low-volume Autosampler and split/splitless injector or an Agilent 6890 GC equipped with a Mass Selective Detector (5973 or 5975), a 7683/7683b Low-volume Autosampler and a split/splitless injector. 5.11 J&W Scientific DB5 Column (or equivalent), 30 meters in length, 0.25 pm film thickness, and 0.25 mm I.D 5.12 10 pL syringe for the AOC20i/7683/7683b Autosamplers 5.13 Ultra-high purity helium 5.14 Fused Silica Retention Gap, 5 meters in length, 0.53 mm I.D. 6.0 REAGENTS 6.1 Deionized water 6.2 Pesticide grade hexane and methylene chloride 6.3 Method 625 spike solutions prepared from stock solutions obtained from an accredited supplier. The solution used is dependent on the clients target analyte list. ■ Chlorinated Pesticides ■ PCB Congeners ■ Base/Neutral Extractables ■ Acid Extractables 6.4 Anhydrous granular sodium sulfate 6.5 Concentrated sulfuric acid Laboratory Operating Procedure Method 625, Revision E Page 8 of 18 6.6 Stock solutions. All stock solutions are purchased from NIST traceable commercial suppliers. Store at or below 4 °C and protect from light. Stock standards shall be replaced after one year or sooner if comparison with check standards indicates a problem. 6.7 Calibration Standards. Prepare a minimum of five concentration levels for each parameter of interest. One of the concentration levels shall be near the method detection limit. The remaining concentration levels shall bracket the expected concentrations found in the samples. Calibration solutions shall be replaced after 6 months or sooner if a problem is indicated. 6.8 Internal Standards. Select one or more internal standards that are similar in analytical behavior to the compounds of interest. The analyst shall demonstrate that the selected compound(s) is not affected by the method or matrix interference. 6.8.1 Just prior to analysis, add a known constant amount of internal standard to all calibration solutions, blanks, and samples. 6.9 Recovery Surrogates. Select one or more internal standards that are similar in analytical behavior to the compounds of interest. 6.9.1 Prior to the extraction of the samples, add a known amount of recovery surrogate to all blanks and samples. See Methods 3510 and 3545 for additional information about this procedure. 6.10 Sodium Hydroxide 7.0 CALIBRATION AND MAINTENANCE 7.1 Shimadzu QP2010 or Agilent 6890 GC/MS 7.1.1 GC Oven Operating Conditions: Initial Oven Temperature =45 °C Initial Hold = 5 min Ramp 1 = 20 °C/min to 125 °C Hold Time = 0 min Ramp 2 = 2.5 °C/min to 285 °C Hold Time = 17 min 7.1.2 Injector Operating Conditions: Injector = Splitless or On-Column Mode = Track Oven Temperature (On-Column Only) Laboratory Operating Procedure Method 625, Revision E Page 9 of 18 Nominal Initial Pressure = 23.5 psi (on) 7.1.3 Column Operating Conditions: Max Temp = 325 °C Mode = Constant Flow Initial Flow = 1.5 mL/min Average Carrier Velocity = 40 cm/sec Carrier Gas = Helium 7.1.4 Detector Operating Conditions: Transfer Line Temperature = 285 °C Ionization Voltage = 70 ev Gain = +100 to +300 volts over standard sensitivity target tune 7.1.5 Autosampler Operating Conditions (Back Injector): Sample Washes = 2 Sample Pumps = 2 Injection Volume = 2.0 pL Syringe Size = 10 pL Post Injection Washes Solvent A = 3 Post Injection Washes Solvent B = 3 Plunger Speed = Fast 7.1.6 System Maintenance Prior to each set of samples, remove ca. 30 cm of the retention gap or column, replace injector septum if needed, and refill the solvent wash bottles. Clean glass inlet liners or replace as needed. Replace the gas cartridges every 6 months. Replace the GC columns as needed. Enter all maintenance actions into the instrument maintenance logbook. 8.0 QUALITY CONTROL 8.1 With each batch of samples (maximum 20 samples per batch), a procedural blank is extracted and analyzed to demonstrate that procedural interferences are under control. Deionized water is used as the blank matrix. Laboratory Operating Procedure Method 625, Revision E Page 10 of 18 8.2 With each batch of samples, a duplicate sample and/or matrix spike/matrix spike duplicate (MS/MSD) set of samples is analyzed with the appropriate extraction procedure to measure the precision of the extraction procedure. A non-spiked sample of an MS/MSD set is analyzed to determine background concentrations for each parameter of interest. The MS/MSD samples are spiked with specific parameters at a concentration greater than ten times the method detection limit and analyzed to determine the percent recovery of the spiked compounds. For concentrations at ten times the method detection limit, a precision factor between the duplicate samples or MS/MSD samples is calculated and compared to the corresponding QC acceptance criteria. 8.3 Every sample, spike set, and blank is spiked with an appropriate surrogate spike solution consisting of 1 to 6 surrogate compounds. The surrogate spike is used to demonstrate the efficiency of the extraction and analytical procedure by allowing calculation of the percent recovery of each surrogate compound. Control charts and control limits are generated by measuring the mean and standard deviation of the surrogate percent recovery for the previous 20 samples. Upper and lower warning limits are calculated at two times the standard deviation from the mean. Upper and lower control limits are calculated at three times the standard deviation from the mean. Surrogate control limits and results are presented with the analytical results. When surrogate results indicate atypical method performance, a quality control check sample is analyzed and an evaluation of the procedure and instrumentation is made. 8.4 If any individual parameter falls outside of the designated range for percent recovery, that parameter has failed the acceptance criteria. An evaluation of the method procedure and instrumentation shall be made to uncover evidence of any atypical performance. If there is atypical performance of the method procedure and/or instrumentation, the problem shall be immediately identified and corrected prior to the analysis of any further samples. A re-spike and/or quality control check sample shall be analyzed and evaluated. If possible, all samples from the suspect batch shall be re-analyzed under corrected method conditions. If samples can not be re- analyzed, the analytical results for the non-spiked samples are suspect and shall be reported with the result flagged and followed by an explanation of the problem. Laboratory Operating Procedure Method 625, Revision E Page 11 of 18 8.5 QA/QC records are maintained to document the quality of data generated. If any constituent falls outside the designated range, that compound has failed the acceptance criteria. Failure to meet the stated requirement shall require that corrective action be taken to eliminate the problem prior to the analysis of any samples. Samples from the batch being analyzed at the time the failure is detected shall be reanalyzed after the corrective action has been taken. A batch is defined as 20 or less samples. If any sample cannot be reanalyzed, the result for that element shall be flagged and a detailed report is included with the result. 8.5.1 Initial Calibration Check- Prior to analyzing any samples, using a second-source calibration standard an initial calibration of the instrument is performed with each batch of samples. This calibration shall be within 15% of the initial calibration curve. 8.5.2 Calibration Check- Using a second-source calibration standard, a calibration check will be performed every 12 hours and at the end of every batch of samples. The calibration check shall be within 15% of the initial calibration curve. 8.5.3 Matrix Spikes- Matrix spike and matrix spike duplicates as well as duplicate samples shall be analyzed with each batch of samples to determine the precision for each compound. A control chart is generated to document the precision. Control limits are established by using the mean and standard deviation from 20 results. Upper and lower warning limits are two times the standard deviation and upper and lower "out of control" limits are three times the standard deviation for those compounds that are greater than 10 times the method detection limit. 8.5.4 CRM/LCM- Certified reference materials and/or lab control materials shall be analyzed with each batch of samples. The reported value shall be within the limits set forth by the agency providing the material. 8.5.5 Blanks- Lab reagent blanks shall be analyzed with each batch of samples. No compound shall be detected at greater than 3 times the method detection limit. 8.5.6 QCS- A method standard is extracted along with each batch of samples. Prepare the QC check standard to 1 L of reagent water. Laboratory Operating Procedure Method 625, Revision E Page 12 of 18 8.5.6 Internal Standards- Internal standards shall be added in known amounts to blanks, calibration standards, continuing calibration check solutions, and samples to compensate for instrumental drift. 8.5.7 Recovery Surrogates- Recovery surrogates shall be added in known amounts to all blanks and samples to indicate sample processing efficiency. Sample results shall not be adjusted for surrogate recovery efficiency unless specifically requested by the client. 8.5.8 Daily GCMS Performance Test- At the beginning of each batch of samples, the GCMS system must be checked to see of acceptable performance criteria are achieved for DFTPP. The criteria are presented in the following table. Mass m/z Abundance Criteria 69 0-100 percent of Mass 198 70 < 2 percent of Mass 69 127 40-60 percent of Mass 198 198 Base peak, 100 percent relative abundance 199 5-9 percent of Mass 198 275 10-30 percent of Mass 198 365 > 1 percent of Mass 198 441 Present but < Mass 443 442 > 40 percent of Mass 198 443 17-23 percent of Mass 442 9.OSAMPLE COLLECTION, PRESERVATION, AND HANDLING 9.1 All samples are collected in amber glass jars with Teflon-lined screw caps. All samples are kept at 4 ± 2 °C from the time of collection until extraction. 9.2 If Residual Chlorine is present, add 80mg of sodium thiosulfate per liter of sample and mix well. Please refer to the SOP for Residual Chlorine determination. 10.0 PROCEDURE 10.1 Glassware cleaning procedure: High-temperature oven option Wash glassware with non-ionic detergent and water. Rinse glassware thoroughly with tap water, then rinse once with deionized Laboratory Operating Procedure Method 625, Revision E Page 13 of 18 water. Place glassware in high temperature oven and bake at a minimum of 1000 ± 50 OF for 2 hours according to the following conditions: Set initial temperature ramp to 536°C over 1 hours then hold for 3 hours. Once the oven program shuts off, the oven begins to cool back down to 30 °F. Consecutive oven runs can be done once the oven has cooled to less than 150 °F. CAUTION: Do not open oven door or turn off blower until over temperature is below 570 °F. Once the glassware has cooled, cover all exposed areas that will touch the sample with aluminum foil or place it upside down onto foil until use. 10.2 Glassware cleaning procedure: Solvent rinse option Wash glassware with non-ionic detergent and water. Rinse glassware thoroughly with tap water, then rinse once with deionized water. Let dry, then use Teflon squeeze bottles to rinse three times with methylene chloride and three times with hexane. 10.3 Sodium sulfate cleaning procedure Clean sodium sulfate either by heating in the high-temperature oven using the same program as the glassware cleaning procedure or by rinsing with several mLs of methylene chloride. 10.4 Glass wool cleaning procedure Clean glass wool either by heating in the high-temperature oven using the same program as the glassware cleaning procedure or by rinsing with several mLs of methylene chloride. 10.5 Sample extraction 10.5.1 Remove sample from the refrigerator and bring to room temperature. 10.5.2 Decant some of the sample into the sink, if necessary, to allow for the addition of solvent. Laboratory Operating Procedure Method 625, Revision E Page 14 of 18 10.5.3 Use a gas-tight volumetric syringe to pipette the appropriate QC surrog tes into the sample. The surrogate solution(s) should be at room temperature prior to use. Record the sample ID, name and volume of surrogate used, standard solutions logbook page number containing details of solution preparation, and analyst initials in the laboratory notebook. 10.5.4 For matrix spike/matrix spike duplicate samples, use a gas- tight volumetric syringe to pipette the appropriate QA/QC spikes into the sample. The spike solution(s) should be at room temperature prior to use. Record the sample ID, name and volume of spike used, standard solutions logbook page number containing details of solution preparation, and analyst initials in the laboratory notebook. 10.5.5 Adjust the pH to >11 using NaOH solution. Then use the 100 mL graduated cylinder to measure 100mL of methylene chloride and add it directly to the sample bottle. Recap the bottle tightly and shake it continuously and vigorously for at least 2 minutes. 10.5.6 Allow the sample bottle to sit untouched for 5 minutes so that the organic solvent and aqueous layers can separate. 10.5.7 Decant approximately half of the sample into the 2 L Erlenmeyer flask and the remainder, including the solvent layer, into the separatory funnel. Allow the organic and aqueous layers in the separatory funnel to separate for 5 minutes. 10.5.8 Prepare the collection flask as follows: Place a small amount of glass wool into the bottom of a glass filter funnel, then add approximately 50 g of anhydrous sodium sulfate. Place the funnel into the neck of a 250 mL round bottom flask. 10.5.9 Filter the solvent extract through the sodium sulfate and collect it in the 250 mL round bottom flask. 10.5.10 Add 75 mL methylene chloride to the empty sample bottle and swirl it around thoroughly to wash down the walls of the bottle. Pour the sample portions from the Erlenmeyer flask and the separatory funnel back into the sample bottle and repeat the shaking step in 10.4.5. Allow for layer separation, decant, and collect the extract in the same 250 mL flask. Laboratory Operating Procedure Method 625, Revision E Page 15 of 18 10.5.11 For samples being analyzed only for Base/Nuetral compounds only, the third extraction is identical to the second. For samples being analyzed for acid extractable compounds, adjust the sample pH to less than 2 by adding a small amount of concentrated sulfuric acid prior to the shaking step of the third extraction. The third extraction is otherwise identical to the second. 10.5.12 After the third extraction is complete, measure the total volume of the sample using the 2 L graduated cylinder and record it in the laboratory notebook. 10.6 Sample concentration 10.6.1 Prepare the roto-evaporator for use according to the following parameters: water bath temperature at 30 ± 5 °C chiller temperature at 10 ± 5 °C or cool tap water 10.6.2 Attach the 250 mL round bottom flask to the distillation trap and secure it with a plastic spring clip. 10.6.3 Close the stopcock and lower the flask into the water bath. Turn on the roto-evaporator motor and adjust the rotation to a medium speed. Adjust the vacuum so that no solvent flashes up into the distillation trap. 10.6.4 Concentrate the sample to approximately 10 mL. Break the internal vacuum by opening the stopcock. Stop the motor, raise the arm, and remove the flask from the trap. 10.6.5 Use a Pasteur pipette to transfer the sample to a 25 mL pear-shaped flask. Rinse the 250 mL flask three times with approximately 1 mL methylene chloride and transfer each rinse to the 25 mL flask. 10.6.6 Attach the 25 mL pear-shaped flask to the distillation trap using the adaptor and concentrate the sample to approximately 500 µL. Take care not to let the sample go to dryness. 10.6.7 Transfer the sample to an autosampler vial using a Pasteur pipette. Rinse the 25 mL flask three times with approximately Laboratory Operating Procedure Method 625, Revision E Page 16 of 18 250 µL methylene chloride, transfering each rinse to the autosampler vial. 10.6.8 The sample extract is now ready for instrumental analysis. 10.7 Using the Shimadzu/Agilent data system, load the appropriate method for the parameters of choice. 10.8 Using the Shimadzu/Agilent data system, set up a sequence table for the analysis of the samples. The sequence table should include all calibrations necessary for five calibration levels of each parameter of interest, the recovery surrogate solution, a calibration check solution for every 12 hours of operation, and all blanks and samples. 10.9 Place the vials in the autosampler tray insuring that they are in the same order as the sequence table. 10.10 Load and run the sequence file and insure that the autosampler operates correctly. 10.11 From the results of the calibrations, build a calibration table. 10.120nce the calibration table is completed, load the result file for each sample and print the appropriate report. 11.0 CALCULATIONS 11.1 The qualitative identification of compounds determined by this method is based on retention time matching. Results are confirmed by quantification using a specific mass for each compound and comparison wiith the retention times. 11.2 An internal standard calibration procedure is used by calculating the relative response factor (RRF) for each analyte using the following formula: (AX)(Cis) RRF = (Ais)(Cx) Where: AX= Area of the Target Analyte Peak Cis = Mass of the Internal Standard A,s = Area of the Internal Standard Peak Cx = Concentration of the Target Analyte Laboratory Operating Procedure Method 625, Revision E Page 17 of 18 11.3 The quantitation of each analyte of interest shall be based on the area of the peak of each ion at the retention corresponding to the calibration standard. The concentration is calculated using the following formula: (AUNK)(CIS) Concentration = (AIS)(RRFTA)(SW) Where: AUNK = Peak area of the sample CIS = Mass of the Internal Standard AIS = Area of the Internal Standard Peak RRFTA = Relative Response Factor for the Target Analyte SW= Weight of sample extracted 11.4 The Method Detection Limit (MDL) is defined as the minimum concentration of a compound that can be measured and reported with 99% confidence that the value is greater than zero. The MDLs listed in Table 1 were determined using a clean marine sediment sample following US EPA guidelines in 40CFR. Laboratory Operating Procedure Method 625, Revision E Page 18 of 18 Appendix E Attachment 2: Standard Operating Procedure for Method 2540G 1 : Percent Solids Determination For Sediments CRG MARINE LABORATORIES 820 S.Seaside Avenue,Terminal Island,CA 90731,(310)519-4007 PERCENT SOLIDS DETERMINATION FOR SEDIMENT SAMPLES Approved by: Rhonda Moeller, QA Officer Date Richard Gossett, Laboratory Manager Date Laboratory Operating Procedure Method 2540G1, Revision A Page 1 of 5 METHOD 2540G1: PERCENT SOLIDS DETERMINATION FOR SEDIMENTS REFERENCE: Standard Methods for the Examination of Water and Wastewater, Section 2540, 19th Ed., 1995. 1.0 SCOPE AND APPLICATION 1.1 This method covers the determination of percent solids (i.e. dry/wet ratio) for sediment samples. 1.2 The approximate detection limit for this method, based on a 20 g wet sediment sample, is 0.1%. 2.0 SUMMARY OF METHOD A measured mass of wet sediment is dried to constant weight in a convection oven at 105 ± 5 °C. The dry/wet mass ratio obtained is multiplied by 100% to give percent solids. 3.0 PREVENTION OF INTERFERENCES 3.1 Sediment samples should be completely thawed and thoroughly homogenized before use. 4.0 SAFETY 4.1 It is mandatory to wear a laboratory coat, closed-toe shoes and safety glasses in the laboratory. Gloves are to be worn when working with samples. 4.2 Extreme caution, awareness, and the proper use of equipment are required. Care should be taken when reaching into a hot oven. If the analyst has any questions regarding safety, he or she should contact a supervisor or the laboratory director prior to the start of this procedure. 5.0 APPARATUS AND MATERIALS Laboratory Operating Procedure Method 2540G1, Revision A Page 2 of 5 5.1 Analytical balance 5.2 Numbered aluminum weighing boats 5.3 Convection oven: set at 105 ± 5 °C 5.4 Desiccator 6.0 REAGENTS This section is not applicable to this method. 7.0 CALIBRATION AND MAINTENANCE 7.1 An analytical balance calibration check is to be performed prior to the implementation of this method. Refer to LOPM 0200. 8.0 QUALITY CONTROL 8.1 With each batch of samples (maximum 20 samples per batch), a procedural blank is processed to demonstrate that procedural interferences are under control. The blank consists of an empty aluminum weighing boat. 8.2 With each batch of samples, a duplicate sample is processed to give an indication of the precision of the method. For percent solids at or above ten times the method detection limit, a precision factor between the duplicate samples is calculated and compared to the corresponding QC acceptance criteria. 9.0 SAMPLE COLLECTION, PRESERVATION AND HANDLING This section is not applicable to this method. 10.0. PROCEDURE 10.1 Remove a batch of sediment samples from the refrigerator or freezer and bring them to room temperature. Laboratory Operating Procedure Method 2540G1, Revision A Page 3 of 5 10.2 Clean the aluminum weighing boats by placing them in the convection oven, set at 105 °C, for 1 hour. 10.3 Remove the pans from the oven and allow them to cool completely. 10.4 Perform a calibration check on the analytical balance and recalibrate it if necessary. Refer to LOPM 0020. 10.5 Tare the balance, then place an aluminum weighing boat on the balance pan. Record its number and mass in the laboratory notebook. 10.6 Place approximately 20 grams of a thoroughly homogenized wet sediment sample into the boat, recording the sample ID and gross weight (boat + sediment) in the laboratory notebook. 10.7 Repeat steps 10.5 and 10.6 for each sample in the batch (omit step 10.6 for the blank). 10.8 Place the samples into the 105 °C convection oven for 24 hours. 10.9 Remove the samples from the oven, place them in a desiccator, and allow to cool completely. 10.10 Measure the mass of each sample and record it in the laboratory notebook. 10.11 Place the samples back into the oven for 2 hours or until the mass measured after complete cooling is within ±0.02 g of the mass measured in step 10.10. Record this mass in the laboratory notebook. 11.0 CALCULATIONS The solids content of a sediment sample is reported as a percentage and is calculated as: % solids= and —Mb x 100% MW —Mb where and = mass of aluminum boat plus dry sediment [g] (step 10.11) Mb = mass of aluminum boat [g] (step 10.5) m, = mass of aluminum boat plus wet sediment [g] (step 10.6) Laboratory Operating Procedure Method 2540G1, Revision A Page 4 of 5 Laboratory Operating Procedure Method 2540G1, Revision A Page 5 of 5 Appendix E Attachment 3 : Standard Operating Procedure for Method 3610/3630: Column Clean-Up and Chromatographic Separation CRG MARINE LABORATORIES 2020 Del Arno Blvd Ste 200,Torrance,CA 90501,(310)533-5190 Column Clean-up and Chromatographic Separation Approved by: Rhonda Moeller, QA Officer Date Richard Gossett, Laboratory Manager Date Laboratory Operating Procedure Method 3610/3630, Revision B Page 1 of 7 METHOD 3610/3630: Column Clean-up and Chromatographic Separation 1.0 SCOPE AND APPLICATION This method is a procedure for performing sample clean-up and chromatographic separation of aliphatic hydrocarbons (Ahs), polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), chlorinated pesticides (DDTs) and linear alkyl benzenes (LABs) from biological tissues, marine sediments water column particles, sediment interstitial water, and other aqueous samples. 2.0 SUMMARY OF METHOD A column is packed with the required amount of adsorbents (Alumina/Silica) and the sample is introduced into the column. The desired fractions of analytes are eluted using suitable solvents. The eluated are then concentrated for GC/MS analysis. 3.0 PREVENTION OF INTERFERENCES 3.1 Solvents, glassware, and other processing apparatus are to be free of any interferences. A procedural blank is be analyzed with each sample batch to demonstrate the absence of any method interferences. 3.2 High purity solvents are to be used to minimize interferences. 3.3 Phthalate esters and PCBs are contaminants found in many types of products commonly used in the laboratory. Care should be taken to avoid or eliminate the use of plastic products during sample processing and handling. 3.4 Column saturation can reduce analyte recoveries. To avoid column saturation divide 25,000 by the Theoretical Lipid wt. (Theoretical Lipid wt. Is determined by gravimetric analysis.) of the sample. This will give you the volume of sample in µL that will saturate the column. Adjust the number of columns needed for clean up accordingly. Laboratory Operating Procedure Method 3610/3630, Revision B Page 2 of 7 4.0 SAFETY 4.1 It is mandatory to wear a laboratory coat, closed-toe shoes and safety glasses in the laboratory. Gloves are to be worn when working with samples. 4.2 Use of a respirator and appropriate safety gloves are recommended for working with solvents. 4.3 Material Safety Data Sheets (MSDS) are on file in the laboratory and are available to all personnel involved in the use of hazardous materials during any procedure. 4.4 Extreme caution and the proper use of safety equipment are required during the handling of any hazardous material. If the analyst has any questions regarding satety, he or she should contact a supervisor or the laboratory director prior to the start of this procedure. 5.0 APPARATUS AND MATERIALS 5.1 Glassware A. Chromatography column: 11 x 300 mm and a Teflon stopcock. B. Pear-shaped flasks: 75 mL, 100 mL C. Graduated cylinder: 25 mL,50 mL D. Pasteur pipettes or Gastight volumetric syringes: 1000 µL E. Glass beaker, 50 mL 5.2 Autosampler vials with Teflon-lined screw caps: 2 mL 5.3 Baked Glass wool 5.4 Roto-evaporator system with aspirator pump and water bath set at 35 ± 5°C 5.5 Chiller unit set at <5 °C or cool tap water 5.6 High-temperature kiln set at 535°C 5.7 Non-ionic detergent Laboratory Operating Procedure Method 3610/3630, Revision B Page 3 of 7 6.0 REAGENTS 6.1 Methylene Chloride 6.2 30% Methylene Chloride/Hexane 6.3 Hexane 6.4 Silica gel: 60 — 200 mesh 6.5 Alumina: 60 — 325 mesh 7.0 CALIBRATION AND MAINTENANCE This section is not applicable to this method. 8.0 QUALITY CONTROL 8.1 A procedural blank is processed for every batch of newly prepared adsorbents. 9.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING 9.1 Cover/line all working area with aluminum foil and be sure there is a fresh piece of aluminum foil for all syringes and other implements to rest. 10.0 PROCEDURE 10.1 Preparation of Adsorbents 10.1.1 To a 1-L beaker add approximately 350g of silica gel and 900 mL of redistilled methanol. 10.1.2 To another 1-L beaker add 500 g of alumina and 500 mL of redistilled methanol. 10.1.3 Sonicate the mixtures for 30 min. Decant the Methanol. 10.1.4 Rinse the adsorbents three times with 100 to 200 mL of methylene chloride. Decant the methylene chloride. Laboratory Operating Procedure Method 3610/3630, Revision B Page 4 of 7 10.1.5 Add 500 mL of methylene chloride to each of the adsorbents and sonicate for 30 min. Decant the methylene chloride. 10.1.6 Allow the adsorbents to dry in the hood overnight. Cover the beakers with aluminum foil with punctures to permit escape of vapors but prevent entry of particulate matters. 10.1.7 Activate silica gel at 180 °C and alumina at 250 °C overnight. 10.1.8 Allow the adsorbents to cool to room temperature, and then weigh into a tared glass-stoppered bottle. Record the weight of the adsorbents. 10.1.9 Add 3% by weight of water to the adsorbents and shake the flasks vigorously. Allow the flasks (covered with ground glass joint) to sit overnight to equilibrate. 10.1.10 Add dry hexane to the flasks. The adsorbents are now ready to use for column chromatography. 10.2 Packing the Column 10.2.1 Plug the glass column equipped with a Teflon stopcock with pre-combusted glass wool. 10.2.2 Rinse the inner walls of the column with approximately 10 mL of dry hexane to remove glass fibers and any residual contaminants in the apparatus. Allow this to run through the stopcock. 10.2.3 Close the stockcock and add 12 mL of dry hexane. 10.2.4 Open the stopcock and add silica gel to the column as a slurry to a height of 12 cm. Occasionally tap the column with a plastic rod to pack the column and remove the bubbles. Keep rinsing the walls of the column with hexane to prevent build-up of dry silica gel during packing (always keep the silica gel wet with solvent). 10.2.5 Using a separate pipette, add 6 cm of alumina slurry over the silica gel. Laboratory Operating Procedure Method 361013630, Revision B Page 5 of 7 10.2.6 Lower the solvent level to just above the alumina surface and close the stopcock. 10.3 Chromatographic Separation of Sediment, water and low lipid tissues. 10.3.1 Place a 100 mL pear-shaped flask beneath the column to collect the sample extract. 10.3.2 Solvent exchange sample into hexane and concentrate to 0.5 mL. 10.3.3 Add the 0.5 mL concentrated sample to the top of the alumina layer of the column and allow it run through the column, until it reaches the top of the alumina. 10.3.4 Rinse the flask three times with hexane and add each rinse to the top of the alumina allowing it to run through the column until the solvent reaches the top of the alumina. Be careful not to add more than ca. 1 mL of hexane rinse to the column. 10.3.5 Add 15 mL of Hexane and allow it to run through the column until it reaches the top of the alumina layer. 10.3.6 Add 15 mL of 30% methylene chloride/hexane solution and allow it to run through the column until it reaches the top of the alumina layer. 10.4.7 10.3.7 Add 30 mL of methylene chloride and allow the column to run to dryness. If the sample is being analyzed for Organophosphorus Pesticides then add an additional 15 mL of Methylene chloride before allowing the column to run to dryness. 10.3.8 Concentrate the extract collected in the 100 mL pear flask to a final volume of 0.5 mL using a rotovap. 10.3.9 Transfer the final extract into an auto-sampler vial. Rinse the walls of the flask with two 0.5 mL hexane rinses and add them to the vial. 10.4 Chromatographic Separation of high lipid tissues. 10.4.1 Place a 100 mL pear-shaped flask beneath the column to collect the sample extract. Laboratory Operating Procedure Method 3610/3630, Revision B Page 6 of 7 10.4.2 Solvent exchange sample into hexane and concentrate to 1 mL. 10.4.3 Add the 1 mL concentrated sample to the top of the alumina layer of the column and allow it run through the column, until it reaches the top of the alumina. 10.4.4 Rinse the flask three times with hexane and add each rinse to the top of the alumina allowing it to run through the column until the solvent reaches the top of the alumina. 10.4.5 Add 30 mL of Hexane and allow it to run through the column until it reaches the top of the alumina layer. 10.4.6 Add 30 mL of 30% methylene chloride/hexane solution and allow it to run through the column until it reaches the top of the alumina layer. 10.4.8 Replace the 100 mL pear flask with a 75 mL pear flask to collect 30 mL of methylene chloride and allow the column to run to dryness. If the sample is being analyzed for Organophosphorus Pesticides then add an additional 15 mL of Methylene chloride before allowing the column to run to dryness. 10.4.8 Concentrate the extract collected in the 100 mL pear flask to a final volume of 0.5 mL using a rotovap. Transfer the final extract into an auto-sampler vial. Rinse the walls of the flask with two 0.5 mL hexane rinses and add them to the vial. 10.4.9 Concentrate the extract collected in the 75 mL pear flask to a final volume of 0.5 mL using a rotovap. Transfer the final extract into a separate auto-sampler vial. Rinse the walls of the flask with two 0.5 mL hexane rinses and add them to the vial. Make sure you label the vial as "DCM" indicating that it is the last fraction collected during the column cleaning procedure. 11.0 CALCULATIONS 11.1 This section is not applicable to this method. Laboratory Operating Procedure Method 3610/3630, Revision B Page 7 of 7 Appendix E Attachment 4: Standard Operating Procedure for Method 5520b: Determination of Lipid Content in Tissue Samples CRG MARINE LABORATORIES 2020 Del Arno Blvd.Suite 200,Torrance,CA 90501,(310)533-5190 DETERMINATION OF LIPID CONTENT IN TISSUE SAMPLES Approved by: Rhonda Moeller, QA Officer Date Richard Gossett, Laboratory Manager Date Laboratory Operating Procedure Method 55208, Revision B Page 1 of 4 METHOD 5520B: DETERMINATION OF LIPID CONTENT IN TISSUE SAMPLES REFERENCE: Standard Methods for the Examination of Water and Wastewater, Section 5520, 19" Ed., 1995. 1.0 SCOPE AND APPLICATION 1.1 This method covers the procedure for the determination of lipid content in tissue samples. It is to be used in conjunction with Laboratory Operating Procedure Method (LOPM) 3545: Pressurized Fluid Extraction Procedure. 2.0 SUMMARY OF METHOD A measured volume of sample extract is put into a glass vial of known weight and the solvent is allowed to evaporate completely. The vial is then reweighed and the resulting data are used to calculate the lipid content of the tissue sample. 3.0 PREVENTION OF INTERFERENCES 3.1 Solvents, glassware are to be free of any interferences. A procedural blank is analyzed with each sample batch to demonstrate the absence of any method interferences. Methylene chloride is used as the blank matrix. 3.2 High purity solvents are to be used to minimize interferences. 4.0 SAFETY 4.1 It is mandatory to wear a laboratory coat, closed-toe shoes and safety glasses in the laboratory. Gloves are to be worn when working with samples. 4.2 Use of a respirator and appropriate safety gloves are recommended for working with solvents. 4.3 Material Safety Data Sheets (MSDS) are on file in the laboratory and are available to all personnel involved in the use of hazardous materials during any procedure. Laboratory Operating Procedure Method 552013, Revision B Page 2 of 4 4.4 Extreme caution and the proper use of safety equipment are required during the handling of any hazardous material. If the analyst has any questions regarding safety, he or she should contact a supervisor or the laboratory director prior to the start of this procedure. 5.0 APPARATUS AND MATERIALS 5.1 Gas-tight volumetric syringe: 1 mL 5.2 Glass vial: 2 mL 5.3 AND HR200 analytical balance 6.0 REAGENTS This section is not applicable to this method. 7.0 CALIBRATION AND MAINTENANCE 7.1 A balance calibration check shall be performed prior to the analysis of any samples using this method. Refer to LOPM 0020. 8.0 QUALITY CONTROL 8.1 The quality control samples analyzed here are the same as those extracted using LOPM 3545; namely, one blank, one LCM/CRM, and one duplicate and/or MS/MSD set for each batch of samples. Refer to LOPM 3545. 9.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING This section is not applicable to this method. 10.0 PROCEDURE 10.1 Perform a balance calibration check on the AND HR200 analytical balance and recalibrate it if necessary. Refer to LOPM 0020. Laboratory Operating Procedure Method 5520B, Revision B Page 3 of 4 10.2 Pre-weigh the glass vials by first taring the balance, then place a glass vial on the balance pan. Record the mass of the vial in the laboratory notebook to the nearest 0.1 mg. 10.3 Having completed section 10.8.4 of LOPM 3545, use a 1 mL gas- tight volumetric syringe to measure the total sample extract volume. Dispense a half of the extract into the pre-weighed glass vial and return the rest to the pear-shaped flask from which it came. 10.4 Place the vial into the fume hood and allow the solvent to evaporate completely from the glass vial for a minimum of 24 hours, which leaves the lipid portion of the sample behind. 10.5 Measure and record the gross weight of the glass vial. 10.6 Return the vial to the fume hood for another 2 hours and re-weigh the vial. Continue to evaporate the sample until a constant weight is achieved. 11.0 CALCULATIONS 11.1 The lipid content of a tissue sample is expressed as a percentage of the wet weight of the sample and is calculated as follows: %Lipid= m g —m c x 2 x 100 MS where m9 = gross weight of vial plus lipid in grams (step 10.5) mc = tare weight of vial in grams (step 10.2) ms = total wet mass of tissue sample extracted in grams (LOPM 3545) The Microsoft Excel file named Lipid Template can be used to calculate lipid values for multiple samples using this equation. Laboratory Operating Procedure Method 552013, Revision B Page 4 of 4 Appendix E Attachment 5: Standard Operating Procedure for Method 300. 1 : Determination of Anions by Ion Chromatography CRG MARINE LABORATORIES 2020 Del Amo Blvd,Suite 200,Torrance,Ca 90501 310 533-5190 DETERMINATION OF ANIONS BY ION CHROMATOGRAPHY- METHOD 300.1 Approved by: Rhonda Moeller, QA Officer Date Richard Gossett, Laboratory Manager Date Laboratory Operating Procedure Method 300.1, Revision 1 Pagel of 9 METHOD 300.1 DETERMINATION OF ANIONS BY ION CHROMATOGRAPHY REFERENCE: [US EPA Method 300.1 and Standard Methods 19th Edition- SM4110 B] 1.0 SCOPE AND APPLICATION 1.OThis method is used to determine the concentration of various anions in water, seawater and sediments. 2.0 'SUMMARY OF METHOD 2.1 This method is based upon EPA Method 300.1 A drinking water, groundwater or wastewater sample is filtered and introduced to an ion chromatograph (IC) instrument (Metrohm 761), which contains a chromatography column that separates the anions and a conductivity cell that detects them. The detector output is recorded and integrated, and the integrated signals are compared to those from standard solutions of known anion concentrations to calculate the anion concentrations in the sample. Anions are identified by their characteristic retention times, also known from standard solutions. The following anions are calibrated for bromide, chloride, fluoride, nitrate-nitrogen, nitrite-nitrogen, phosphate and sulfate. The Metrohm- peak operating manual must be read and understood prior to performing this method. 3.0 SAFETY 3.1 Good safety habits and laboratory techniques should be used throughout the procedure. Consult the Material Safety Data Sheet for information specific to the reagents used. For additional information, refer to Section 3. 3.2 It is mandatory to wear a laboratory coat, closed toe shoes, and safety glasses in the Laboratory. Gloves shall be worn while working with solvents and other reagents. 3.3AI1 steps involving the use of large volumes of solvents shall be performed in a fume hood. 3.4 Material Safety Data Sheets (MSDS) are on file and available at all times to personnel using hazardous materials. It is the responsibility of everyone using these materials to be familiar with the potential hazards of the chemicals in their work area. If the analyst is uncertain of the potential hazards of specific chemicals, contact the supervisor prior to Laboratory Operating Procedure Method 300.1, Revision 1 Page 2 of 9 using the chemicals. 3.5 Extreme caution, awareness, knowledge of the location and safe use of fire extinguishers, eye wash fountains, and safety showers are required. 4.OSAMPLE COLLECTION, PRESERVATION AND STORAGE 4.1 Samples are collected in plastic containers without chemical preservation. 4.2 Samples must be kept at 4°C during storage prior to analysis. 4.3The holding time varies according to analyte: 48 hrs for nitrate, nitrite and phosphate; 28 days for chloride, sulfate, bromide and fluoride. 5.0 INTERFERENCES 5.1 Contamination of reagents will lead to changed retention times and peak properties. 6.0STANDARDS 6.1 Stock standards are stable for at least one month at 4°C (refrigerator temperature). 6.2 Prepare dilute working standards daily, as nitrite is relatively unstable. The working standards are used to run calibrations, prepare spikes, etc., as detailed below. 6.3STOCK STANDARD: This is bought ready made from Fischer Scientific. Fluoride as F 20 ppm Chloride as Cl 50 ppm Nitrite as N 25 ppm Bromide as Br 100 ppm Nitrate as N 25 ppm Phosphate as PO4 150 ppm Sulfate as SO4 150 ppm 6AWORKING STANDARDS: Prepare 6 dilutions of stock standard to yield the following anion concentrations: 0.005, 0.01, 0.05, 0.1, 0.5 and 2.5 ppm for nitrate and nitrite. These concentrations span two Laboratory Operating Procedure Method 300.1, Revision 1 Page 3 of 9 orders of magnitude, giving a sufficiently large calibration range. The calibration is performed at least once per quarter and detailed as below. 6.5 CALIBRATION VERIFICATION: The table below summarizes all the concentration levels for each anion. F Cl NO, Br NO3 PO' so, Level m /L m /L m /L m /L m /L m /L m /L 1 0.004 0.01 0.005 0.02 0.005 0.03 0.03 2 0.008 0.02 0.01 0.04 0.01 0.06 0.06 3 0.04 0.1 0.05 0.2 0.05 0.3 0.3 4 0.08 0.2 0.1 0.4 0.1 0.6 0.6 5 0.4 1 0.5 2 0.5 3 3 6 2 5 2.5 10 2.5 15 15 6.6 Second source anion standards (purchased from a different manufacturer) are prepared in the same manner as previously discussed and used to verify the calibration standards. 6.7 LCS and LCSD: These are lab reagent water, spiked at 0.5 ppm with a second source standard. 6.8 MS and MSD: These are field samples spiked at 0.5 ppm with a second source standard. 6.9 Calibration verification standard: Lab reagent water spiked at the same concentration as level 6 standard. 7.0 INSTRUMENT AND APPARATUS 7.1 Syringes with filter disks, 0.45 pm pore size 7.2Analytical balance 7.3 Metrohm-peak ion chromatograph, whose components include: 7.3.1 Eluent reservoir bottle 7.3.2 Regenerant reservoir bottle 7.3.3 Delivery pump, to deliver a constant flow of eluent at moderate pressure. 7.3.4 Auto sampler, to introduce the sample to the instrument. 7.3.5 Sample loop (20 pL), to conduct the sample to the columns. Laboratory Operating Procedure Method 300.1, Revision 1 Page 4 of 9 7.3.6 Guard column, to protect the separator column from particulates and organic material. 7.3.7 Separator (analytical) column (6.1006.020 metrosep anion dual 1), to separate the anions by selective adsorption. 7.3.8 Suppressor (chemical suppression), to convert the eluent and analyte anions to their acidic form. 7.3.9 Conductivity detector (digital output), to quantify the analytes. 7.3.10 Waste bottle, to collect the effluent. 7.3.11 Recorder (software), to note the output of the detector for further processing. 7.3.12 Integrator (software), to process the recorded signals to yield meaningful data. 7AVolumetric flasks and pipettes. All glassware used should be class A. 8.0 REAGENTS 8.1 It is important that all solutions for ion chromatography be prepared using de-ionized water, free of the anions of interest. Use de-ionized water with resistivity of at least 16.67 mS/cm, as per manufacturer's specifications. All reagents must be of high quality (>99% pure), dried at 105 °C for 60 min prior to use, and stored in a desiccator. 8.2Carbonate-bicarbonate (2.5 mM sodium carbonate, Na2CO3/2.4 mM sodium bicarbonate, NaHCO3). 8.3To prepare stock eluent, use an analytical balance to weigh out 16.95 g Na2CO3 and 4.2 g NaHCO3. Transfer the weighed salts analytically to a 500 mL volumetric flask and dilute to the mark. 8.4 The eluent is made by diluting 10 mL of the stock eluent to 1000 mL with de-gassed, de-ionized water. Carbonate and bicarbonate solutions are sensitive to atmospheric carbon dioxide and will change composition over time, store the eluent away from air and use the solution promptly. This is a minor concern considering the projected daily consumption of eluent and should not affect our analyses. 9.0 PROCEDURE 9.1 To set up instrument, verify that the eluent is flowing and that the baseline detector output is steady (13-16 pS for eluent). Laboratory Operating Procedure Method 300.1, Revision 1 Page 5 of 9 9.2 From the systems window, click on control and choose startup hardware (measure baseline). This allows the instrument to warm up. Let it warm up for at least 20 minutes or until the baseline is stable. 9.3 Using the software, prepare a sample schedule (sequence) to be run. For each sample, choose the appropriate method. This method file contains the system parameter settings established for the particular system. Analyze the initial calibration standards described above. The correlation coefficient should be 0.995 or better for each analyte. If not, correct the problem and re-analyze the initial calibration. If the continuing calibration standards do not meet the criteria found in the Quality Control section of this LOPM, the initial calibration must be repeated. 9.4 Initiate the run. As defined in the selected method, the system parameters are controlled by the software. In the ICnet 2.3 main menu, click on the systems icon from the file dropdown menu, click on open and choose method. 9.5 From the systems window, click on system and choose a sample queue. Make sure that all samples have the correct method assigned. Check on the boxes that say "shut down system when this run ends" and "Close this window when this run ends". 9.6Type sample IDs in the sample column. When calibration standard is chosen, Level 1,2,3,4, 5 or 6 must be selected under the level column. Save the changes on the queue and finally check the box that says, "Shut down after queue finishes". 9.7 Prepare the samples by filtering about 10 mL of each using the syringe + filter disk. This prolongs column life and keeps the sample path clean by removing sizeable particles. Filtration is not necessary when using the advanced auto sampler with in-line filter. Next, fill each sample vial with about 10 mL of sample and load the vials in the auto sampler according to the schedule already defined. To verify the operation of the system, we include calibration standards, blanks and spikes as described in the Quality Control section below. 9.8 Before starting the run, make sure that the eluent flow and column pressure readings are appropriate (0.7 mL/min and 10-14 psi respectively). 9.9 When baseline is stable, click on "start" on the sample queue window. 9.10 When the run is complete, the system settings are set automatically to inactive status as defined in the method. Laboratory Operating Procedure Method 300.1, Revision 1 Page 6 of 9 10.0 CALCULATIONS 10.1 The software is highly automated and does all the calculations. After reviewing the output (chromatograms and tabular integration and quantification results), reprocess the raw data using the IC-net 2.3 software. 10.2 The signals for each of the five calibration standards are integrated. 10.3 Baseline subtraction is automatic. Standards are designated as such, with their analyte concentrations in the schedule. 10.4 A linear calibration is performed using the 5 data points for each anion. If the correlation coefficient R <0.995, the calibration data are rejected and the process is repeated. 10.5 The slope and intercept of each line are used to interpret the signals for a given analyte in the samples of that run. In this manner area counts (in pS-min) are converted to concentrations (in mg/L). Analytes are identified by retention time; the software allows some flexibility in these times, as they vary slightly from sample to sample. The separations are quite good, so generally there is no difficulty in associating a signal with the proper anion. 10.6 LCS/LCSD recovery % Recovery = Result from instrument X 100 Actual Value 10.7 MS/MSD recovery % Recovery = Sf— So/D X 100 SP where Sf = Final value of spiked sample So = Original value of sample without spike Sp= Expected spike value D = Dilution factor 11.0 QUALITY CONTROL 11.1 Analyze a laboratory reagent blank sample after every 10 samples to verify the baseline reading. The blank sample is the same de- ionized water used to prepare the eluent and all solutions. All blank samples must contain less than Y the reporting limit of all analytes. If Laboratory Operating Procedure Method 300.1, Revision 1 Page 7 of 9 this is not the case, all samples associated with the blank must be re- analyzed. 11.2 The initial calibration verification standard, prepared from a source different from the calibration, is analyzed after each calibration. All standards must meet 90-110 % recovery limits. If this is not the case, the calibration must be repeated. 11.3 Analyze an instrument performance check (CCV, "continuing cal check") sample immediately after calibration, after every 10 samples and at the end of the run. The ICV and CCV results must be 90-110 % of the true value. If they are not passing, they must be repeated. If a second result is still outside of the limits, identify the cause, recalibrate and re-run the samples that have been analyzed since the last passable CCV check. 11.4 Analyze a matrix spike sample per batch of 20 samples. The recommended spike recovery is in the 80-120 % range. The MS/MSD sample is prepared similar to the LCS/LCSD sample, except that a suitable sample is used instead of de-ionized water. The same equation is used except that the background concentration B is the result obtained from the prior analysis of the unspiked sample. No specific corrective action is taken if the MS/MSD recovery is not 80- 120 %; however the analyst must make certain that systematic spike failures are not occurring due to changes in spiking solutions, etc. 11.5 Analyze a sample duplicate every batch of 20 samples. The duplicate RPD should be +/- 20 %. No specific corrective action is taken if the RPD criterion is not met, however the analyst must make certain that systematic failures are not occurring. This may indicate that the IC instrument is not functioning properly and that maintenance is needed. 11.6 Annually (or if a significant system change occurs, e.g. moving the entire setup) perform an MDL study by analyzing 7 replicate samples of 0.01 ppm standard over 3 days. 11.7 Every batch must be accompanied by qualifying QC data. This will include a method blank (reagent water), laboratory control spikes (LCS/LCSD), matrix spikes (MS/MSD) and a calibration verification standard. 11.8 The recovery limits for the LCS, LCSD and calibration standard should be 90-110 percent with RPD of 20. 11.9 The recovery limits for MS and MSD should be 80-120 percent with Laboratory Operating Procedure Method 300.1, Revision 1 Page 8 of 9 RPD of 20. 12.0 DATA ASSESSMENT AND CORRECTIVE ACTIONS 12.1 All sample results must be evaluated for adherence with the QC requirements discussed in the preceding section. 12.2 No samples should be analyzed without demonstrating that the blank is interference free (concentration is below 1/2 the reporting limit). A blank is analyzed every 20 samples. Those samples that are associated with a contaminated blank must be reanalyzed. 12.3 Evaluation of continuing calibration standard (CCV) data: Evaluation of the performance of this analytical method is primarily controlled by the recovery that is obtained in the CCV sample. A CCV is analyzed every 10 samples and the standard is prepared from a source different from the one used for calibration. Since there are no matrix interferences present in the CCV, the recoveries should always fall within the 90-110 % limits. Samples that are associated with a CCV having lower than expected recoveries must be re-analyzed. If the CCV recovery exceeds criteria and no analyte is detected in the sample, then the data is acceptable without re-analysis since the bias was high and the sample was non-detect. Corrective action for CCV recoveries outside of criteria most often would be re-calibration. If this does not correct the problem, prepare the CCV solution afresh. 12.4 Initial Calibration: Each analyte must first have an acceptable initial calibration. 12.5 The calibration must contain the appropriate number of standards for the method and should cover the expected linear concentration range of the method with the lowest standard close to or at the reporting limit and the highest standard near the linear range. 12.6 Samples that have analyte concentrations exceeding the highest standard must be diluted to bring the concentration near the middle of the calibration. There are several calibration scenarios: linear calibration (preferred), quadratic (used for non-linear calibrations) and average response factor. A correlation coefficient of 0.995 to be considered acceptable. Corrective actions for calibrations which do not meet this requirement would be to drop the low or high level standard and add levels which cover a narrower range. It also may be necessary to prepare all standards fresh and repeat the run. 13.0 POLLUTION PREVENTION AND WASTE MANAGEMENT 13.1 All hazardous materials that are generated during the testing of Laboratory Operating Procedure Method 300.1, Revision 1 Page 9 of 9 samples must be properly collected and stored. Drums are available in the storage room for the following types of wastes- acidic, basic and solvents. There are no hazardous wastes generated from this test. 14.0 REFERENCES 14.1 Standard Methods 19th Edition. 14.2 Metrohm system operating manual. 14.3 National Environmental Methods Index (NEMI). Laboratory Operating Procedure Method 300.1, Revision 1 Page 10 of 9 Appendix E Attachment 6: Standard Operating Procedure for Method 6020: Determination of Trace Elements in Solid Matrices by Inductively Coupled Plasma Mass Spectrometry CRG MARINE LABORATORIES 2020 Del Amo Blvd.,Suite 200,Torrance,CA 90501,(310)533-5190 TRACE METALS IN SOLID MATRICES BY INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY Approved by: Rhonda Moeller, QA Officer Date Richard Gossett, Laboratory Manager Date Laboratory Operating Procedure Method 6020 Page 1 of 10 METHOD 6020: DETERMINATION OF TRACE ELEMENTS IN SOLID MATRICES BY INDUCTIVELY COUPLED PLASMA MASS SPECTROMETRY REFERENCE: EPA Method 6020: Inductively Coupled Plasma — Mass Spectrometry 1.0 SCOPE AND APPLICATION .1 This method provides procedures for total and dissolved elements from sediment and tissue samples which can subsequently be analyzed by inductively coupled plasma mass spectrometry (ICP-MS). This method utilizes stringent quality control (QC) and sample handling procedures necessary to avoid contamination and ensure the validity of analytical results during sampling and analysis for metals. .2 This method is applicable to the following analytes: Chemical Abstract Services Registry Number Analyte Symbol (CASRN) Aluminum (AI) 7429-90-5 Antimony (Sb) 7440-36-0 Arsenic (As) 7440-38-2 Barium (Ba) 7440-39-3 Beryllium (Be) 7440-41-7 Boron (B) Cadmium (Cd) 7440-43-9 Chromium (Cr) 7440-47-3 Cobalt (Co) 7440-48-4 Copper (Cu) 7440-50-8 Iron (Fe) Lead (Pb) 7439-92-1 Manganese (Mn) 7439-96-5 Molybdenum (Mo) 7439-98-7 Mercury (Hg) 7439-97-6 Nickel (Ni) 7440-02-0 Selenium (Se) 7782-49-2 Silver (Ag) 7440-22-4 Strontium (Sr) Thallium (TI) 7440-28-0 Tin (Sn) 7440-31-5 Titanium (Ti) Vanadium (V) 7440-62-2 Zinc (Zn) 7440-66-6 Laboratory Operating Procedure Method 6020 Page 2 of 10 2.0 SUMMARY OF METHOD 2.1 A measured aliquot of well-mixed homogenous sample is accurately weighed or measured for sample processing. For total recoverable analysis of solid samples, analytes are digested with a wet oxidation procedure using nitric/hydrochloric acids. The sample is heated in a closed Teflon cell using microwave energy to perform an incomplete digestion of the sample matrix (tissues are typically completely digested). The sample is then analyzed using Inductively Coupled Plasma Mass Spectrometry (ICPMS) by pumping the sample through a nebulizer producing a fine spray. An argon carrier gas atomizes the sample which is ionized and detected with a mass spectrometer. Qualitative identification is based on the mass to charge ratio for each element. It is recommended that samples be analyzed within 1 day of digestion. 3.0 PREVENTION OF INTERFERENCES 3.1 Improper assembly of the digestion vessels may cause the vessel relief system to vent causing loss of analytes. 3.2 To avoid contamination by the Laboratory environment, keep samples and glassware covered when possible. 3.3 Chemical interferences are characterized by molecular compound formation, ionization effects and solute vaporization effects. These effects are not usually pronounced with the ICPMS technique due to the high temperature of the torch. 3.4 Isobaric interferences are caused by isotopes of different elements which form singly or doubly charged ions of the same nominal mass-to-charge ratio and which cannot be resolved by the mass spectrometer. All elements determined by this method have one isotope free of isobaric elemental interference except Selenium-82, which has isobaric interference from the Krypton impurities in the Argon gas supply. This interference can be minimized by using high purity argon. All data must be corrected by measuring the signal from another isotope of the interfering element and subtracting the appropriate signal ratio from the isotope of interest. 3.5 Wing overlap interferences may occur when a small ion peak is being measured adjacent to a large one. The potential for these interferences should be recognized and the spectrometer resolution adjusted to minimize them. 3.6 Polyatomic interferences are caused by ions consisting of more than one atom which have the same nominal mass-to-charge ratio as the isotope of interest, and which cannot be resolved by the mass spectrometer. The ions may be formed in the plasma or interface system from support gases or sample components. Most of the common interferences have been identified and are Laboratory Operating Procedure Method 6020 Page 3 of 10 listed within the instrument data system along with the elements affected. All data shall be corrected by measuring the signal from another isotope of the interfering element and subtracting the appropriate signal ratio from the isotope of interest. Equations for the correction of the data are presented below in Table 2. Table 2. ELEMENT MASS EQUATION Vanadium 51 (51)- - (53)-3.127 + (52)-0.353 Arsenic 75 (75)-1 - 77 "3.132 + 82 *2.736 - 83 *2.761 Selenium 82 82 *1 - 83 *1.0087 Molybdenum 98 98 *1 - 99 *.0146 Cadmium 111 111 *1 - 108 *1.073 + 106 *0.764 Indium 1 115 115 *1 - 118 *0.016 3.7 Physical interferences are effects associated with the sample nebulization and transport processes. Properties such as the change in viscosity and surface tension can cause significant inaccuracies, especially in samples which may contain high dissolved solids and/or acid concentrations. These interferences are greatly reduced in this procedure by the use of mass flow controllers for controlling the argon flow rate, the use of a peristaltic pump for sample introduction, and the use of internal standards. 4.0 SAFETY 4.1 It is mandatory to wear a laboratory coat, closed toe shoes, and safety glasses in the Laboratory. Gloves shall be worn while working with samples and acids. 4.2 All steps involving the use of acids shall be performed in a fumehood. 4.3 Material Safety Data Sheets (MSDS) are on file and available at all times to personnel using hazardous materials. It is the responsibility of everyone using these materials to be familiar with the potential hazards of the chemicals in their work area. If the analyst is uncertain of the potential hazards of specific chemicals, contact the supervisor prior to using the chemicals. 4.4 Extreme caution, awareness and knowledge of the location and safe use of fire extinguishers, eye wash fountains, and safety showers are required. 4.5 Personnel performing this procedure shall be instructed in the safe use of acids, the requirements for protective equipment, and acid spill cleanup procedures. 5.0 APPARATUS AND MATERIALS Laboratory Operating Procedure Method 6020 Page 4 of 10 5.1 Hewlett Packard 4500 Inductively Coupled Plasma Mass Spectrometer with Automatic Sampler 5.2 CEM Automated Microwave Digestion System 5.3 Funnels 5.4 Plastic centrifuge tubes with screw cap, 50 mL graduated 5.5 Volumetric flasks 5.6 Ceramic or plastic spoons 5.7 Wash bottles 5.8 Whatman No. 40 filter paper 6.0 REAGENTS 6.1 Calibration standards prepared from commercially available single-element or multi-element stock standards using 2% HNO3 and 1% HCI 6.2 Internal standards prepared from commercially available single-element or multi- element stock standards 6.3 ICPMS tuning solution containing Lithium, Yttrium, and Thallium at 10 pg/mL 6.4 Optima HCI 6.5 Optima HNO3 6.6 Ultra-pure deionized water 6.7 High purity argon Laboratory Operating Procedure Method 6020 Page 5 of 10 7.0 CALIBRATION AND MAINTENANCE 7.1 Trace metal concentrations are determined by comparison to the response of a known standard obtained from a certified source traceable to NIST. 7.2 The instrument is calibrated covering the expected range of concentrations in the samples including near the method detection limit before each set of samples and at a frequency of every 24 hours during sample analyses. This calibration is verified using a second-source standard. 7.3 Periodic inspection and cleaning of the microwave door seals and cavity interior is necessary. Clean these areas with warm soapy water applied with a paper towel. Do not use abrasive cleansers to clean the microwave as these may scratch the fluorocarbon cavity coating and degrade its ability to resist corrosive odors. 7.4 An instrument maintenance schedule is maintained for the Hewlett Packard 4500 ICPMS. Dates and initials are recorded in a notebook located near the instrument. 7.4.1 The instrument is serviced by the manufacturer at least once per year. 8.0 QUALITY CONTROL 8.1 QA/QC records are maintained to document the quality of data generated. If any element falls outside the designated range, that element has failed the acceptance criteria. Failure to meet the stated requirement shall require that corrective action be taken to eliminate the problem prior to the analysis of any samples. Samples from the batch being analyzed at the time the failure is detected shall be reanalyzed after the corrective action has been taken. A batch is defined as 20 or less samples. If any sample cannot be reanalyzed, the result for that element shall be flagged and a detailed report is included with the result. 8.1.1 Calibration Curve- A calibration curve is generated daily for each run of samples. At least 5 calibration standard concentrations must be used for each run. Standard counts must bracket sample counts, thus more than 5 standard concentrations are used to measure high and low counts from a single extract. 8.1.2 Calibration Check- A calibration check using a second-source standard will be performed every 12 hours and at the end of every batch of samples. The calibration check shall be within 15% of the initial calibration curve. Laboratory Operating Procedure Method 6020 Page 6 of 10 8.1.3 Matrix Spikes- Matrix spike and matrix spike duplicates as well as duplicate samples shall be analyzed with each batch of samples to determine the precision for each element. A control chart is generated to document the precision. The relative standard deviation for all elements combined in the matrix spike/matrix spike duplicate shall be within 15% and no single element shall be greater than 30% for those elements that are greater than 10 times the method detection limit. Matrix spike and matrix spike duplicates shall be performed using replicate samples supplied by the client so that the matrix is representative of the type of sample being analyzed. If the client does not provide enough sample for spiking, then a laboratory control material of similar matrix should be used. If a laboratory control material is not available, then at a minimum blank water should be used. 8.1.4 CRM/LCM- Certified reference materials and/or lab control materials shall be analyzed with each batch of samples. The reported value shall be within published acceptance limits. 8.1.5 Blanks- Lab reagent blanks shall be analyzed with each batch of samples. No element shall be detected at greater than 3 times the method detection limit. 8.1.6 Internal Standards- Internal standards shall be added in known amounts to blanks, calibration standards, continuing calibration check solutions, and samples to compensate for instrumental drift. Elements that may be used are presented in Table 3. Relative response factors are used to correct responses of the target analytes. Table 3. Internal Standards INTERNAL STANDARD MASS Scandium Sc 45 Yttrium Y 89 Rhodium Rh 103 Terbium (Tb) 159 Thulium (Tm) 169 Bismuth (Bi) 1209 9.0 SAMPLE COLLECTION, PRESERVATION AND HANDLING Wet samples submitted in the frozen state are stored frozen at -20 ± 4 °C in the original labeled container until sample preparation. Laboratory Operating Procedure Method 6020 Page 7 of 10 10.0 PROCEDURE 10.1 Sample Digestion 10.1.1 Inspect the microwave door, interior and vent to insure that it is in proper operating condition. 10.1.2 Label microwave vessels which will be used to digest the samples with sample identifications. All digestion vessels shall have been soaking in 5% HNO3 acid and thoroughly cleaned prior to use. 10.1.3 Weigh about 1-3 g of thoroughly mixed sample into the pre-tared digestion liners. 10.1.4 Add 15 ml of digestion acid to Teflon vessels with sample. 10.1.5 Assemble the vessels according to the manufacturers' directions and place them in microwave carousel. 10.1.6 Place the carousel in the microwave oven and select the SEDIMENT METALS method from the front panel display. This method programs the oven for digestion at a 100% power setting for ca. 25 minutes by ramping the temperature to 175 °C over 15 minutes, then holding for 10 minutes at a maximum pressure of 150 psi. For tissues, select the TISSUE method from the front panel display. 10.1.7 After cooling to room temperature, open the vessel and filter the digested sample through Whatman No. 40 filter paper into a labeled 50 ml centrifuge tube. 10.1.8 Using de-ionized water, rinse the entire contents of the digestion vessel into the filters and bring up the final volume to 50 ml. 10.1.9 Spike all samples and standards with internal standards. 10.1.10 Record any comments regarding the digestion process into the log book. 10.2 Sample Analysis 10.2.1 Use volumetric flasks and calibrated pipettors to make calibration standards by diluting 10 mL of a commercially prepared stock solution to 100 mL. Mix standards by inverting and shaking a minimum of 10 times. A dilution stock of 2% HNO3 and 1% HCI is used for all dilutions. Prepare 5 concentrations of calibration standards ranging from near the method Laboratory Operating Procedure Method 6020 Page 8 of 10 detection limit to at or above the maximum expected concentration in the sample. 10.2.2 Instrument parameters are stored in the computer program which operates the ICPMS. These parameters are listed in Table 4. Table 4. Instrument Parameters PARAMETER SETTING RF Power 1350 watts Acquisition Mode Spectrum Analysis Detector Mode Auto Acquisition Points/Mass 3 Acquisition Repetitions 3 Argon Flow Rate 16 L/min Nebulizer Concentric Sample Uptake Rate 0.4 mL/min Sample Uptake Time 60 sec Pump Stabilization Time 40 sec Rinse Time 60 sec Carrier Gas Flow Rate 1.26 L/min Auxilliary Gas Flow Rate 1.0 L/min Spray Chamber Temperature 2 °C Sample Depth 17.5 mm 10.2.3 Fill the autosampler rinse container with deionized water. 10.2.4 Empty the spray chamber drain bottle and fill to approximately 1/4 full with tap water. It is important that the drain line from the spray chamber be immersed in water to prevent fluctuations in the plasma. 10.2.5 Turn on the argon gas supply. 10.2.6 Ignite the plasma and allow a minimum of 30 minutes for stabilization. 10.2.7 Check the system operating conditions by tuning the instrument according to the parameters listed in Table 5. If parameters do not fall within these limits, retune the instrument per manufacturers procedures. Once you are satisfied with the tune, save the parameters and print out a copy for the laboratory notebook. Table 5. Optimal Tune Results PARAMETER OPTIMAL RESULT Sensitivity for AMU 2 7,000 counts Laboratory Operating Procedure Method 6020 Page 9 of 10 Sensitivity for AMU 89 15,000 counts Sensitivity for AMU 205 10,000 counts RSD for AMU 2, 89, & 205 < 5% Pulse to Analog Factors 100 ± 1 Doubly Charged Ions < 3% Oxides < 1% Axis ± 0.05 AMU Peakwidth 0.65 - 0.75 AMU at 10% 10.2.8 Load the appropriate method file into the Chemstation data system. Complete the sample sequence table with the specified sample information and dilution factors. Load the samples into the autosampler according to the order listed in the sequence file. Double check to make sure the standards, blanks, and samples are in the correct autosampler position assigned in the sequence file. NOTE: The instrument may be set for automatic shutoff at the end of the sequence by adding the following command in the last line of the sequence file: TYPE = Keyword KEYWORD = Command KEYWORD COMMAND = tune "macro'shutdown.mac',go" (this must be typed exactly as written here) 10.2.9 Start the analytical sequence and make sure that it is operating properly. 11.0 CALCULATIONS The instrument data system reports the sample concentration by comparing the response of the target isotope (See Table 1) with its corresponding standard. An internal standard quantitation is used and the standard response factors are calculated using the best-fit regression equation; (Y = aX + b). Sample weight and dilution factors used in the calculation are entered into the sequence table. Results are reported by the instrument in the units specified in the calibration table. Laboratory Operating Procedure Method 6020 Page 10 of 10 Appendix E Attachment 7: Standard Operating Procedure for Method 8270: Acid and Base/Neutral Extractable Compounds by Gas Chromatography/Mass Spectrometry (Full Scan) CRG MARINE LABORATORIES 2020 Del Amo Blvd,Suite 200,Torrance,CA 90503,(310)533-5190 ACID AND BASE/NEUTRAL EXTRACTABLE CONPOUNDS BY GAS CHROMATOGRAPHY/MASS SPECTROMETRY (FULL SCAN) Approved by: Rhonda Moeller, QA Officer Date Richard Gossett, Laboratory Director Date Laboratory Operating Procedure Method 8270, Revision A Page 1 of 13 METHOD 8270: ACID AND BASE/NEUTRAL EXTRACTABLE COMPOUNDS BY GAS CHROMATOGRAPHY/MASS SPECTROMETRY (FULL SCAN) REFERENCE: EPA, 40 CFR Part 122 through 270, SW846 Volume 1 B 1.0 SCOPE AND APPLICATION 1.1 This method is used to determine the concentration of various organic. Table 1 indicates compounds that may be determined by this method and their approximate retention times. Table 1. Target Compound List COMPOUND RETENTION METHOD TIME DETECTION DB-5 COLUMN LIMIT (pg/kg) D5-Phenol 8.00 (Recovery Surrogate) Naphthalene-d8 (Recovery 13.34 Surrogate) 2-Fluorophenol 15.00 (Recovery Surrogate) Acenaphthene-d10 (Recovery 21.49 Surrogate) 2,4,5,6-Tetrachloro-m-xylene 26.45 (Recovery Surrogate) 2,4,6-Tribromophenol 27.17 (Recovery Surrogate) PCB030 31.66 (Recovery Surrogate) Phenanthrene-d10 (Recovery 32.29 Surrogate) Anth racene-d 10 32.84 Internal Standard PC6112 46.29 (Recovery Surrogate) 2,2'-5,5'-Tetrabromobiphenyl 52.07 Internal Standard Chrysene-d12 56.25 (Recovery Surrogate) PCB198 60.57 (Recovery Surrogate) Laboratory Operating Procedure Method 8270, Revision A Page 2 of 13 Perylene-d12 68.49 (Recovery Surrogate) Phenol 8.21 100 2-Chloro henol 10.56 50 Aniline 11.37 100 2,4-Dimeth I phenol 11.11 100 bis 2-Chloroethox methane 11.44 50 1,3-Dichlorobenzene 11.98 10 1,4-Dichlorobenzene 12.13 10 1,2-Dichlorobenzene 12.39 10 Benz I Alcohol 12.23 100 2-Nitro phenol 12.41 100 bis 2-Chloroiso ro I ethane 12.61 50 2,4-Dichloro henol 12.83 50 N-nitrosodi-n- ro lamine 12.95 50 N-nitrosodimeth lamine 12.97 50 Hexachloroethane 13.15 50 Nitrobenzene 13.32 50 Naphthalene 13.39 1.0 Iso horone 13.99 50 Dichlorvos 14.52 10 bis 2-Chloroeth I ether 14.59 50 1,2,4-Trichlorobenzene 14.81 10 Benzidine 15.31 50 4-Ch loro-3-meth I phenol 15.59 100 4-Chloroaniline 15.74 50 2-Methyl na hthalene 15.98 1.0 Hexachlorobutadiene 16.24 50 1-Meth Ina hthalene 16.39 1.0 2,4,6-Trichloro henol 17.42 50 Benzoic Acid 17.70 100 Biphenyl 18.30 1.0 2,6-Dimeth Inaphthalene 19.05 1.0 Mevin hos 19.55 10 Hexachloroc clo entadiene 19.83 50 Acena hth Iene 20.47 1.0 Dimeth I Phthalate 20.56 5 Acena hthene 21.74 1.0 4-Nitroaniline 21.82 50 2,4-Dinitro henol 22.27 100 4-Nitro phenol 23.30 100 2,3,5-Trimeth Ina hthalene 24.42 1.0 3-Nitroaniline 24.57 50 Laboratory Operating Procedure Method 8270, Revision A Page 3 of 13 Fluorene 25.18 1.0 Diethyl Phthalate 25.45 5 2,6-Dinitrotoluene 25.89 50 2-Meth I-4,6-dinitro henol 26.04 100 Dibenzofuran 26.12 50 Demeton 26.21 10 2,4-Dinitrotoluene 26.55 10 Ethoprop 26.83 10 4-Chloro hen I phenyl ether 28.97 50 2-Nitroaniline 29.13 50 Phorate 29.17 10 N-nitrosodi hen lamine 30.04 50 Azobenzene 30.21 50 Dimethoate 30.60 5 Pentachloro henol 31.70 50 Phenanthrene 32.67 1.0 4-Bromo hen I phenyl ether 32.96 50 Anthracene 32.96 1.0 al ha-BHC 33.26 1.0 Diazinon 33.48 5 Disulfoton 33.65 10 Hexachlorobenzene 33.90 1.0 beta-BHC 35.29 1.0 gamma-BHC 35.79 1.0 Methyl Parathion 36.69 10 delta-BHC 37.56 1.0 Fenchloro hos 37.91 10 1-Meth I henanthrene 38.01 1.0 Dibut I Phthalate 39.46 5 Marathion 39.91 5 Fenthion 40.38 10 Chlorpyrifos 40.53 5 Heptachlor 41.36 1.0 Trichloronate 41.44 10 Fluoranthene 42.98 1.0 Aldrin 43.99 1.0 P rene 44.85 1.0 Tetrachlorvin hos 45.61 10 Tokuthion 46.91 10 Heptachlor Epoxide 47.00 1.0 Bolstar 47.40 10 gamma-Chlordane 48.77 1.0 2,4'-DDE 49.18 1.0 Endosulfan 1 49.69 1.0 Laboratory Operating Procedure Method 8270, Revision A Page 4 of 13 alpha-Chlordane 49.91 1.0 Fensulfothion 50.10 10 trans-Nonachlor 50.29 1.0 4,4'-DDE 51.50 1.0 Mer hos 51.55 10 Dieldrin 51.61 1.0 2,4'-DDD 52.11 1.0 But Ibenz I Phthalate 53.13 5 Endrin 53.19 1.0 Endosulfan II 53.84 1.0 4,4'-DDD 54.53 1.0 2,4'-DDT 54.79 1.0 Endrin Aldehyde 55.20 1.0 Benz a anthracene 56.25 1.0 Chrysene 56.52 1.0 Endosulfan Sulfate 56.93 1.0 4,4'-DDT 57.24 1.0 bis- 2-eth Ihex I Phthalate 59.24 5 Endrin Ketone 60.23 1.0 Guthion 60.47 10 Couma hos 60.52 10 Methoxychlor 61.36 1.0 M i rex 64.27 1.0 Di-n-oct I Phthalate 64.71 5 Benzo b fluoranthene 65.47 1.0 Benzo k fluoranthene 65.87 1.0 Benzo a rene 67.71 1.0 Benzo a rene 68.07 1.0 Perylene 68.77 1.0 3,3'-Dichlorobenzidine 72.45 50 Indeno 1,2,3-c,d rene 76.29 1.0 Dibenz a,h anthracene 76.68 1.0 Benzo[g,h,i]perylene 77.87 1.0 PCBs By Congener 1 PCBs By Aroclor I 1 10 2.0 SUMMARY OF METHOD A 1-2 pL sample is injected into a gas chromatograph (GC) equipped with a mass selective detector. The GC is temperature programmed to separate the compounds and confirmation is achieved for the single component peaks using ions specific to each target compound. Compounds eluting from the GC are identified by matching the retention Laboratory Operating Procedure Method 8270, Revision A Page 5 of 13 times of the unknown peaks with those from a known calibration standard and the concentration of each identified component is measured by comparison of the responses. 3.0 PREVENTION OF INTERFERENCES 3.1 Refer to Method 3510 or 3545 for interference caused during sample extraction and handling. During sample analysis, these same precautions should be followed. 3.2 Impurities in the carrier and makeup gases may be avoided by using Ultra-High purity gases and/or gas purifying cartridges. See the instrument manufacturer for guidelines. 3.3 Contamination by carryover may occur whenever high level and low-level samples are sequentially analyzed. To reduce carryover, the syringe used for sample injection shall be rinsed a minimum of 5 times between samples using n-hexane. Whenever possible, samples shall be analyzed from low to high concentrations. 3.4 A procedural blank shall be analyzed with each batch of 20 or less samples to check for contamination during sample processing. 4.0 SAFETY 4.1 It is mandatory to wear a laboratory coat, closed toe shoes, and safety glasses in the Laboratory. Gloves shall be worn while working with solvents. 4.2 All steps involving the use of large volumes of solvents shall be performed in a fumehood. 4.3 Material Safety Data Sheets (MSDS) are on file and available at all times to personnel using hazardous materials. It is the responsibility of everyone using these materials to be familiar with the potential hazards of the chemicals in their work area. If the analyst is uncertain of the potential hazards of specific chemicals, contact the supervisor prior to using the chemicals. 4.4 Extreme caution, awareness and knowledge of the location and safe use of fire extinguishers, eye wash fountains, and safety showers is required. Laboratory Operating Procedure Method 8270, Revision A Page 6 of 13 4.5 Personnel performing this procedure shall be instructed in the safe use of solvents, the requirements for protective equipment, and solvent spill cleanup procedures. 5.0 APPARATUS AND MATERIALS 5.1 Hewlett Packard 5973 Inert GC/MS or a Shimadzu QP2010 GC/MS 5.2 J&W Scientific XLB Column (or equivalent), 60 meters in length, 0.25 pm film thickness, and 0.25 mm I.D 5.3 10 pL syringe 5.4 Ultra-high purity helium 6.0 REAGENTS 6.1 HPLC or Pesticide grade n-hexane, methanol and methylene chloride. 6.2 Stock solutions. All stock solutions are purchased from NIST traceable commercial suppliers. Store at or below 4 °C and protect from light. Stock standards shall be replaced after one year or sooner if comparison with check standards indicates a problem. 6.3 Calibration Standards. Prepare a minimum of five concentration levels for each parameter of interest. One of the concentration levels shall be near the method detection limit. The remaining concentration levels shall bracket the expected concentrations found in the samples. Calibration solutions shall be replaced after 6 months or sooner if a problem is indicated. 6.4 Internal Standards. Select one or more internal standards that are similar in analytical behavior to the compounds of interest. The analyst shall demonstrate that the selected compound(s) is not affected by the method or matrix interference. 6.4.1 Just prior to analysis, add a known constant amount of internal standard to all calibration solutions, blanks, and samples. 6.5 Recovery Surrogates. Select one or more internal standards that are similar in analytical behavior to the compounds of interest. Laboratory Operating Procedure Method 8270, Revision A Page 7 of 13 6.5.1 Prior to the extraction of the samples, add a known amount of recovery surrogate to all blanks and samples. See Methods 3510 and 3545 for additional information about this procedure. 7.0 CALIBRATION AND MAINTENANCE 7.1 Shimadzu QP2010 or Agilent 6890 GC/MS 7.1.1 GC Oven Operating Conditions: Initial Oven Temperature =45 °C Initial Hold = 5 min Ramp 1 = 20 °C/min to 125 °C Hold Time = 0 min Ramp 2 = 2.5 °C/min to 285 °C Hold Time = 17 min 7.1.2 Injector Operating Conditions: Injector = Splitless or On-Column Mode = Track Oven Temperature (On-Column Only) Nominal Initial Pressure = 23.5 psi (on) 7.1.3 Column Operating Conditions: Max Temp = 325 °C Mode = Constant Flow Initial Flow = 1.5 mL/min Average Carrier Velocity = 30-40 cm/sec Carrier Gas = Helium 7.1.4 Detector Operating Conditions: Transfer Line Temperature = 285 °C Ionization Voltage = 70 ev Gain = +100 to +300 volts over standard sensitivity target tune 7.1.5 Autosampler Operating Conditions (Back Injector): Sample Washes = 2 Sample Pumps = 2 Injection Volume = 2.0 pL Syringe Size = 10 pL Post Injection Washes Solvent A = 3 Post Injection Washes Solvent B = 3 Plunger Speed = Fast 7.1.6 System Maintenance Laboratory Operating Procedure Method 8270, Revision A Page 8 of 13 Prior to each set of samples, remove ca. 30 cm of the retention gap or column, replace injector septum if needed, and refill the solvent wash bottles. Clean glass inlet liners or replace as needed. Replace the gas cartridges every 6 months. Replace the GC columns as needed. Enter all maintenance actions into the instrument maintenance logbook. 8.0 QUALITY CONTROL 8.1 With each batch of samples (maximum 20 samples per batch), a procedural blank is extracted and analyzed to demonstrate that procedural interferences are under control. Deionized water is used as the blank matrix. 8.2 With each batch of samples, a duplicate sample and/or matrix spike/matrix spike duplicate (MS/MSD) set of samples is analyzed with the appropriate extraction procedure to measure the precision of the extraction procedure. A non-spiked sample of an MS/MSD set is analyzed to determine background concentrations for each parameter of interest. The MS/MSD samples are spiked with specific parameters at a concentration greater than ten times the method detection limit and analyzed to determine the percent recovery of the spiked compounds. For concentrations at ten times the method detection limit, a precision factor between the duplicate samples or MS/MSD samples is calculated and compared to the corresponding QC acceptance criteria. 8.3 Every sample, spike set, and blank is spiked with an appropriate surrogate spike solution consisting of 1 to 6 surrogate compounds. The surrogate spike is used to demonstrate the efficiency of the extraction and analytical procedure by allowing calculation of the percent recovery of each surrogate compound. Control charts and control limits are generated by measuring the mean and standard deviation of the surrogate percent recovery for the previous 20 samples. Upper and lower warning limits are calculated at two times the standard deviation from the mean. Upper and lower control limits are calculated at three times the standard Laboratory Operating Procedure Method 8270, Revision A Page 9 of 13 deviation from the mean. Surrogate control limits and results are presented with the analytical results. When surrogate results indicate atypical method performance, a quality control check sample is analyzed and an evaluation of the procedure and instrumentation is made. 8.4 If any individual parameter falls outside of the designated range for percent recovery, that parameter has failed the acceptance criteria. An evaluation of the method procedure and instrumentation shall be made to uncover evidence of any atypical performance. If there is atypical performance of the method procedure and/or instrumentation, the problem shall be immediately identified and corrected prior to the analysis of any further samples. A re-spike and/or quality control check sample shall be analyzed and evaluated. If possible, all samples from the suspect batch shall be re-analyzed under corrected method conditions. If samples can not be re- analyzed, the analytical results for the non-spiked samples are suspect and shall be reported with the result flagged and followed by an explanation of the problem. 8.5 QA/QC records are maintained to document the quality of data generated. If any constituent falls outside the designated range, that compound has failed the acceptance criteria. Failure to meet the stated requirement shall require that corrective action be taken to eliminate the problem prior to the analysis of any samples. Samples from the batch being analyzed at the time the failure is detected shall be reanalyzed after the corrective action has been taken. A batch is defined as 20 or less samples. If any sample cannot be reanalyzed, the result for that element shall be flagged and a detailed report is included with the result. 8.5.1 Initial Calibration Check- Prior to analyzing any samples, using a second-source calibration standard an initial calibration of the instrument is performed with each batch of samples. This calibration shall be within 15% of the initial calibration curve. 8.5.2 Calibration Check- Using a second-source calibration standard, a calibration check will be performed every 12 hours and at the end of every batch of samples. The calibration check shall be within 15% of the initial calibration curve. 8.5.3 Matrix Spikes- Matrix spike and matrix spike duplicates as well as duplicate samples shall be analyzed with each batch of samples to determine the precision for each compound. A Laboratory Operating Procedure Method 8270, Revision A Page 10 of 13 control chart is generated to document the precision. Control limits are established by using the mean and standard deviation from 20 results. Upper and lower warning limits are two times the standard deviation and upper and lower "out of control" limits are three times the standard deviation for those compounds that are greater than 10 times the method detection limit. 8.5.4 CRM/LCM- Certified reference materials and/or lab control materials shall be analyzed with each batch of samples. The reported value shall be within the limits set forth by the agency providing the material. 8.5.5 Blanks- Lab reagent blanks shall be analyzed with each batch of samples. No compound shall be detected at greater than 3 times the method detection limit. 8.5.6 QCS- A method standard is extracted along with each batch of samples. Prepare the QC check standard to 1 L of reagent water. 8.5.6 Internal Standards- Internal standards shall be added in known amounts to blanks, calibration standards, continuing calibration check solutions, and samples to compensate for instrumental drift. 8.5.7 Recovery Surrogates- Recovery surrogates shall be added in known amounts to all blanks and samples to indicate sample processing efficiency. Sample results shall not be adjusted for surrogate recovery efficiency unless specifically requested by the client. 8.5.8 Daily GCMS Performance Test- At the beginning of each batch of samples, the GCMS system must be checked to see of acceptable performance criteria are achieved for DFTPP. The criteria are presented in the following table. Mass m/z Abundance Criteria 69 0-100 percent of Mass 198 70 < 2 percent of Mass 69 127 40-60 percent of Mass 198 198 Base peak, 100 percent relative abundance 199 5-9 percent of Mass 198 275 10-30 percent of Mass 198 365 > 1 percent of Mass 198 Laboratory Operating Procedure Method 8270, Revision A Page 11 of 13 441 Present but < Mass 443 442 > 40 percent of Mass 198 443 17-23 percent of Mass 442 9.0 SAMPLE COLLECTION, PRESERVATION,AND HANDLING This section is not applicable to this method. 10.0 PROCEDURE 10.1 Using the Shimadzu/Agilent data system, load the appropriate method for the parameters of choice. 10.2 Set up a sequence table for the analysis of the samples. The sequence table should include all calibrations necessary for five calibration levels of each parameter of interest, the recovery surrogate solution, a calibration check solution for every 12 hours of operation, and all blanks and samples. 10.3 Place the vials in the autosampler tray insuring that they are in the same order as the sequence table. 10.4 Load and run the sequence file and insure that the autosampler operates correctly. 10.5 From the results of the calibrations, build a calibration table. 10.6 Once the calibration table is completed, load the result file for each sample and print the appropriate report. 11.0 CALCULATIONS 11.1 The qualitative identification of compounds determined by this method is based on retention time matching. Results are confirmed by quantification using a specific mass for each compound and comparison wiith the retention times. 11.2 An internal standard calibration procedure is used by calculating the relative response factor (RRF) for each analyte using the following formula: (AX)(Cis) RRF = Laboratory Operating Procedure Method 8270, Revision A Page 12 of 13 (Als)(CX) Where: AX= Area of the Target Analyte Peak Cis = Mass of the Internal Standard A,s = Area of the Internal Standard Peak CX = Concentration of the Target Analyte 11.3 The quantitation of each analyte of interest shall be based on the area of the peak of each ion at the retention corresponding to the calibration standard. The concentration is calculated using the following formula: (AUNK)(CIS) Concentration = (AIS)(RRFTA)(SW) Where: AUNK = Peak area of the sample CIS = Mass of the Internal Standard A,s = Area of the Internal Standard Peak RRFTA = Relative Response Factor for the Target Analyte SW= Weight of sample extracted 11.4 The Method Detection Limit (MDL) is defined as the minimum concentration of a compound that can be measured and reported with 99% confidence that the value is greater than zero. The MDLs listed in Table 1 were determined using a clean marine sediment sample following US EPA guidelines in 40CFR. Laboratory Operating Procedure Method 8270, Revision A Page 13 of 13 Appendix E Attachment 8: Standard Operating Procedure for Method 4500-P E Determination of Ortho and Total Phosphorus by Colorimetry CRG MARINE LABORATORIES 2020 Del Amo Blvd,Suite 200,Torrance,Ca 90501 310 533-5190 DETERMINATION OF ORTHO AND TOTAL PHOSPHORUS BY COLORIMETRY Approved by: Rhonda Moeller, QA Officer Date Richard Gossett, Laboratory Manager Date Laboratory Operating Procedure Method 4500-P E Page 1 of 5 METHOD 4500-P E DETERMINATION OF ORTHO AND TOTAL PHOSPHORUS BY COLORIMETRY REFERENCE: [Standard Methods 20th Edition-SM4500-P E] 0.-1 SCOPE AND APPLICATION 0.1 This method is used to determine the concentrations of Ortho and Total Phosphorus in water, seawater or sediments. 1.-1 SUMMARY OF METHOD 1.1 Persulfate digestion/vanadomolybdophosphoric acid colorimetric methods are used. Total phosphorus analysis is a digestion followed by the colorimetric analysis. Ammonium molybdate reacts in an acid medium with dilute solutions of phosphorus to form molybdophosphoric acid. This complex reacts with vanadium to form the yellow vanadomolybdophosphoric acid. The intensity of this color is proportional to the phosphorus concentration. Polyphosphates (and some organic phosphorus compounds) may be converted to the orthophosphate form by sulfuric acid hydrolysis. Organic phosphorus compounds may be converted to the orthophosphate form by persulfate digestion. Samples for total phosphorus must be digested before analysis. 2.-1 SAFETY 2.1 Good safety habits and laboratory techniques should be used throughout the procedure. Consult the Material Safety Data Sheet for information specific to the reagents used. For additional information, refer to Section 3. 2.2 It is mandatory to wear a laboratory coat, closed toe shoes, and safety glasses in the Laboratory. Gloves shall be worn while working with solvents. 2.3 All steps involving the use of large volumes of solvents shall be performed in a fume hood. 2.4 Material Safety Data Sheets (MSDS) are on file and available at all times to personnel using hazardous materials. It is the responsibility of everyone using these materials to be familiar with the potential hazards of the chemicals in their work area. If the analyst is uncertain of the potential hazards of specific chemicals, contact the supervisor prior to using the chemicals. 2.5 Extreme caution, awareness and knowledge of the location and safe use of fire extinguishers, eye wash fountains, and safety showers are required. Laboratory Operating Procedure Method 4500-P E Page 2 of 5 3.0 SAMPLE COLLECTION, PRESERVATION AND STORAGE 3.1 Samples are collected in plastic or glass bottles with a minimum volume of 250mL. 3.2 Refrigerate all samples at 4 degrees C. 3.3 For total phosphorus the samples are preserved with 2 ml of 50 percent H2SO4 per liter of sample. 3.4 Samples for dissolved total Phosphorus must be filtered through 0.45 microns filter prior to preservation. 3.5 The holding time is 28 days for total phosphorus, assuming the sample is preserved. 4.0 INTEFERENCES 4.1 Arsenates react with the molybdate reagent to give a blue color similar to that formed with phosphate. Arsenate concentrations as low as 0.1 mg/L interfere with the phosphorus determination. Hexavalent chromium and nitrite interfere to give results about 3 percent low at concentrations of 1 mg/L and 10-15 percent low at 10 mg/L. The method is applicable to drinking water and wastewater samples. 5.0 REAGENTS 5.1 5N Sulfuric Acid: Dilute 140 ml of conc. H2SO4 with deionized water to 1 liter. 5.2 Molybdovanadate reagent, potassium persulfate powder pillows, Sodium Hydroxide Solution (1.54 N), Water-deionized. Note: All these reagents are provided in the Hach's total high range Test 'N Tube(TM) reagent set 5.3 Phenolphthalein indicator. 5.4 Sodium hydroxide solution 1 N: Carefully add 40 grams of NaOH to 1-liter beaker add water and mix. Allow to cool bring to volume 5.5 Stock Phosphorus solution: This is bought ready made from Fisher scientific 5.6 Intermediate Standard Phosphorus Solution: Dilute 10.0 ml of 1000 ppm stock to 100 ml with D.1. water. This standard is 100.0 ppm phosphorus. 6.0 APPARATUS 6.1 DR 4000V Spectrophotometer. 6.2 Hach's total high range Test 'N Tube(TM) reagent set which includes: molybdovanadate reagent, potassium persulfate powder pillows, Sodium Hydroxide Solution (1.54 N), Total Phosphorus Test Vials, Water-deionized 6.3 Class 'A' 50 and 100 ml volumetric flasks. Laboratory Operating Procedure Method 4500-P E Page 3 of 5 6.3.1 Dilute 1.25 ml of 100 ppm stock to 5ml. This LCS/LCSD standard is 25 mg/L for total phosphorus 6.3.2 Dilute 3.75 ml of 100 ppm stock to 5ml. This standard is 75 mg/L for total phosphorus 6.4 Use the Hach programs with preset calibration for the determination of total phosphates. 6.5 Standards are digested similar to the samples for total phosphorus. 7.0 PROCEDURE 7.1 Phosphorus, Total 7.1.1 pH correction. Add one drop of phenolphthalein indicator add several drops of 0.1 N NaOH until a pink color develops. Add 1 N H2SO4 drop wise and discharge the pink color. 7.1.2 Add 5 mL of samples or standards to the total phosphorus vials from the Hach kit. 7.1.3 Add one pillow of Potassium Persulfate reagent, screw the cap tightly and shake to dissolve. 7.1.4 Place the vials in a COD reactor and boil at 150 degrees centigrade for 30 minutes. 7.1.5 Allow the vials to cool to 18-25 degrees. 7.1.6 Add 2.0 mL of 1.54N NaOH to each vial followed by 0.5 mL of the molybdovanadate reagent. 7.1.7 Using Hach's program 3040, start the timer for a 7 minutes reaction. 7.1.8 Use the blank to zero, then read all the standards and samples recording both the absorbance and concentrations on the bench sheet. 8.0 QUALITY CONTROL 8.1 Batching concept of samples must be adhered to. 8.1.1 A Batch is comprised of no more than 20 field samples. Each batch must be accompanied by QC samples which consist of a Blank sample, laboratory control samples (LCS/LCSD), matrix spike (MS) and matrix spike duplicate (MSD). If less than 20 samples are analyzed in a 24 hour period, then it will be necessary to analyze a blank and LCS/LCSD with those samples. 8.1.2 Blank Sample— is a reagent water sample that is treated in the same way as any field sample to determine if there are any method contaminations or interferences from the laboratory, technician, or reagents. The blank is also digested similar to the samples. 8.1.3 LCS/LCSD is reagent water that has been spiked at 25 ppm and analyze as above. The recovery limits are 85-115 percent for total phosphorus. If recoveries are outside of these limits, then the problem must be identified, and the Laboratory Operating Procedure Method 4500-P E Page 4 of 5 samples reanalyzed. If there is limited sample available, or if the analysis cannot be repeated for any reason, then a new sample should be obtained. For total phosphorus analysis, all the QC samples are also digested. 8.1.4 MS and MSD are field samples that are spiked at 25 ppm from a second source of standards. Analyze for phosphorus and calculate the percent recovery, recovery criteria are 80- 100 percent. Do not reanalyze samples if MS/MSD recoveries are outside QC criteria. 8.1.5 Criteria for RPD on duplicate and an MS/MSD sample is 20 percent. Laboratory Operating Procedure Method 4500-P E Page 5 of 5 Appendix E Attachment 9: Standard Operating Procedure for Method 2340 B: Hardness by Calculation CRG MARINE LABORATORIES 2020 Del Amo Blvd.,Suite 200,Torrance,CA 90501,(310)533-5190 Hardness by Calculation Approved by: Richard Gossett, Laboratory Manager Date Laboratory Operating Procedure Method 2340B Page 1 of 2 METHOD 2340 B: Hardness by Calculation REFERENCE: CRG LOP Method 200.8, Revision B., Standard Methods (1995), Hardness by Calculation, EPA Methods for Chemical Analysis of Water and Wastes, Method 200.8, Revision 5.4 (May, 1994); NOAA Sampling and Analytical Methods of the National Status and Trends Program, Volume III, (1993) 1.0 SCOPE AND APPLICATION This method provides a procedure for the determination of Calcium (Ca) and Magnesium (Mg) in waters, wastewaters and surface run-off analyzed by Inductively Coupled Plasma Mass Spectrometry (ICP-MS). 2.0 SUMMARY OF METHOD The concentrations of calcium and magnesium are determined by Inductively Coupled Plasma Mass Spectrometry (ICP-MS). Refer to CRG LOP Method 200.8, Revision B. 3.0 PROCEDURE Calcium and Magnesium can occur at high levels. Samples to be analyzed for hardness must be diluted 10X to 100X to match the calibration curve of the ICP- MS. 4.0 CALCULATIONS The resultant Calcium and Magnesium concentrations (in parts per million) are used to calculate Hardness, mg equivalent CaCO3/L= 2.497 (Ca, mg/L) + 4.118 (Mg, mg/L) Laboratory Operating Procedure Method 2340B Page 2 of 2 Appendix E Attachment 10: Standard Operating Procedure for Method 2540 D: Determination of Total Suspended Solids (Non-Filterable Residue) CRG MARINE LABORATORIES 2020 Del Amo Blvd,Suite 200,Torrance,Ca 90501 310 533-5190 DETERMINATION OF TOTAL SUSPENDED SOLIDS (Non-Filterable Residue) — SM 2540D Approved by: Richard Gossett, Laboratory Manager Date Laboratory Operating Procedure Method 2540 D, Revision B Page 1 of 5 METHOD 2540 D DETERMINATION OF TOTAL SUSPENDED SOLIDS (Non-Filterable Residue) REFERENCE: [Standard Methods 19th Edition — 2540 C and US EPA Method 160.2(lssued 1971)] 0.4 SCOPE AND APPLICATION 0.1 This method is used to determine total suspended solids in drinking, surface, and saline waters. It is also applicable to industrial wastes. 0.2 The practical range for this method is 4 to 20,000 mg/L and approximate detection limit is 4.0 mg/L. 1.4 SUMMARY OF METHOD 1.1 A representative portion of sample is filtered through a pre-weighed glass fiber filter, and the residue on the filter is heated to dryness to a constant weight at 105°C. 2.4 SAFETY 2.1 Good safety habits and laboratory techniques should be used throughout the procedure. Consult the Material Safety Data Sheet for information specific to the reagents used. For additional information, refer to Section 3. 2.2 It is mandatory to wear a laboratory coat, closed toe shoes, and safety glasses in the Laboratory. Gloves shall be worn while working with any chemicals. 2.3 Material Safety Data Sheets (MSDS) are on file and available at all times to personnel using hazardous materials. It is the responsibility of everyone using these materials to be familiar with the potential hazards of the chemicals in their work area. If the analyst is uncertain of the potential hazards of specific chemicals, contact the supervisor prior to using the chemicals. 2.4 Extreme caution, awareness, knowledge of the location and safe use of fire extinguishers, eye wash fountains, and safety showers are required. 3.4 SAMPLE COLLECTION, PRESERVATION AND STORAGE 3.1 Samples should be collected in clean plastic bottles and stored at 4°C. Laboratory Operating Procedure Method 2540 D, Revision B Page 2 of 5 3.2 Chemical preservation is not used. 3.3 Samples must be analyzed within 7 days of sampling. 4.0 INTERFERENCES 4.1 Floating particles such as leaves and sticks are not representative of the sample and should be removed prior to the analysis. 4.2 The sample volume used should not yield more than 20 mg of residue. Too much residue on the filter paper will crust over and entrap water that will not be driven off during drying. 5.0 APPARATUS AND MATERIALS 5.1 Glass fiber filter disks 5.2 Millipore filtration apparatus 5.3 Suction flask 5.4 Evaporating oven, 103-105°C 5.5 Analytical balance able to measure 0.1 mg accurately 5.6 De-ionized water 5.7 Desiccator. 6.0 PROCEDURE 6.1 An analytical balance calibration check is to be performed daily prior to the implementation of this method. Refer to LOPM 0200. 6.2 Preparation of fiber filter 6.2.1 Place disk with wrinkled surface up in the filtration apparatus. Apply vacuum and wash disk with three successive 20 mL portions of de-ionized water. Continue suction to remove all water. 6.2.2 Dry the filters at 105 °C and keep them in a desiccator until ready to use. 6.2.3 One can also use pre-weighed filters bought ready to use from vendors. 6.3 Selection sample sizes Laboratory Operating Procedure Method 2540 D, Revision B Page 3 of 5 The sample volume should yield between 10 and 20 mg of dried residue. If filtration is very slow, reduce the volume size. 6.4 Sample Analysis 6.4.1 Set up the filtration apparatus and begin suction. 6.4.2 Shake the sample bottle rigorously to ensure homogeneity. 6.4.3 Transfer a measured volume (400mL) to the filter and rinse with three successive 10 mL portions of de-ionized water. Continue suction for 3 min after filtration is complete. 6.4.4 Transfer the filters to the oven and heat to dryness at 105°C. This should take at least one hour. Let it cool in a desiccator and weigh it out. 6.4.5 Repeat 6.4.4 until the weight change is less than 4% or 0.5 mg of the previous weight, whichever is less. 6.4.6 Note: samples should be brought to room temperature prior to analysis. 7.0 CALCULATIONS 7.1 TSS (mg/L) = (A-B) x 1000 Sample Volume (L) A = weight of filter+ Residue (g) B = weight filter (g) 8.0 QUALITY CONTROL 8.1 Each batch of samples (maximum 20 samples per batch) must have a method blank and a sample duplicate (R2). For more than 15 samples, two sets of sample duplicates are required. 8.2 The relative percent difference between the sample and sample duplicate (R1/R2) should be±20%. 9.0 REPORTING RESULTS 9.1 Units of measure: mg/L 9.2 Significant figures: 3 9.3 Reporting limit: 5 mg/L Laboratory Operating Procedure Method 2540 D, Revision B Page 4 of 5 Appendix E Attachment 11 : Standard Operating Procedure for Method 4500-NH3-N F: Determination of Ammonia- N by Colorimetry Using the Phenate Method CRG MARINE LABORATORIES 2020 Del Amo Blvd,Suite 200,Torrance,Ca 90501 310 533-5190 DETERMINATION OF AMMONIA-N BY COLORIMETRY Approved by: Rhonda Moeller, QA Officer Date Richard Gossett, Laboratory Manager Date Laboratory Operating Procedure Method 4500-NH3-N F, Revision B Page 1 of 5 METHOD 4500-NH3-N F DETERMINATION OF AMMONIA-N BY COLORIMETRY USING THE PHENATE METHOD REFERENCE: [US EPA Method 350.1 and Standard Methods 19th Edition- SM4500-NH3 F] 0.0 SCOPE AND APPLICATION 0.1 This method is used to determine the concentration of Ammonia-N in water, seawater or sediments. 1.0 SUMMARY OF METHOD 1.1 An intensely blue compound, indophenol, is formed by the reaction of ammonia, hypochlorite, and phenol catalyzed by sodium nitroprusside. 2.0 SAFETY 2.1 Good safety habits and laboratory techniques should be used throughout the procedure. Consult the Material Safety Data Sheet for information specific to the reagents used. For additional information, refer to Section 3. 2.2 It is mandatory to wear a laboratory coat, closed toe shoes, and safety glasses in the Laboratory. Gloves shall be worn while working with solvents. 2.3 All steps involving the use of large volumes of solvents shall be performed in a fume hood. 2.4 Material Safety Data Sheets (MSDS) are on file and available at all times to personnel using hazardous materials. It is the responsibility of everyone using these materials to be familiar with the potential hazards of the chemicals in their work area. If the analyst is uncertain of the potential hazards of specific chemicals, contact the supervisor prior to using the chemicals. 2.5 Extreme caution, awareness and knowledge of the location and safe use of fire extinguishers, eye wash fountains, and safety showers are required. 3.0 SAMPLE COLLECTION, PRESERVATION AND STORAGE 3.1 Samples should be collected in glass or plastic bottles that are thoroughly cleaned and rinsed with deionized water. 3.2 If samples are analyzed within 24 hrs of collection, refrigerate at Laboratory Operating Procedure Method 4500-NH3-N F, Revision B Page 2 of 5 4°C. For preservation for up to 28 days, freeze at -20°C or acidify to pH <2 with H2SO4 and store cooled to 4°C until analyzed. If acid preservation is used, the sample pH must be restored to neutral just prior to analysis using NaOH. 4.-1 INTERFERENCES 4.1 Magnesium and calcium interference can be eliminated by the addition of citrate. 4.2 Remove interfering turbidity by distillation or filtration. 4.3 Hydrogen sulfide interference can be removed by acidifying the sample using HCI and aerating the sample until the odor can no longer be detected. 4.4 Check the sample for the presence of Residual Chlorine. If Residual Chlorine is present add 80mg of sodium thiosulfate per liter of sample and shake thoroughly. 5.-1 STANDARDS 5.1 All standards are bought ready for use from Fischer scientific. 5.2 LCS and LCSD: these are lab reagent water spiked at 0.25 ppm with the second source standard. 5.3 MS and MSD: these are field samples spiked at 0.25 ppm with the second source standard. 5.4 Calibration verification standard: this is lab reagent water spiked at 0.75 ppm with the first source standard 6.-1 REAGENTS 6.1 Ammonia-free water 6.2 Phenol Solution: Mix 11.1 mL liquefied phenol with ethanol to a final volume of 100mL. Prepare weekly. 6.3 Sodium nitroprusside, 0.5% w/v: Dissolved 0.5g sodium nitroprusside in 100mL of deionized water. Store in amber bottle for up to one month. 6.4 Alkaline Citrate: Dissolve 200g trisodium citrate and 10g NaOH in deionized water. Dilute to 1000mL. 6.5 Sodium Hypochlorite: Purchase from commercial supplier at a 5% concentration. 6.6 Oxidizing solution: Mix 100mL alkaline citrate solution with 25mL sodium hypochlorite. Prepare fresh daily. 6.7 Ammonium Chloride: Dilute the NH3C1 stock solution purchased from a commercial supplier to appropriate concentrations to establish a calibration curve. 7.-1 PROCEDURE Laboratory Operating Procedure Method 4500-NH3-N F, Revision B Page 3 of 5 7.1 Preliminary Distillation 7.1.1 Add 500 mL water and 20 mL borate buffer adjust pH to 9.5 with 6N NaOH solution, and add to a distillation flask. Add a few glass beads or boiling chips and use this mixture to steam out the distillation apparatus until distillate shows no trace of ammonia. 7.1.2 Use 500 mL de-chlorinated sample or a know portion diluted to 500 mL with water. When NH3-N concentration is less than 0.1 mg/L, use samples volume of 1000 mL. Remove residual chlorine by adding de-chlorinating agent equivalent to the chlorine residual. 7.1.3 Add 25 mL borate buffer solution and adjust the pH to 9.5 with 6N NaOH using a pH meter. 7.1.4 Immediately transfer sample flask to the distillation apparatus. Distill at a rate of 6 to 10 mL/min with the tip of the delivery tube below the surface of acid receiving solution. Collect the distillate in a 500 mL Erlenmeyer flask containing 50 mL 0.04N H2SO4. Collect at least 200 mL distillate. 7.1.5 Lower the distillation receiver so that the end of the delivery tube if free of contact with the liquid and continue distillation the last minute of two to cleanse condenser and delivery tube. Dilute to 500 mL with water. 7.1.6 Neutralize the distillate with 1 N NaOH solution prior to analysis using the Phenoate Method. 7.2 Sample Analysis 7.2.1 Place 25mL of sample into a 50mL Erlenmeyer flask. 7.2.2 Add 1 mL of the phenol solution, 1 mL of sodium nitroprusside solution, and 2.5mL oxidizing solution. 7.2.3 Cover samples with plastic wrap or paraffin wrapper film. 7.2.4 Let the color develop at room temperature in subdued light for at least 1 hr. The color is stable for 24hr. 7.2.5 Measure absorbance at 640nm. 7.2.6 Prepare a blank, blank spikes (LCS/LCSD), and second- source calibration standard using the same procedure. 8.4 CALCULATIONS 8.1 Prepare a standard curve by plotting absorbance readings of standards against ammonia concentrations of standards. Compute sample concentration by comparing to sample absorbance with the standard curve. 9.-1 QUALITY CONTROL Laboratory Operating Procedure Method 4500-NH3-N F, Revision B Page 4 of 5 9.1 Every batch must be accompanied with qualifying QC data. This will include a method blank (reagent water), laboratory control spikes (LCS and L CSD), matrix spike (MS) matrix spike duplicate (MSD) and a calibration verification standard. 9.2 The recovery limits for the LCS, LCSD and calibration standard should be 90-110 percent with RPD of 20 9.3 The recovery limits for MS and MSD should be 80-120 percent. Laboratory Operating Procedure Method 4500-NH3-N F, Revision B Page 5 of 5 Appendix E Attachment 12: Standard Operating Procedure for Method 351 .3 : Total Kj eldahl Nitrogen (Titrimetric) STANDARD OPERATING PROCEDURE Document No.: SOP-M747 Title: EPA Method 351.3:Total Kjeldahl Nitrogen (Titrimetric) Revision No. : 1.0 Calscience Environmental Laboratories, Inc. Effective Date: 04/18/03 Page 1 of 12 Title EPA Method 351.3: Total Kjeldahl Nitrogen (Titrimetric) Document No. SOP-M747 Revision No. 1.0 Supersedes : None �NCC:IT� LLC� i:: Y PROPRIETARY INFORMATION STATEMENT This document has been prepared by and remains the property of Calscience Environmental Laboratories, Inc. (Calscience), 7440 Lincoln Way, Garden Grove, California, 92841-1432. Distribution of this document to parties external to Calscience is solely for the purpose of evaluating Calscience's qualifications in association with the specific purpose for which it was furnished. The user agrees by use of this document to not distribute, reproduce, or use the information contained herein for any purpose other than for which it was specifically furnished and to return it upon Calscience's request. For further information, please contact our Quality Assurance Department at (714) 895-5494. APPROVED FOR RELEASE BY: i �3 MANAGEMENT DATE C)j 6 n 0 *(QA DEPARTMENT DATE STANDARD OPERATING PROCEDURE Document No.: SOP-M747 Title: EPA Method 351.3:Total Kjeldahl Nitrogen (Titrimetric) Revision No. : 1.0 Calscience Environmental Laboratories, Inc. Effective Date: 04/18/03 Page 2 of 12 1. METHOD IDENTIFICATION 1.1. Nitrogen, Kjeldahl, Total, EPA Method 351.3 (Colorimetric; Titrimetric; Potentiometric). 2. APPLICABLE MATRICES 2.1.1. This method may be applied to drinking water, surface water and saline water, domestic and industrial wastes. 3. DETECTION LIMITS 3.1. Three determinative methods may be used following distillation and each produces varying approximate detection limits. The titrimetric method yields detection limits of 0.5 mg/L in aqueous samples, and 8 mg/Kg in solids. 4. SCOPE AND APPLICATION 4.1. This method converts nitrogen components of biological origin (amino acids, proteins and peptides) to ammonia. 4.2. The method may not, however, convert nitrogenous compounds from industrial wastes (amines, nitro compounds, hydrazones, oximes, semicarbazones, and some refractory tertiary amines.) 5. METHOD SUMMARY 5.1. The sample is heated in the presence of concentrated sulfuric acid, K2SO4 and HgSO4 and evaporated until S03 fumes are obtained and the solution becomes colorless or pale yellow. The residue is cooled, diluted, and treated and then made alkaline with a hydroxide-thiosulfate solution. 5.2. The ammonia is distilled and subjected to titration, Nesslerization or potentiometry. 6. DEFINITIONS 6.1. Acceptance Criteria: Specified limits placed on characteristics of an item, process, or service defined in requirement documents. 6.2. Accuracy: The degree of agreement between an observed value and an accepted reference value. Accuracy includes a combination of random error (precision) and systematic error (bias) components which are due to sampling and analytical operations; a data quality indicator. 6.3. Batch: Environmental samples, which are prepared and/or analyzed together with the same process and personnel, using the same lot(s) of reagents. A preparation batch is composed of one to 20 environmental samples of the same NELAC-defined matrix, meeting the above mentioned criteria and with a maximum time between the start of processing of the first and last sample in the batch to be 24 hours. An analytical batch is composed of prepared environmental samples (extracts, digestates or concentrates) which are analyzed together as a group. An analytical batch can include prepared samples originating from various environmental matrices and can exceed 20 samples. STANDARD OPERATING PROCEDURE Document No.: SOP-M747 Title: EPA Method 351.3:Total Kjeldahl Nitrogen (Titrimetric) Revision No. : 1.0 Calscience Environmental Laboratories, Inc. Effective Date: 04/18/03 Page 3 of 12 6.4. Blank: A sample that has not been exposed to the analyzed sample stream in order to monitor contamination during sampling, transport, storage or analysis. The blank is subjected to the usual analytical and measurement process to establish a zero baseline or background value and is sometimes used to adjust or correct routine analytical results. 6.5. Calibration: To determine, by measurement or comparison with a standard, the correct value of each scale reading on a meter or other device. The levels of the applied calibration standard should bracket the range of planned or expected sample measurements. 6.6. Corrective Action: The action taken to eliminate the causes of an existing nonconformity, defect or other undesirable situation in order to prevent recurrence. 6.7. Data Reduction: The process of transforming raw data by arithmetic or statistical calculations, standard curves, concentration factors, etc., and collation into a more useable form. 6.8. Holding Times (Maximum Allowable Holding Times): The maximum times that samples may be held prior to analysis and still be considered valid or not compromised. 6.9. Laboratory Control Sample (however named, such as laboratory fortified blank, spiked blank, or QC check sample): A sample matrix, free from the analytes of interest, spiked with verified known amounts of analytes or a material containing known and verified amounts of analytes. It is generally used to establish intra- laboratory or analyst-specific precision and bias or to assess the performance of all or a portion of the measurement system. 6.10. Laboratory Duplicate: Aliquots of a sample taken from the same container under laboratory conditions and processed and analyzed independently. 6.11. Method Blank: A sample of a matrix similar to the batch of associated samples (when available) that is free from the analytes of interest and is processed simultaneously with and under the same conditions as samples through all steps of the analytical procedures, and in which no target analytes or interferences are present at concentrations that impact the analytical results for sample analyses. 6.12. Method Detection Limit: The minimum concentration of a substance (an analyte) that can be measured and reported with 99% confidence that the analyte concentration is greater than zero and is determined from analysis of a sample in a given matrix containing the analyte. 6.13. Precision: The degree to which a set of observations or measurements of the same property, obtained under similar conditions, conform to themselves; a data quality indicator. Precision is usually expressed as standard deviation, variance or range, in ,either absolute or relative terms. 6.14. Preservation: Refrigeration and/or reagents added at the time of sample collection (or later)to maintain the chemical and/or biological integrity of the sample. 6.15. Pure Reagent Water: Shall be water (defined by national or international standard) in which no target analytes or interferences are detected as required by the analytical method. STANDARD OPERATING PROCEDURE Document No.: SOP-M747 Title:EPA Method 351.3:Total Kjeldahl Nitrogen (Titrimetric) Revision No. : 1.0 Calscience Environmental Laboratories, Inc. Effective Date: 04/18/03 Page 4 of 12 6.16. Quality Assurance: An integrated system of activities involving planning, quality control, quality assessment, reporting and quality improvement to ensure that a product or service meets defined standards of quality with a stated level of confidence. 6.17. Quality Control: The overall system of technical activities whose purpose is to measure and control the quality of a product or service so that it meets the needs of users. 6.18. Quantitation Limits: Levels, concentrations, or quantities of a target variable (e.g., target analyte) that can be reported at a specific degree of confidence. 6.19. Raw Data: Any original factual information from a measurement activity or study recorded in a laboratory notebook, worksheets, records, memoranda, notes, or exact copies thereof that are necessary for the reconstruction and evaluation of the report of the activity or study. Raw data may include photography, microfilm or microfiche copies, computer printouts, magnetic media, including dictated observations, and recorded data from automated instruments. If exact copies of raw data have been prepared (e.g., tapes which have been transcribed verbatim, data and verified accurate by signature), the exact copy or exact transcript may be submitted. 6.20. Reagent Blank (method reagent blank): A sample consisting of reagent(s), without the target analyte or sample matrix, introduced into the analytical procedure at the appropriate point and carried through all subsequent steps to determine the contribution of the reagents and of the involved analytical steps. 6.21. Standard: The document describing the elements of laboratory accreditation that has been developed and established within the consensus principles of NELAC and meets the approval requirements of NELAC procedures and policies. 6.22. Standard Operating Procedure (SOP)-. A written document which details the method of an operation, analysis or action whose techniques and procedures are thoroughly prescribed and which is accepted as the method for performing certain routine or repetitive tasks. 7. INTERFERENCES 7.1. High nitrate concentrations result in low TKN results. The reaction between nitrate and ammonia can be prevented by the use of an anion exchange resin (chloride form) to remove the nitrate prior to the TKN analysis. 8. SAFETY 8.1. The toxicity, carcinogenicity and other health hazards associated with the use of most laboratory chemicals have not been precisely defined. Each chemical should be handled as a potential health hazard. 8.2. Exposure to these chemicals should be minimized through the use of proper protective equipment and safe laboratory practices as referenced in the current Calscience Health & Safety Manual. In general, safety glasses and lab coats are STANDARD OPERATING PROCEDURE Document No.: SOP-M747 Title: EPA Method 351.3:Total Kjeldahl Nitrogen(Titrimetric) Revision No. : 1.0 Calscience Environmental Laboratories, Inc. Effective Date: 04/18/03 Page 5 of 12 required to be worn in all designated laboratory areas. Protective gloves shall be worn when handling chemicals. 8.3. Material Safety Data Sheets (MSDSs) are available for each laboratory standard and reagent chemical. Employees should review and be familiar with the hazards and precautions outlined in the MSDS for all chemicals to be used prior to handling. 9. APPARATUS AND MATERIALS 9.1. Digestion apparatus: Kjeldahl digestion apparatus with 400-ml flasks and suction takeoff to remove S03 fumes and water. 9.2. Distillation apparatus: Distillation flask connected to a condenser and an adapter so the distillate can be collected. 9.3. Beaker: Pyrex, 300-ml. 9.4. Buret: 50-ml 9.5. Magnetic stirrer: Variable speed. 9.6. Stirring bars: Teflon TM. 9.7, Balance: Analytical. 9.8. Volumetric flasks: 100-ml, 1000-ml, and 2000-ml. 10. REAGENTS AND STANDARDS 10.1. Reagent water: Ammonia-free. Use to prepare all solutions. 10.2. Mercuric sulfate solution: Dissolve 8 grams of red mercuric oxide (HgO) in 50 ml of 1:4 sulfuric acid (1 part concentrated H2SO4 to 4 parts reagent water), and dilute to 100 ml with reagent water. 10.3. Sulfuric acid-mercuric sulfate-potassium sulfate solution: Dissolve 267 g K2SO4 in 1300 ml reagent water and 400 ml concentrated H2SO4. Add 50 ml mercuric sulfate solution (from section 10.2) and dilute to 2 liters with reagent water. 10.4. Sodium hydroxide — sodium thiosulfate solution: Dissolve 500 grams NaOH and 25 grams Na2S203 • 5H2O in reagent water and dilute to 1 liter. 10.5. Mixed indicator: Mix 2 volumes of 0.2% methyl red in 95% ethanol with 1 volume of 0.2% methylene blue in ethanol. Prepare fresh every 30 days. 10.6. Boric acid solution: Dissolve 20 grams boric acid, H31303, in water and dilute to 1 liter with reagent water. 10.7. Sulfuric acid, standard solution: 0.02N, Commercially available. Standardize the approximate 0.02 N acid against 0.0200 N Na2CO3 solution. This last solution is prepared by dissolving 1.060 g anhydrous Na2CO3, oven dried at 140°C, and diluting to 1 liter with CO2-free reagent water. 1 ml = 0.28 mg NH3-N. 10.8. Ammonium chloride, stock solution: Dissolve 3.819 g NH4CI in reagent water and bring to 1 liter in a volumetric flask. 1.0 ml = 1.0 mg NH3-N. STANDARD OPERATING PROCEDURE Document No.: SOP-M747 Title: EPA Method 351.3:Total Kjeldahl Nitrogen(Titrimetric) Revision No. : 1.0 Calscience Environmental Laboratories, Inc. Effective Date: 04/18/03 Page 6 of 12 10.9. Ammonium chloride, standard solution: Dilute 10.0 ml of the stock solution (see section 10.8) using reagent water. Bring to volume in a 1-liter volumetric flask. 1.0 ml = 0.01 mg NH3-N. 10.10. Nessler reagent: Commercially available. This reagent must be away from direct light; and is stable for one year. 11. SAMPLE COLLECTION, PRESERVATION, CONTAINERS AND HOLDING TIMES 11.1. Samples are preserved with 2 ml of concentrated H2SO4, and stored at <_6°C but above freezing. 11.2. Samples must be analyzed as soon as possible, but within 28 days from collection. 12. QUALITY CONTROL 12.1. One method blank is analyzed with every 20 samples, or portion thereof. 12.2. The laboratory must, on an ongoing basis, demonstrate through the analysis of quality control check standard (LCS) that the measurement system is operating within predetermined control criteria. 12.3. A sample duplicate shall be analyzed for every batch of 20 samples or every 24 hours, whichever is more frequent. The relative percent difference (RPD) between the original and duplicate result shall not exceed 25%. If the percent difference is greater than 25%, halt analysis, effect corrective action and recheck calibration. 12.4. All quality control data should be maintained and available for easy reference and inspection. 12.5. General acceptance criteria and corrective actions can be found in SOP-T020, Internal Quality Control Checks SOP. The QC policies set forth in SOP-TO20 must be followed, unless superseded in this document. 13. CALIBRATION AND STANDARDIZATION 13.1. None. 14. PROCEDURE 14.1. The distillation apparatus is pre-steamed before use by distilling a 1:1 mixture of distilled water and sodium hydroxide-sodium thiosulfate solution until the distillate is ammonia-free. This should be repeated each time that the apparatus is out of service for more than 4 hours. 142 Macro Kjeldahl System 14.2.1. Place 200 mis of the sample into a 400-ml Kjeldahl flask containing 3-4 boiling chips. 14.2.2.Add 40 mis sulfuric acid-mercuric sulfate-potassium sulfate solution. Evaporate the mixture in the Kjeldahl apparatus until S03 fumes are given off STANDARD OPERATING PROCEDURE Document No.: SOP-M747 Title: EPA Method 351.3:Total Kjeldahl Nitrogen (Titrimetric) Revision No. : 1.0 Calscience Environmental Laboratories, Inc. Effective Date: 04/18/03 Page 7 of 12 and the solution turns colorless or pale yellow. Continue heating for 30 additional minutes. Cool the residue and add 300 mis reagent water. 14.2.3. Make the digestate alkaline by careful addition of 40 mis sodium hydroxide- thiosulfate solution, without mixing. 14.2.3.1. Slow addition of this heavy caustic solution down the tilted neck of the flask will cause the heavier solution to underlay the aqueous sulfuric acid solution without losing the free-ammonia. Do not mix until the digestion flask has been connected to the distillation apparatus. 14.2.4. Connect the distillation flask to the condenser with the tip of the condenser or an extension of the condenser tip below the level of the boric acid solution. 14.2.5. Distill 200 ml at the rate of 6-10 ml/min. into 50-m1 of 2% boric acid, contained in a 300 ml beaker. 14.2.6.The ammonia is then determined titri metrically. 14.3. Determination of Ammonia in the Distillate by Titration 14.3.1.Titrate ammonia in distillate with standard 0.02N H2SO4 titrant until indicator turns to a pale lavender color. Record volume of titrant used. 14.3.2. Repeat with all samples. 15. CALCULATIONS 15.1. The concentration of TKN in a sample is calculated as follows: TKN VT X 280 = AS where: TKN = Kjeldahl Nitrogen in sample (mg/1) VT = Volume of titrant (ml) As = Amount of sample (ml for aqueous samples g for solid/non-aqueous samples) 15.2. The relative percent difference (RPD) is calculated as follows: IG —C2I %RPD = X 100 (G + C21 l 2 J where: %RPD = Relative percent difference C, = Original sample concentration C2 = Duplicate sample concentration Note: Concentrations must be in equivalent units STANDARD OPERATING PROCEDURE Document No.: SOP-M747 Title:EPA Method 351.3:Total Kjeldahl Nitrogen (Titrimetric) Revision No. : 1.0 Calscience Environmental Laboratories, Inc. Effective Date: 04/18/03 Page 8 of 12 16. METHOD PERFORMANCE 16.1. None. 17. POLLUTION PREVENTION 17.1. The toxicity, carcinogenicity and other health hazards associated with the use of most laboratory chemicals have not been precisely defined. Each chemical should be handled assuming it is a potential health hazard. 17.2. Exposure to these chemicals should be minimized through the use of proper protective equipment and safe laboratory practices as referenced in the current revision of Calscience's Health, Safety, and Respiratory Protection Manual. In general, protective eyewear (e.g. safety glasses or goggles), and protective apparel (e.g. lab coats) and gloves are required to be worn when handling chemicals. 17.3. The following additional precautions should be taken, as necessary, when handling high concentrations of hazardous materials: 17.3.1.A NIOSH approved air-purifying respirator with cartridges appropriate for the chemical handled. 17.3.2. Extended length protective gloves. 17.3.3. Face shield. 17.3.4. Full-length laboratory apron. 17.4. Processes that promote vaporization of volatile chemicals should be performed in an area well ventilated to the exterior of the laboratory to prevent contamination to other areas in the laboratory. 17.5. When working with large amounts of volatile chemicals, the Coordinator must be cautious of the risk of high levels of volatile displacing the atmospheric air within the work area; therefore causing asphyxiation. Air purification respirators are ineffective in this situation and must not be used. The Coordinator must immediately vacate the area until ventilation has effectively reduced the concentration of volatiles. Alternatively, the Coordinator may utilize a self-contained breathing apparatus or other supplied air system if appropriately trained and approved by the Health and Safety Manager. 17.6. Material Safety Data Sheets (MSDSs) are available for each laboratory standard and reagent chemical. Employees should review and be familiar with the hazards and precautions outlined in the MSDS for all chemicals to be used prior to handling. 18. DATA ASSESSMENT AND ACCEPTANCE CRITERIA 18.1. The acceptance criterion for LCS varies depending upon historical data. The upper and lower acceptance limits for %REC and RPD are based upon the historical average recovery ±3S. The LCS must be within acceptance limits. If the LCS recovery is not acceptable, the problem must be identified and corrected. STANDARD OPERATING PROCEDURE Document No.: SOP-P.4747 Title: EPA Method 351.3:Total Kjeldahl Nitrogen (Titrimetric) Revision No. : 1.0 Calscience Environmental Laboratories, Inc. Effective Date: 04/18/03 Page 9 of 12 18.1.1. If the LCS %REC is outside of the acceptance limits high, and all target analytes in the associated samples are not detected, the sample data can be reported without qualification. 18.2. Ideally, the concentration of target analytes in a MB should be less than the respective reporting limits (RLs). If the concentration of any target analyte exceeds its RL, the source of contamination must be investigated and, if possible, eliminated. The acceptance criteria for MBs is as follows: 18.2.1. If a target analyte is found in the MB but not in the associated samples, report the sample and MB data without qualification. 18.2.2. If a target analyte is found in the MB and in the associated samples, evaluate the analyte in question to determine the effect on the analysis of samples. Determine and eliminate the source of contamination. Professional judgment should be exercised to determine if the data should be qualified or rejected and the samples re-extracted and/or re-analyzed. 18.3.1.Where sample dilution is required, depending on the dilution factor, the surrogate recovery will be low or not detected. This is an expected occurrence and reference should be made to the MB surrogate recovery that must be reported to the client. 18.4.Additional information regarding internal quality control checks is provided in SOP-T020. 18.5.All concentrations shall be reported in mg/L (ppm) for water samples and mg/kg (ppm)for oil, soil and solid waste samples. 18.6.The data reported should adhere to the significant figures, rounding, and data reporting procedures outlined in the current revision of SOP-T009. 19. CORRECTIVE ACTIONS 19.1. If on the basis of internal or external systems or performance audits, routine monitoring of laboratory support equipment, or QC sample analysis results, analytical systems fail to meet the established criteria, an appropriate corrective action must be implemented. 19.1. The Operations Manager, Project Manager, Quality Control Manager, Group Leader and analyst may be involved in identifying the most appropriate corrective action. If previously reported data are affected or if corrective action will impact the project budget or schedule, the action may directly involve the Laboratory Director. 19.1. Corrective actions are generally of two types, immediate and long-term actions. 19.3.1. An immediate action is designed to correct or repair nonconforming instruments and measurement systems. The analyst or Group Leader as a result of calibration checks and other QC sample analyses most frequently will identify the need for such an action. 19.3.2. A long-term action is designed to eliminate causes of nonconformance. The need for such actions is identified by systems and performance audits. The systematic nonconformances identified during the data generation STANDARD OPERATING PROCEDURE Document No.: SOP-M747 Title: EPA Method 351.3:Total Kjeldahl Nitrogen (Titrimetric) Revision No. : 1.0 Calscience Environmental Laboratories, Inc. Effective Date: 04/18/03 Page 10 of 12 process and the appropriate corrective measures taken are thoroughly documented in the Corrective Action Record. Examples of this type of action include: 19.3.2.1. Remedial training of staff in technical skills, technique or implementation of operating procedures. 19.3.2.2. Rescheduling of analytical laboratory routine to ensure analysis within holding times. 19.3.2.3. Revision of standard operating procedures. 19.3.2.4. Replacing personnel, as necessary. 19.1. For either type of corrective action, the sequential steps that compose a close-loop corrective action system are as follows: 19.4.1. Define the problem. 19.4.2. Assign responsibility for investigating the problem. 19.4.3. Investigate and determine the cause of the problem. 19.4.4. Assign and accept responsibility for implementing the corrective action. 19.4.5. Determine effectiveness of the corrective action and implement correction. 19.4.6. Verify that the corrective action has eliminated the problem. 19.1. Depending on the nature of the problem, the corrective action employed may be formal or informal. In either case, occurrence of the problem, the corrective action employed, and verification that the problem has been eliminated must be properly documented on a Corrective Action Record. 16.1.1.The analyst must immediately inform the Group Leader of all out of control situations for specific handling instructions. 16.1.2. Event must be documented in detail on an "Out of Control Corrective Action" form and reviewed by the Group Leader. The Group Leader shall implement corrective action, list the specific procedures employed and their outcome on the corrective action form. 16.1.3.A copy of the completed Out of Control Corrective Action form must be included with all affected data packages. 16.1.4.The Group Leader should consult with the Technical Manager and/or Quality Control Manager regarding procedural inquiries and recommendations for method modification. 16.1.5. Modifications to the analytical process are approved by Management and the QA department as documented in a revised SOP. 20.CONTINGENCIES FOR OUT-OF-CONTROL OR UNACCEPTABLE DATA 20.1. Out-of-control data are reviewed and verified by the technical director of the appropriate department. All samples associated with an unacceptable QC set is then subject to reanalysis, depending upon the QC type in question. STANDARD OPERATING PROCEDURE Document No.: SOP-M747 Title:EPA Method 351.3:Total Kjeldahl Nitrogen (Titrimetric) Revision No. : 1.0 Calscience Environmental Laboratories, Inc. Effective Date: 04/18/03 Page 11 of 12 20.2.1. LCS/LCSD: Because they denote whether the analytical system is operating within control, it is imperative that the LCS recoveries obtained are within acceptability criteria. If the recoveries fail for a given reported compound, the technical director confirms the unacceptable result. 20.2.1.1. If the LCS results are verified as acceptable, no corrective action is required. 20.2.1.2. If the LCS result is verified as out-of-control, and the subject compound is to be reported in samples within that analytical batch, the samples reported with that failed compound must be reanalyzed with a valid LCS recovery for the compound. 20.2.1.3. If the LCS result is verified as out-of-control, and the subject compound is NOT to be reported in the samples within that analytical batch, the samples are not subject to reanalysis. No corrective action is required for that batch. 21.WASTE MANAGEMENT 21.1. The proper disposal of analytical samples and laboratory wastes is not only good laboratory practice, but also regulated by a variety of local, state, and federal laws. In order to remain compliant with these laws, and at the same time keep sample disposal costs at a minimum, the samples and wastes are identified, segregated, and either returned to the client (preferable) or placed into the proper laboratory waste stream. 21.2. Unused or remaining soil or liquid samples and all other solid or liquid wastes resulting from our laboratory operations are considered hazardous for disposal purposes. 21.3. All laboratory personnel must be aware of the types of chemicals they are using and the appropriate procedures for their disposal. 21.4. Each specific laboratory area shall maintain clearly labeled waste containers for small quantity waste collection. These waste containers shall be used for temporary collection of residual sample from aliquotting procedures, contaminated consumables, sample extracts, purged aqueous samples, and other wastes that require disposal as hazardous waste. 21.5. To ensure compliance with Federal RCRA regulations, the Hazardous Waste Coordinator collects and disposes of the hazardous waste at each satellite collection point no less than monthly. 21.6. In order to maintain accountability for all samples received by Calscience, when a sample is used in its entirety for analysis, the empty container(s) are returned to Sample Control for placement in analytical storage. 21.7. Waste management procedures shall adhere to the current revision of SOP-T005, "Disposal of Laboratory Samples and Waste." STANDARD OPERATING PROCEDURE Document No.: SOP-M747 Title:EPA Method 351.3:Total Kjeldahl Nitrogen(Titrimetric) Revision No. : 1.0 Calscience Environmental Laboratories, Inc. Effective Date: 04/18/03 Page 12 of 12 23. REFERENCES 23.1. "Nitrogen, Kjeldahl, Total, Method 351.3 (Colorimetric; Titrimetric; Potentiometric)," Methods for Chemical Analysis of Water and Wastes, USEPA-600/4-79-020, March 1983. 24.TABLES, CHARTS, DIAGRAMS AND VALIDATION DATA 24.1. None. Appendix E Attachment 13 : Standard Operating Procedure for Total Particle Size (Light Scattering Method) STANDARD OPERATING PROCEDURE FOR TOTAL PARTICLE SIZE (LIGHT SCATTERING METHOD) Endpoint Description The range of particle size distribution is displayed from 0.02 to 2000 µm and is based on Mie and Fraunhofer scattering theory. Method References Particle size distribution analysis preformed for sediment at Aquatic Bioassay is conducted in accordance with Standard Methods for the Examination of Water and Wastewater(APHA, 20th Edition) Section 2560 D. Materials 1. Horiba LA-920 2. Computer- IBM ThinkPad 3. DI Water Sample Collection Sediment collected for particle size testing is distributed into a clean 8 oz jar or plastic bag. Samples are to be kept at 4° C until analysis and analysis should occur within 6 months of collection. Analytical Procedure The Horiba LA-920 is connected to an IBM ThinkPad. The LA-920 is warmed up for at least 30 minuets. Deionized water is added to the sample cell and the lasers are aligned. Before the analysis of each sample, the LA-920 is blanked. The sample is mixed then added to the sample cell. The sample is circulated through the flow cell with the centrifugal pump. Eighty-seven detectors determine the particle size distribution of the sample. The data is displayed and saved in the computer. Quality Control Particle size analysis requires an experienced analyst capable of judgment in recognizing unusual behavior of the instrument. In addition to the analyst's judgment, standards are purchased from Duke Scientific. A 300 nm standard and Quartz reference material NR. 68 and 69 is tested after every 100 samples to determine the machine is properly operating. If the machine is not operating properly, it is shipped to Horiba to be recalibrated. References APHA. 1998. Standard Methods for the Examination of Water and Wastewater(20th Edition). Aquatic Bioassay&Consulting Laboratories Rev 001. June 14,2005 Appendix E Attachment 14: Standard Operating Procedure for Total Organic Carbon Content of Sediments by Coulometric Detection Revision 6 Original Date:January 10,1994 Revision Date:February 23,2001 Page 1 of 9 APPLIED MARINE SCIENCES, INC. Standard Operating Procedure SOP 2201 Written By: Kenneth S. Davis, Revision By: Mike A. Seymour TOTAL ORGANIC CARBON CONTENT OF SEDIMENTS BY COULOMETRIC DETECTION Prepared By: Date: Approved By: Date: Laboratory Manager Date: QA Officer Revision 6 Original Date:January 10,1994 Revision Date:February 23,2001 Page 2 of 9 APPLIED MARINE SCIENCES, INC. Standard Operating Procedure SOP 2201 Written By: Kenneth S. Davis, Revision By: Mike A. Seymour TOTAL ORGANIC CARBON CONTENT OF SEDIMENTS BY COULOMETRIC DETECTION 1.0 INTRODUCTION This Standard Operating Procedure (SOP) describes a method to determine the total organic carbon content(TOC)of sediments. Total organic carbon concentrations are useful parameters when interpreting trace organic data. TOC measurements are determined on dry samples using a high-temperature tube furnace to combust the material to carbon dioxide (CO2) in a pure oxygen atmosphere. The combustion product gas flows through a Balston filter to remove water vapor. The gas is then flowed through two reaction chambers: the first containing magnesium perchlorate [Mg(C104)2] to remove water vapor, the second containing both acid dichromate on Silocel [as K2Cr207 and H2SO4] and manganese dioxide [as Mn021 to adsorb SOX and NO, products. The CO2-gas stream then passes to a UIC 5012 Carbon Dioxide Coulometer that determines the CO2 within the gas stream by coulometric titration via a photoelectric detection cell. Data output is sent to a computer that calculates the TOC present in the sample and prints the results. 2.0 REFERENCES EPA, 1995. SW-846 Method 9060. Total Organic Carbon EPA Region 11, 1986. Determination of Total Organic Carbon in Sediment(Kahn Method). 3.0 SAMPLE COLLECTION, PRESERVATION,AND STORAGE 3.1 Sample Collection Sediment samples should be collected in pre-cleaned glass jars with Teflon-lined lids, aluminum foil, or core liners. Cool samples to 4°C for shipment to laboratory. Revision 6 Original Date:January 10, 1994 Revision Date:February 23,2001 Page 3 of 9 APPLIED MARINE SCIENCES, INC. Standard Operating Procedure SOP 2201 Written By: Kenneth S. Davis, Revision By: Mike A. Seymour 3.2 Sample Preservation and Storage Samples should be shipped to the laboratory and stored at 4°C until analysis. After subsampling, excess material is archived at 4°C in darkness. The samples should be analyzed within 28 days of the date of collection. See SOP 1301 for more information. 4.0 SUPPLIES AND EQUIPMENT 4.1 Laboratory Equipment and Apparatus The following labware and equipment is needed to perform the TOC analysis: * UIC Model 5012 Carbon Dioxide Coulometer * Bottled Pure Oxygen, Laboratory Grade * Platinum Electrode (UIC No. CM101-135) * Silver Electrode (UIC No. CM101-033) * Combustion Tube (UIC No. CM211-005) * Analytical Balance, (0.0001 g sensitivity) * Drying Oven (Maintain 70°C, +/- 0.5°C) * Mortar and Pestle * Glazed Porcelain Boats (Coors 60028) 4.2 Reagents The following reagents are required to perform the total organic carbon analysis: * Distilled Water * Carbon anode solution(UIC No. CM300-002). * Carbon cathode solution (UIC No. CM300-001). * Potassium Iodide (CAS No. 7681-11-0, Certified ACS Grade) * Magnesium Perchlorate (CAS No. 10034-81-8, Reagent Grade) * Potassium Hydroxide Solution (CAS No. 1310-58-3, Certified ACS Grade) * Acid Dichromate on Silocel (UIC No. CM300-008) * Hydrochloric Acid(CAS No. 7647-01-0,NF/FCC Grade) * Barium Chromate (UIC No. CM211-011) * Barium Chromate with Reduced Silver(UIC CM211-002) * 2%Carbon Standard(MESS-3) Revision 6 Original Date:January 10,1994 Revision Date:February 23,2001 Page 4 of 9 APPLIED MARINE SCIENCES, INC. Standard Operating Procedure SOP 2201 Written By: Kenneth S. Davis, Revision By: Mike A. Seymour * 4.8% Carbon Standard(NIST SRM 1941a) * 12% Carbon Standard(LECO No. 501-034) * 42.1%Carbon Standard (LECO No. 501-046) 5.0 PROCEDURE 5.1 Sample Preparation Samples with no material larger than 2.0 mm can be aliquoted into a clean 20 ml scintillation vial. Materials larger than 2.0 mm should be removed by sieving through a #10 (2.00 mm) sieve. If samples are highly oiled and/or clumped,remove large particles by hand with clean tweezers. After removing any material larger than the#10 sieve, aliquot a small portion(-10 g) into the 20 ml scintillation vial, and dry the samples at 70°C for 12 hours. After the samples are dry, grind the sample using a clean mortar and pestle. Pour the ground sample back into its scintillation vial and acidify by adding 2M HC1 until no reaction is observed. Allow the sample to equilibrate for one hour, and then wash using deionized water until the sample is neutral in pH(usually 7-8 times). Dry the sample in the oven at 70°C for 12 hours. If the sample is to be removed from the oven, store it in a desiccator to prevent absorption of atmospheric moisture. 5.2 Coulometer System Preparation 5.2.1 Preparing the Coulometer Furnace Change the solution in the oxygen gas pre-scrubber, using fresh potassium hydroxide solution. Fill the scrubber apparatus to approximately 40% full. Reinstall the scrubber, and attach the oxygen lines. Turn the master control valve on the oxygen tank counter clockwise to allow gas flow to the coulometer. Using the left-side flow meter on the coulometer,turn the gas control valve counter clockwise until approximately 125 ml/min is flowing to the combustion tube. Using the control pad in the center of the furnace module, press the up arrow to turn on the furnace module and adjust the temperature to 900°C. Retrieve the post-combustion scrubber tubes from the desiccator, and change the magnesium perchlorate(white and granular in color). Check that the barium chromate in the second post-combustion tube is brownish-gold and not"green" in color. This indicates exhaustion of the material and the contents should be changed before samples are run. Be sure the magnesium perchlorate is placed before the barium chromate when finishing the assembly. Revision 6 Original Date:January 10,1994 Revision Date:February 23,2001 Page 5 of 9 APPLIED MARINE SCIENCES, INC. Standard Operating Procedure SOP 2201 Written By: Kenneth S. Davis, Revision By: Mike A. Seymour 5.2.2 Preparing the Coulometer Module The coulometer module consists of two parts; a larger section called the body and the smaller section called the side arm. Begin with the preparation of the detection cell. Place a small stir bar in the larger cell body. Fill the larger cell with 100 to 125 ml of the carbon cathode solution. Pour potassium iodide into the side cell until it fills to a depth of 0.25". Then pour carbon anode solution into the cell until it is 1/8"below the level of the cathode level. Place the silver and platinum electrodes and caps onto the detection cell. Place the cell inside the coulometer body, and rotate cell in the body until the light path is not blocked by the electrodes. Plug in the electrode leads, and screw the CO2 gas feed lines onto their fittings. Check that the cell current switch is in the neutral position, and turn the main power to"on". Adjust the%T knob clockwise to its stopping point. Readjust the oxygen flow on the furnace module to 125 ml/min. Rotate the detection cell in the main body so that the highest%T reading is obtained. Slowly adjust the %T knob until the digital display reads "100". Turn the cell current switch to the "on" position and allow the coulometer to equilibrate. After equilibration,the display should read 29 to 30 and the cell current should read zero. 5.2.3 Computer Start Up and Printer Set The computer should be turned on and program selected to receive and analyze data. Please see Appendix A for a detailed instruction sheet for the computer and program currently in use at Applied Marine Sciences Inc. 5.3 Total Organic Carbon Determination 5.3.1 Initial Blank Analysis An initial blank calibration will be run before analyzing carbon standards. The initial blank is determined by combusting a series of empty boats until the final three (3)results are within 10%RPD. 5.3.2 Initial Four-Level Calibration A calibration analysis will be performed before any samples are analyzed. A 2.0%, 4.8%, 12%, and 42.1%carbon standard will be analyzed to determine the calibration of the coulometer. The calibration check must fall within 5% RPD of the known carbon content of the standard for all four values before sample analyses will be accepted. Revision 6 Original Date:January 10,1994 Revision Date:February 23,2001 Page 6 of 9 APPLIED MARINE SCIENCES, INC. Standard Operating Procedure SOP 2201 Written By: Kenneth S. Davis, Revision By: Mike A. Seymour In addition, a continuing calibration check will be performed with each group of 20 field samples using the 4.8%NIST standard. All values must be within 5%RPD. See SOP 1103 for more information. 5.3.3 Sample Analysis Tare the combustion crucible to a zero value on the balance. Using a clean scoopula, place approximately 0.0200 g of sample into the crucible. Record the weight value in the laboratory notebook. Insert the sample I.D. number in the computer, and input the weight. Form feed the printer to a clean sheet of paper. Place the crucible into the combustion tube. Close the combustion tube, and insert the crucible ladle into the furnace using the magnetic slide. Hit the return key on the computer to start sample analysis. The coulometer analysis is complete when two consecutive readings fall within a preset difference. After the sample analysis is complete, record the %C, µg C, and blank values into the laboratory notebook. Repeat this process for all samples. 5.3.4 Continuing Blank and Continuing Calibration Standard A new blank will be analyzed with every twenty(20) samples as noted in 5.3.1. In addition, a 4.8% carbon standard should be analyzed with every ten(10) samples. 6.0 STANDARDIZATION AND CALCULATIONS 6.1 Standardization The accuracy of the coulometer is verified by performing an initial four-level calibration with 2.0%, 4.8%, 12%, and 42.1% carbon standards. The standard analysis is the same as for sample analysis. The results of standard analysis are compared to the known values, and RPD is calculated. No sample analysis is to be done unless the RPD values for all four standards is within 5% of the known value. The calibration is to be done on a weekly basis. Revision 6 Original Date:January 10,1994 Revision Date:February 23,2001 Page 7 of 9 APPLIED MARINE SCIENCES, INC. Standard Operating Procedure SOP 2201 Written By: Kenneth S. Davis, Revision By: Mike A. Seymour 6.2 Calculations 6.2.1 Calculation of Total Organic Carbon(TOC) TOC =Pesult W I Blank J1)x 100 Where: Result = µg C Blank = µg C W = Weight of Sample (µg) 6.2.2 Calculation of Relative Percent Difference (RPD) DuplicateA—DuplicateBl C DuplicateA+DuplicateBl 2 /I 7.0 QUALITY CONTROL Quality control samples are processed in the same manner as samples. See SOP 1103 and the AMS Quality Manual for more information. 7.1 Standard Reference Material(SRM) To document accuracy, one SRM(KIST 1941a) is analyzed with each batch of 20 field samples. The result must be within 5%RPD of the average value (4.8%C +/- 1.2%)for acceptable accuracy. 7.2 Method Blank One method blank will be processed with each batch of 20 samples, or with every sample set, whichever is more frequent. A method blank consists of following all preparation and analytical steps conducted with a sample except that the sample (i.e. sediment) is not added to the combustion crucible. An acceptable procedural blank must be less than one- tenth of the lowest sample signal (S:N=10:1) for the batch of samples. Revision 6 Original Date:January 10,1994 Revision Date:February 23,2001 Page 8 of 9 APPLIED MARINE SCIENCES, INC. Standard Operating Procedure SOP 2201 Written By: Kenneth S. Davis, Revision By: Mike A. Seymour 7.3 Duplicate One duplicate sample will be run with each batch of 20 samples, or with every sample set, whichever is more frequent. Duplicates should be within 25%RPD. Duplicates may be less precise for inhomogeneous samples (i.e. peat, and samples containing twigs, grasses, algae, etc.). 8.0 REPORTING AND PERFORMANCE CRITERIA 8.1 Reporting Units Reporting units are in percent total organic carbon on a dry weight basis. All sample weights, instrument readings, analysis date, and calculated percent TOC are recorded in the project notebook. 8.2 Minimum Method Performance Criteria The minimum method performance standard for the method is detection of 0.0 1%carbon in a sample. 8.3 Significant Figures All results are reported to three significant figures. 8.4 Duplicate Analysis All duplicates are reported. Duplicates are analyzed with every 20 field samples or one per batch, whichever is more frequent. 8.5 Standard Reference Materials Standard reference materials include the MESS-3 (2%), NIST 1941a(4.8% C), and LECO 12% (CaCO3) and 42.1% (Sucrose) C samples. Initial and continuing calibrations will be reported. Revision 6 Original Date:January 10,1994 Revision Date:February 23,2001 Page 9 of 9 APPLIED MARINE SCIENCES, INC. Standard Operating Procedure SOP 2201 Written By: Kenneth S. Davis, Revision By: Mike A. Seymour 8.6 Method Blank Method blanks will be reported. Blank runs are analyzed with every 20 field samples or one per batch, whichever is more frequent. 9.0 SAFETY The technician will be instructed in and made aware of the safety considerations in using this method including the following: * Protective clothing and eyewear is to be worn while in the laboratory, especially due to the use of caustic and acidic chemicals. * The location and use of eyewashes, emergency showers, fire extinguishers, fire blankets, and first aid kits will be given. * The proper handling and disposal of samples and reagents necessary to the procedure will be followed. * The proper handling of gas tanks. This is in addition to standard laboratory safety practices, including but not limited to, the guidelines specified in the AMS Laboratory Safety Guide and SOP 1304. Appendix E Attachment 15: Standard Operating Procedure for Total Kj eldahl Nitrogen In Aqueous Matrices Method:TKN-WaterBlue Revision:2 Date: 10/23/05 Page: 1 of 7 Thomas Analytical Services,Inc. 2151 Harvey Mitchell Pkwy., South, Suite 303 College Station, TX 77840-5237 TITLE: TOTAL KJELDAHL NITROGEN IN AQUEOUS MATRICES (Indophenol Blue (Phenate)Method) Written by: Jacob Alaniz (Laboratory Director) TABLE OF CONTENTS 1.0 Introduction 2.0 Scope and Application 3.0 Summary of Method 4.0 Interferences 5.0 Apparatus and Materials 6.0 Reagents 7.0 Procedure 8.0 Calculations 9.0 Quality Control 10.0 References Method:TKN-WaterBlue Revision:2 Date: 10/23/05 Page:2 of 7 Total Kjeldahl Nitrogen in Aqueous Matrices (Indophenol Blue (Phenate)Method) 1.0 Introduction Total Kjeldahl nitrogen is defined as the sum of ammonia-nitrogen and organically bound nitrogen compounds which are converted into ammonium sulfate under the conditions of digestion described by this method. Organic nitrogen may be determined by the difference between total Kjeldahl nitrogen (determined by this procedure) and ammonia-nitrogen. Alternately, ammonia may be removed prior to digestion and the organic nitrogen determined directly. 2.0 Scope and Application This method is applicable to water, wastewater, and other liquid samples for the determination of total Kjeldahl nitrogen. This procedure determines nitrogen in the trinegative state. Samples of biological origin such as amino acids, proteins and peptides will be converted to ammonia. This method will not account for nitrogen in the form of azide, azine, azo, hydrazone, nitrate, nitrite,nitrile, nitro, nitroso, oxime, semi-carbazone, and some refractory tertiary amines which are components of some industrial wastes. There are three manual alternatives for the determination of ammonia after digestion: the manual titrimetric method, the manual colorimetric method by Nesslerization, and the manual colorimetric indophenol blue, or phenate method which is covered by this SOP. Nesslerization is no longer a popular choice for ammonia determinations because of the mercuric oxide used in preparation of the Nessler reagent and the subsequent hazardous waste generated during the analysis. 3.0 Summary of Method An aqueous sample is heated in the presence of sulfuric acid, potassium sulfate, cupric sulfate, and titanium dioxide at 180°C for one hour(or until SO3 fumes are present), and then at 380°C until the solution becomes colorless or pale green. The solution is then cooled and brought to a known final volume. The ammonia concentration is determined in the digestate by indophenol blue colorimetry. 4.0 Interferences 4.1 High nitrate concentrations (i.e. ten times the TKN level, or greater)can result in low TKN values. High nitrate can oxidize portions of the ammonia released during digestion, producing N2O and resulting in low TKN recovery. Anion exchange resins (i.e. chloride Method:TKN-WaterBlue Revision:2 Date: 10/23/05 Page:3 of 7 form)have been successfully used to remove nitrate prior to digestion, thereby reducing the negative interference. 4.2 The acid and salt combination used in sample digestion is intended to produce a digestion temperature of 380°C. High salt concentrations and high solids encountered in some samples can cause the digestion temperature to rise above 400°C, at which point pyrolytic loss of nitrogen will occur. Addition of more sulfuric acid will maintain the acid to salt balance. Not all salts will have the same effect on digestion temperature,but the addition of 1 ml sulfuric acid for every gram of salt in the sample will give reasonable results. 4.3 During digestion, sulfuric acid oxidizes organic matter to form CO2 and H2O. If a large amount of organic matter is present in the sample, a large amount of acid will be consumed during this oxidation, decreasing the acid to salt ratio, resulting in an increase in digestion temperature, and pyrolytic loss of nitrogen. Addition of more sulfuric acid will maintain the acid to salt balance. An estimate of the additional acid needed is: 10 ml sulfuric acid for every 3 g COD.Note: Any change in the treatment of the sample should be applied to the treatment of the reagent blank. 5.0 Apparatus and Materials 5.1 Digestion apparatus: 5.1.1 Temperature controlled block digestor. 5.1.2 Fume removal system: fume removal manifold with connection for water aspirator, to be used in a fume hood. Note: If a manifold is not available, reflux caps or ribbed watch glasses must be placed on top of each digestion tube and digestion must be carried out in a fume hood. 5.1.3 Digestion tubes, 250 ml capacity, suitable for use in the appropriate block digestor. 5.2 Ammonia determination: 5.2.1 Adjustable UV-VIS Spectrometer (with appropriate filters if necessary) capable of absorbance measurements at 636 nm. 5.2.2 Volumetric glass pipettes, or adjustable air pipettes. Note: If air pipettes are substituted for glass pipettes, the analyst must ensure the pipettes have been properly calibrated. 5.2.3 Test tubes, or suitable sample cup with a 50 ml capacity. Method:TKN-WaterBlue Revision:2 Date: 10/23/05 Page:4 of 7 6.0 Reagents 6.1 Sample Digestion: 6.1.1 Sulfuric acid, concentrated(H-2SO4), ACS reagent grade. 6.1.2 Kjeltab: typical mixture: potassium sulfate (K-,SO4, 94.4%), cupric sulfate (CuSO4, 2.8%),titanium dioxide (TiO2, 2.8%). 6.2 Ammonia determination: 6.2.1 Ammonia-nitrogen (NH4+-N) stock solution: 1000 mg NHL+-N/L. Dissolve 3.819 g ammonium chloride (NH4C1) in DI H2O (6.1.1), and bring to volume in a 1 liter flask. Alternatively, a commercially available stock solution may be used, however, the technician must insure that the reported concentration value is for NH4+-N,not NHL+. 6.2.2 Phenol-nitroprusside reagent: Dissolve 7 g of phenol and 0.034 g of sodium nitroprusside [also named sodium nitroferricyanide (III) dihydrate, or disodium pentacyanonitrosylferrate, Na2Fe(CN)5NO • 2H2O1 in 80 ml of DI H2O (6.1.1) and dilute to 100 ml. Mix well and store in an amber bottle in a refrigerator. 6.2.3 Buffered hypochlorite reagent: Dissolve 1.480 g of sodium hydroxide (NaOH) in 70 ml of DI H2O (6.1.1). Add 4.98 g of sodium monohydrogen phosphate (Na2HPO4) and 20 ml sodium hypochlorite solution (5-5.25%NaOCI). Use less or more hypochlorite solution as needed to compensate for higher or lower concentration than indicated. The pH of the solution should be between 11.4 and 12.2, adjust if necessary. Note: This solution should he made fresh weekly. 6.2.4 EDTA reagent: Dissolve 6 g of ethylenediaminetetraacetic acid disodium salt (EDTA disodium) in 80 ml of DI H2O (6.1.1). Adjust to pH 7, mix well, and dilute to a final volume of 100 ml. 7.0 Procedure 7.1 Sample Digestion: Digestion should be performed on aqueous samples that have been acidified with H2SO4 to a pH<2 at the time of sampling and have been stored at 4°C. Holding time for TKN is 28 days. 7.1.1 Place 150 ml of sample (or suitable size diluted to 150 ml) into a digestion tube and add 1 Kjeltab and 12 ml concentrated H2SO4. Method:TKN-WaterBlue Revision:2 Date: 10/23/05 Page: 5 of 7 7.1.2 Place tube in the digestion block and heat at 180°C for 1 hour or until SO3 are present(volume in tube should be<20 ml). 7.1.3 Cover with appropriate fume capture device (i.e. manifold or reflux cap) and heat sample at 380°C until sample turns colorless or pale green. This may takes 2 to 4 hours depending on sample composition. 7.1.4 Remove from digestion block and allow to cool to room temperature. Bring to a final volume of 50 ml (or suitable volume dictated by detection limit requirements)with DI HBO in a graduated cylinder and pour into a labeled sample container. CAUTION!: Samples will become very hot upon dilution with water. Add water slowly, using appropriate PPE. 7.2 Sample Analysis: 7.2.1 In a graduated cylinder or suitable volumetric flask, add a 5 ml aliquot(or a smaller aliquot as necessary) of the sample digestion and dilute to 25 ml. Pour contents into a sample analysis cup. 7.2.2 Using an adjustable pipette, add 1 ml of the EDTA reagent (6.2.4)to the 25 ml sample and allow to stand for 1 minute. 7.2.3 Add 2 ml of the phenol-nitroprusside reagent (6.2.2), followed by 4 ml of the buffered hypochlorite reagent (6.2.3) and allow color to develop for at least 1 hour. Indophenol blue color is stable for approximately 24 hours. 7.3.2 Determine the absorbance of the colored complex at a wavelength of 636 nm on a spectrophotometer against a reagent blank solution Determine the NH4+- N concentration of the sample by comparison against a calibration curve treated as the unknown samples above. Calibration standards are prepared as follows: 7.3.2.1 Prepare an 25 mg/L intermediate standard solution by diluting 2.50 ml of the ammonia stock solution (6.2.1) to 100 ml in a volumetric flask. In a 25 ml volumetric flask, prepare the following standard concentrations and pour into sample analysis cups (or suitable test tubes): ml Intermediate Standard Solution Concentration N114±-N, mg_A 0.0 0.0 0.1 0.1 0.25 0.25 0.5 0.5 1.0 1.0 8.0 Calculations Method: TKN-WaterBlue Revision:2 Date: 10/23/05 Page:6 of 7 8.1 Calculation for stock standard dilution necessary for curve standards: VIXCi = V2xCz, where, V, =volume of stock solution needed, in ml C1 =concentration of standard stock solution, in ppm VZ= final volume of standard, in ml CZ =target concentration of curve standard, in ppm therefore,the amount of stock solution needed will be: V. _ (V2 x C2) C. 8.2 Calculate the amount of TKN in the sample digestion as follows: mg/L TKN(digest) x x(Sample Abs.)x(Color Final Vol.) (Aliquot for Color) where, x=mean curve value in(mg/L)/Abs. Sample Abs. = sample absorbance read from spectrophotometer. Color Final Vol. = final volume of aliquot dilution used to develop color. Aliquot for color= amount of TKN digestion used in the colorimetric determination. 8.3 Calculate the amount of TKN in the raw sample as follows: mg/L TKN(sample) (mg/L TKN digest)x(Digest Final Vol.) (Sample vol.) where, mg/L TKN digest=result from 8.2 Digest Final Vol. =final volume that the sample digestion is brought to prior to prior to analysis. Sample Vol. =volume of raw sample used for digestion 9.0 Quality Control Method:TKN-WaterBlue Revision:2 Date: 10/23/05 Page: 7 of 7 9.1 All quality control data must be maintained by each technician or department and made available for easy reference or inspection. Quality control data should include: amount of sample distilled, final volume of distillate, amount of distillate used in titration or nesslerization,technician initials, sample preparation date, date of distillation, date and results of any pertinent standardizations, and any analytical curves generated for the calculation of the final concentration. 9.2 A minimum of one method blank per analysis batch, or per set of reagents, must be analyzed to determine if contamination or memory effects are occurring. 9.3 Duplicate samples are to be analyzed at a frequency of 10% for every sample batch, unless specified otherwise by project requirements. Note: The actual number of duplicate samples required is rounded up to the nearest whole number, i.e., 10%duplication= 1 duplicate for every 10 samples; 2 duplicates for 11-20 samples, etc. 9.4 Spiked samples are to be analyzed at a frequency of 10% for every sample batch, unless otherwise specified by project requirements. 9.5 At least on certified reference standard should be carried throughout the entire analysis process, from digestion to ammonia determination, to ensure reliability of this method. 10.0 References 10.1 Methods for Chemical Analysis of Water and Wastes, EPA 600/4-79-020, Method 351.1. 10.2 Standard Methods for the Examination of Water and Wastewater, 19th Edition, Method 4500-Norg, pg. 4-92. Appendix F Example Field Log Sheet and Chain-of-Custody Form Appendix F Attachment 1 : Example Field Log Sheet Station: Date: Latitude: GPS Reading Longitude: GPS Reading Personnel: Field Meter Data Site Discharge Characterization H2O Temp Wet Channel IDH Time LC Ir Depth Width: Stage: I�J Bank Dth Velocity R.Bank Depth Velocity Di stance Distance E.C. Salinity ................................................................................................................................................. (mg/L) /%sat S/cm) Lpo1 _. _ .� ..... _ Turbidity Chlorophyll a Midchannel N( TU) -U /L) Depth ft Samples Collected Sample Sample ID Anal)de Time Depth Notes* _. i Field Observations' Photo ID: _ Photo #: Air Temp Algae Dominant % Bank Vegetation % Shading (OC) % Filamentous % Periphyton Substrate** Left Bank Right Bank Additional Notes or Comments: Weather: Water Color: Odor: In stream Activity: Other Foreign Matter: * SG = Surface Grab, direct to container; BG = Bucket Grab ** See attached "Field Observations" sheet for standard comments Page x and further guidance. Field Observation Guidance and Standard Comments Qualitative Measures 1) Dominant Substrate: Record the dominant substrate in the upstream reach of the sample location using one of the following categories: Boulder (B), cobble (C), gravel (G), sand (S), fines (F) or cement (K). 2) Algae: a) Filamentous: Record the percent of the flowing water surface, up-stream from your sample location, that you estimate is occupied by filamentous algae. b) Other Periphyton: Record the percent of substrate in the wetted channel, looking up stream from your sample location, that you estimate is covered in periphyton. Other periphyton is defined here as the living community attached to the substrate, including algae that is not the green filamentous type, aquatic mosses, fungi, diatoms and sessile invertebrates. To make this estimate feel the surface of the rocks and other substrate materials and estimate the percent of the substrate that is covered with a slimy organic community. 3) Shading: Record the percent of the stream's surface (water surface), up-stream from your sample location, that you estimate would be shaded if the sun was directly over the creek. 4) Plants: a) Bank: Record the percent of the surface of both banks, up-stream from your sample location that you estimate to be covered by vegetation. This estimate refers only to plants and roots at the water's edge. b) In-Stream: Record the percent of the flowing water's surface, up-stream from your sample location that you estimate to be occupied by aquatic vegetation. This is a percent of the total water surface that is occupied by aquatic vegetation. Other Notes Visually assess the stream corridor and comment on anything that you feel may directly affect or contribute to changes in water quality. Some standard comments and categories of observations follow. a) Recent/Current Weather Events: heavy rains, cold front or heat spells b) Water Color: black, brown, yellow, white, green, etc. c) Site Odors: sulfides, sewage, petroleum, unidentifiable odor or none. d) In stream Activities: construction, major erosion events, recent scour or other e) Other Foreign Matter: suspended matter, oily sheen, foam or other debris. f) Biological Activity: Note the presence of fish, birds, mammals or invertebrates observed and record one of the following categories: True count up to 25, then estimate > 25, > 50 or >100. g) Trash : Bank and in stream debris such as fertilizer bags, aerosol cans, batteries human wastes, homeless encampments, dumping of furniture or appliances. Record the true number of paper and recyclable trash items up to 10 items (count 1-10 items of trash), greater than 10 items should be recorded as >10 items of trash. h) Tidal Influences: evidence of recent tidal surge (i.e. kelp or driftwood) or of possible salt- water influence. Page X Appendix F Attachment 2: Example Chain-of-Custody LARRY WALKER ASSOCIATES 429 Santa Monica Blvd,Suite 270,Santa Monica,CA 90401 (Phone:310-394-1036-Fax:310-394-8959) CHAIN-OF-CUSTODY RECORD DATE: Lab ID: DESTINATION LAB: L A R R Y REQUESTED ANALYSIS WALKER ADDRESS: IlkPHONE: FAX: SAMPLED BY: PROJECT:I CCW TMDL Monitoring Program - LWA CONTACT:1 ASSOCIATES LWA PROJECT MANAGER: Client Sample ID Sample Sample Sample Container Date Time Matrix # Type Pres. Notes SENDER COMMENTS: RELINQUISHED BY RELINQUISHED BY Signature: Signature: Print: Print: Company: Company: Date: Time: Date: Time: LABORATORY COMMENTS: RECEIVED BY RECEIVED BY Signature: Si nature: Print: I Print: Com an : Com an : Date: Time: I Date: Time: Appendix G Calculations for Data Quality Assessments This appendix documents the calculations used to assess precision, accuracy, and completeness of the data. Precision Precision is a measure of the degree to which replicate measurements differ from one another. Precision assessed through calculation of field and laboratory duplicates, and matrix spike duplicates is expressed as the Relative Percent Difference (RPD). RPD for laboratory and field duplicates is calculated as follows: RPD = 100 x replicate 1-replicate 21 -)(replicate 1+replicate 2)-2 RPD for matrix spike duplicates is calculated as follows: RPD = 100 x (recovery 1-recovery 21 —)(recovery 1+recovery 2)_2 where Recovery is calculated as described for matrix spikes, below. If assessed with three or more replicate measurements, precision should be expressed as Relative Standard Deviation (RSD). RSD is calculated as: RSD=100 x standard deviation of replicated measurements 1 average of replicate measurements /I Accuracy Accuracy is the degree to which a measured value agrees with a true or expected value for a parameter. Accuracy is typically assessed using standard reference materials, laboratory control samples, and matrix spikes. Recovery of laboratory control samples and standard reference materials is calculated as: %Recovery=100 x recovered concentration true spike concentration Recovery of matrix spikes is calculated as: %Recovery=100 x total recovered concentration-sample concentration true spike concentration When sample concentrations are less than the method detection limit, a value of "0" (zero) will be used as the sample result concentration for purposes of calculating spike recoveries. Completeness Completeness may be defined as the number of valid measurements compared to the total number of measurements collected. Completeness is calculated as: %Completeness —100 x number of valid measurements 1 total number of measurements J Appendix H Chapter 13 QA/QC Data Evaluation from Caltrans Guidance Manual: Stormwater Monitoring Protocols, 2nd Edition SECTION 13 QA/QC DATA EVAL UATION All data reported by the analytical laboratory must be carefully reviewed to determine whether the project's data quality acceptability limits or objectives (DQOs) have been met. This section describes a process for evaluation of all laboratory data, including the results of all QA/QC sample analysis. Before any results are reported by the laboratory, the deliverable requirements should be clearly communicated to the laboratory, as described in the "Laboratory Data Package Deliverables" discussion in Section 12. The current section discusses QA/QC data evaluation in the following two parts: KEY > Initial Data Quality Screening TOPICS > Data Quality Evaluation The initial data quality screening identifies problems with laboratory reporting while they may still be corrected. When the data reports are received, they should be immediately checked for conformity to chain of custody requests to ensure that all requested analyses have been reported. The data are then evaluated for conformity to holding time requirements, conformity to reporting limit requests, analytical precision, analytical accuracy, and possible contamination during sampling and analysis. The data evaluation results in rejection, qualification, and narrative discussion of data points or the data as a whole. Qualification of data, other than rejection, does not necessary exclude use of the data for all applications. It is the decision of the data user, based on specifics of the data application, whether or not to include qualified data points. > INITIAL DATA QUALITY SCREENING The initial screening process identifies and corrects, when possible, inadvertent documentation or process errors introduced by the field crew or the laboratory. The initial data quality control screening should be applied using the following three-step process: 1. Verification check between sampling and analysis plan (SAP), chain of custody forms, and laboratory data reports: Chain of custody records should be compared with field logbooks and laboratory data reports to verify the accuracy of all sample identification and to ensure that all samples submitted for analysis have a value reported for each parameter requested. Any deviation from the SAP that has not yet Implementing the Monitoring Plan 13-1 May 2000 QA/QC Data Evaluation been documented in the field notes or project records should be recorded and corrected if possible. Sample representativeness should also be assessed in this step. The minimum acceptable storm capture parameters (number of aliquots and percent storm capture) per amount of rainfall are specified in Section 10. Samples not meeting these criteria are generally not analyzed; however, selected analyses can be run at the Caltrans task manager's discretion. If samples not meeting the minimum sample representativeness criteria are analyzed, the resulting data should be rejected ("R") or qualified as estimated ("J"), depending upon whether the analyses were approved by Caltrans. Grab samples should be taken according to the timing protocols specified in the SAP. Deviations from the protocols will result in the rejection of the data for these samples or qualification of the data as estimated. The decision to reject a sample based on sample representativeness should be made prior to the submission of the sample to the laboratory, to avoid unnecessary analytical costs. 2. Check of laboratory data report completeness: As discussed in Section 12, the end product of the laboratory analysis is a data report that should include a number of QA/QC results along with the environmental results. QA/QC sample results reported by the lab should include both analyses requested by the field crew (field blanks, field duplicates, lab duplicates and MS/MSD analysis), as well as internal laboratory QA/QC results (method blanks and laboratory control samples). There are often differences among laboratories in terms of style and format of reporting. Therefore, it is prudent to request in advance that the laboratory conform to the style and format approved by Caltrans as shown in Section 14. The Caltrans data reviewer should verify that the laboratory data package includes the following items: ✓ A narrative which outlines any problems, corrections, anomalies, and conclusions. ✓ Sample identification numbers. ✓ Sample extraction and analysis dates. ✓ Reporting limits for all analyses reported. ✓ Results of method blanks. ✓ Results of matrix spike and matrix spike duplicate analyses, including calculation of percent recovered and relative percent differences. ✓ Results of laboratory control sample analyses. ✓ Results of external reference standard analyses. ✓ Surrogate spike and blank spike analysis results for organic constituents. Implementing the Monitoring Plan 13-2 May 2000 QA/QC Data Evaluation ✓ A summary of acceptable QA/QC criteria(RPD, spike recovery) used by the laboratory. Items missing from this list should be requested from the laboratory. 3. Check for typographical errors and apparent incongruities: The laboratory reports should be reviewed to identify results that are outside the range of normally observed values. Any type of suspect result or apparent typographical error should be verified with the laboratory. An example of a unique value would be if a dissolved iron concentration has been reported lower than 500 µg/l, for every storm event monitored at one location and then a value of 2500 µg/L is reported in a later event. This reported concentration of 2500 µg/l, should be verified with the laboratory for correctness. Besides apparent out-of-range values, the indicators of potential laboratory reporting problems include: • Significant lack of agreement between analytical results reported for laboratory duplicates or field duplicates. • Consistent reporting of dissolved metals results higher than total or total recoverable metals. • Unusual numbers of detected values reported for blank sample analyses. • Inconsistency in sample identification/labeling. If the laboratory confirms a problem with the reported concentration, the corrected or recalculated result should be issued in an amended report, or if necessary the sample should be re-analyzed. If laboratory results are changed or other corrections are made by the laboratory, an amended laboratory report should be issued to update the project records. > DATA QUALITY EVALUATION The data quality evaluation process is structured to provide systematic checks to ensure that the reported data accurately represent the concentrations of constituents actually present in stormwater. Data evaluation can often identify sources of contamination in the sampling and analytical processes, as well as detect deficiencies in the laboratory analyses or errors in data reporting. Data quality evaluation allows monitoring data to be used in the proper context with the appropriate level of confidence. QA/QC parameters that should be reviewed are classified into the following categories: ✓ Reporting limits Implementing the Monitoring Plan 13-3 May 2000 QA/QC Data Evaluation ✓ Holding times ✓ Contamination check results (method, field, trip, and equipment blanks) ✓ Precision analysis results (laboratory, field, and matrix spike duplicates) ✓ Accuracy analysis results (matrix spikes, surrogate spikes, laboratory control samples, and external reference standards) Each of these QA/QC parameters should be compared to data quality acceptability criteria, inalso known as the project's data quality objectives (DQOs). The key steps that should be adhered to in the analysis of each of these QA/QC parameters are: 1. Compile a complete set of the QA/QC results for the parameter being analyzed. 2. Compare the laboratory QA/QC results to accepted criteria(DQOs). 3. Compile any out-of-range values and report them to the laboratory for verification. 4. Prepare a report that tabulates the success rate for each QA/QC parameter analyzed. This process should be applied to each of the QA/QC parameters as discussed below. Reporting Limits Stormwater quality monitoring program DQOs should contain a list of acceptable reporting limits that the lab is contractually obligated to adhere to, except in special cases of insufficient sample volume or matrix interference problems. The reporting limits used should ensure a high probability of detection. , Table 12-1 provides recommended reporting limits for selected parameters. Holding Times Holding time represents the elapsed time between sample collection time and sample analysis time. Calculate the elapsed time between the sampling time and start of analysis, and compare this to the required holding time. For composite samples that are collected within 24-hours or less, the time of the final sample aliquot is considered the "sample collection time" for determining sample holding time. For analytes with critical holding times (<_48 hours), composite samples lasting longer than 24-hours require multiple bottle composite samples. Each of these composite samples should represent less than 24 hours of monitored flow, and subsamples from the composites should have been poured off and analyzed by the laboratory for those constituents with critical holding times (see Section 12). It is important to review sample holding times to ensure that analyses occurred within the time period that is generally accepted to maintain stable parameter concentrations. Table 12-1 contains the holding times for selected parameters. If holding times are exceeded, inaccurate concentrations or false negative results may be reported. Implementing the Monitoring Plan 13-4 May 2000 QA/QC Data Evaluation Samples that exceed their holding time prior to analysis are qualified as "estimated", or may be rejected depending on the circumstances. Contamination Blank samples are used to identify the presence and potential source of sample contamination and are typically one of four types: 1. Method blanks are prepared and analyzed by the laboratory to identify laboratory contamination. 2. Field blanks are prepared by the field crew during sampling events and submitted to the laboratory to identify contamination occurring during the collection or the transport of environmental samples. 3. Equipment blanks are prepared by the field crew or laboratory prior to the monitoring season and used to identify contamination coming from sampling equipment(tubing, pumps, bailers, etc.). 4. Trip blanks are prepared by the laboratory, carried in the field, and then submitted to the laboratory to identify contamination in the transport and handling of volatile organics samples. 5. Filter blanks are prepared by field crew or lab technicians performing the sample filtration. Blank water is filtered in the same manner and at the same time as other environmental samples. Filter blanks are used to identify contamination from the filter or filtering process. If no contamination is present, all blanks should be reported as "not detected" or"non- detect" (e.g., constituent concentrations should not be detected above the reporting limit). Blanks reporting detected concentrations ("hits") should be noted in the written QA/QC data summary prepared by the data reviewer. In the case that the laboratory reports hits on method blanks, a detailed review of raw laboratory data and procedures should be requested from the laboratory to identify any data reporting errors or contamination sources. When other types of blanks are reported above the reporting limit, a similar review should be requested along with a complete review of field procedures and sample handling. Often times it will also be necessary to refer to historical equipment blank results, corresponding method blank results, and field notes to identify contamination sources. This is a corrective and documentative step that should be done as soon as the hits are reported. If the blank concentration exceeds the laboratory reporting limit, values reported for each associated environmental sample must be evaluated according to USEPA guidelines for data evaluations of organics and metals (USEPA, 1991; USEPA, 1995) as indicated in Table 13-1. Implementing the Monitoring Plan 13-5 May 2000 QA/QC Data Evaluation Table 13-1. USEPA Guidelines for Data Evaluation Step Environmental Phthalates and Other Organics Metals Sample other common contaminants 1. Sample> 10X blank concentration No action No action No action 2. Sample< lOX Report associated No action Results considered blank concentration environmental an"upper limit"of results as"non- the true detect"at the concentration (note reported contamination in environmental data quality concentration. evaluation narrative). 3. Sample<5X blank Report associated Report associated Report associated concentration environmental environmental environmental results as"non- results as"non- results as"non- detect"at the detect"at the detect"at the reported reported reported environmental environmental environmental concentration. concentration. concentration. Specifically, if the concentration in the environmental sample is less than five times the concentration in the associated blank, the environmental sample result is considered, for reporting purposes, "not-detected" at the environmental sample result concentration (phthalate and other common contaminant results are considered non-detect if the environmental sample result is less than ten times the blank concentration). The laboratory reports are not altered in any way. The qualifications resulting from the data evaluation are made to the evaluator's data set for reporting and analysis purposes to account for the apparent contamination problem. For example, if dissolved copper is reported by the laboratory at 4 µg/L and an associated blank concentration for dissolved copper is reported at 1 µg/L, data qualification would be necessary. In the data reporting field of the database (see Section 14), the dissolved copper result would be reported as 4 µg/L), the numerical qualifier would be reported as "<", the reporting limit would be left as reported by the laboratory, and the value qualifier would be reported as "U" ("not detected above the reported environmental concentration"). When reported environmental concentrations are greater than five times (ten times for phthalates) the reported blank"hit" concentration, the environmental result is reported unqualified at the laboratory-reported concentration. For example, if dissolved copper is reported at 11 µg/L and an associated blank concentration for dissolved copper is reported at 1 µg/L, the dissolved copper result would still be reported as 11 µg/L. Implementing the Monitoring Plan 13-6 May 2000 QA/QC Data Evaluation Precision Duplicate samples provide a measure of the data precision (reproducibility) attributable to sampling and analytical procedures. Precision can be calculated as the relative percent difference(RPD) in the following manner: 2*1Oi—DI RPDi= *100% (Oi+Di) where: RPDi = Relative percent difference for compound i Oi = Value of compound i in original sample Di = Value of compound i in duplicate sample The resultant RPDs should be compared to the criteria specified in the project's DQOs. The DQO criteria shown in Table 13-2 below are based on the analytical method specifications and laboratory-supplied values. Project-specific DQOs should be developed with consideration to the analytical laboratory, the analytical method specifications, and the project objective. Table 13-2 should be used as a reference point as the least stringent set of DQO criteria for Caltrans monitoring projects. Laboratory and Field Duplicates Laboratory duplicates are samples that are split by the laboratory. Each half of the split sample is then analyzed and reported by the laboratory. A pair of field duplicates is two samples taken at the same time, in the same manner into two unique containers. Subsampling duplicates are two unique, ostensibly identical, samples taken from one composite bottle (see Section 10). Laboratory duplicate results provide information regarding the variability inherent in the analytical process, and the reproducibility of analytical results. Field duplicate analysis measures both field and laboratory precision, therefore, it is expected that field duplicate results would exhibit greater variability than lab duplicate results. Subsampling duplicates are used as a substitute for field duplicates in some situations and are also an indicator of the variability introduced by the splitting process. The RPDs resulting from analysis of both laboratory and field duplicates should be reviewed during data evaluation. Deviations from the specified limits, and the effect on reported data, should be noted and commented upon by the data reviewer. Laboratories typically have their own set of maximum allowable RPDs for laboratory duplicates based on their analytical history. In most cases these values are more stringent than those listed in Table 13-2. Note that the laboratory will only apply these maximum allowable RPDs to laboratory duplicates. In most cases field duplicates are submitted "blind" (with pseudonyms)to the laboratory. Implementing the Monitoring Plan 13-7 May 2000 QA/QC Data Evaluation Environmental samples associated with laboratory duplicate results greater than the maximum allowable RPD (when the numerical difference is greater than the reporting limit) are qualified as"J" (estimated). When the numerical difference is less than the RL, no qualification is necessary. Field duplicate RPDs are compared against the maximum allowable RPDs used for laboratory duplicates to identify any pattern of problems with reproducibility of results. Any significant pattern of RPD exceedances for field duplicates should be noted in the data report narrative. Corrective action should be taken to address field or laboratory procedures that are introducing the imprecision of results. The data reviewer can apply "J" (estimated) qualifiers to any data points if there is clear evidence of a field or laboratory bias issue that is not related to contamination. (Qualification based on contamination is assessed with blank samples.) Laboratories should provide justification for any laboratory duplicate samples with RPDs greater than the maximum allowable value. In some cases, the laboratory will track and document such exceedances, however; in most cases it is the job of the data reviewer to locate these out-of-range RPDs. When asked to justify excessive RPD values for field duplicates, laboratories most often will cite sample splitting problems in the field. Irregularities should be included in the data reviewer's summary, and the laboratory's response should be retained to document laboratory performance, and to track potential chronic problems with laboratory analysis and reporting. Accuracy Accuracy is defined as the degree of agreement of a measurement to an accepted reference or true value. Accuracy is measured as the percent recovery (%R) of spike compound(s). Percent recovery of spikes is calculated in the following manner: %R = 100% * [(CS—C)/S] where: %R = percent recovery CS = spiked sample concentration C = sample concentration for spiked matrices S = concentration equivalent of spike added Accuracy(%R) criteria for spike recoveries should be compared with the limits specified in the project DQOs. A list of typical acceptable recoveries is shown in Table 13-2. As in the case of maximum allowable RPDs, laboratories develop acceptable criteria for an allowable range of recovery percentages that may differ from the values listed in Table 13- 2. Implementing the Monitoring Plan 13-8 May 2000 QA/QC Data Evaluation Percent recoveries should be reviewed during data evaluation, and deviations from the specified limits should be noted in the data reviewer's summary. Justification for out of range recoveries should be provided by the laboratory along with the laboratory reports, or in response to the data reviewer's summary. Laboratory Matrix Spike and Matrix Spike Duplicate Samples Evaluation of analytical accuracy and precision in environmental sample matrices is obtained through the analysis of laboratory matrix spike (MS) and matrix spike duplicate (MSD) samples. A matrix spike is an environmental sample that is spiked with a known amount of the constituent being analyzed. A percent recovery can be calculated from the results of the spike analysis. A MSD is a duplicate of this analysis that is performed as a check on matrix recovery precision. MS and MSD results are used together to calculate RPD as with the duplicate samples. When MS/MSD results (%R and RPD) are outside the project specifications, as listed in Table 13-2, the associated environmental samples are qualified as "estimates due to matrix interference". Surrogate standards are added to all environmental and QC samples tested by gas chromatography (GC) or gas chromatography-mass spectroscopy (GC-MS). Surrogates are non-target compounds that are analytically similar to the analytes of interest. The surrogate compounds are spiked into the sample prior to the extraction or analysis. Surrogate recoveries are evaluated with respect to the laboratory acceptance criteria to provide information on the extraction efficiency of every sample. External Reference Standards External reference standards (ERS)are artificial certified standards prepared by an external agency and added to a batch of samples. ERS's are not required for every batch of samples, and are often only run quarterly by laboratories. Some laboratories use ERS's in place of laboratory control spikes with every batch of samples. ERS results are assessed the same as laboratory control spikes for qualification purposes (see below). The external reference standards are evaluated in terms of accuracy, expressed as the percent recovery (comparison of the laboratory results with the certified concentrations). The laboratory should report all out-of-range values along with the environmental sample results. ERS values are qualified as biased high" when the ERS recovery exceeds the acceptable recovery range and "biased low" when the ERS recovery is smaller than the recovery range. Laboratory Control Samples LCS analysis is another batch check of recovery of a known standard solution that is used to assess the accuracy of the entire recovery process. LCSs are much like ERS's except that a certified standard is not necessarily used with LCSs, and the sample is prepared internally by the laboratory so the cost associated with preparing a LCS sample is much lower than the cost of ERS preparation. LCSs are reviewed for percent recovery within Implementing the Monitoring Plan 13-9 May 2000 QA/QC Data Evaluation control limits provided by the laboratory. LCS out-of-range values are treated in the same manner as ERS out-of-range values. Because LCS and ERS analysis both check the entire recovery process, any irregularity in these results supersedes other accuracy-related qualification. Data are rejected due to low LCS recoveries when the associated environmental result is below the reporting limit. A flow chart of the data evaluation process, presented on the following pages as Figures 13-1 (lab-initiated QA/QC samples) and 13-2 (field-initiated QA/QC), can be used as a general guideline for data evaluation. Boxes shaded black in Figures 13-1 and 13-2 designate final results of the QA/QC evaluation. Implementing the Monitoring Plan 13-10 May 2000 QA/QC Data Evaluation Table 13-2. Typical Control Limits for Precision and Accuracy for Analytical Constituents Maximum 70,A Method Number Recovery Recovery Analyte r Standard Method Allowable Upper Limit Lower Limit RPD Conventionals BOD 405.1;SM 5210B 20% 80% 120% COD 410.1;410.4;SM 5220C; 20% 80% 120% SM 5220D Hardness 130.2;130.1;SM 2340B 20% 80% 120% pH 150.1 20% NA NA TOC/DOC 415.1 15% 85% 115% TDS 160.1 20% 80% 120% TSS 160.2 20% 80% 1201/o Turbidity 180.1 20% NA NA Nutrients NH3-N 350.2;3503 20% 80% 120% NO3-N 300.0 20% 80% 120% NO2-N 300.0 20% 80% 120% NO3/NO2-N 353.2 20% 80% 120% P 365.2 20% 80% 120% Ortho-P 365.2;365.3 20% 80% 120% TKN 351.3 200/. 80% 120% Metals Ag 272.2;200.8 20% 75% 125% Al 200.9;200.8 20% 75% 125% Cd 213.2;200.8 200/. 75% 125% Cr 218.2;200.8 20% 75% 125% Cu 220.2;200.8 20% 75% 125% Ni 249.2;200.8 20% 75% 125% Pb 239.2;200.8 20% 75% 125% Zn 289.2;200.8 20% 75% 125% As 206.3;200.8 20% 751/o 125% Fe 200.9;SM 3500-Fe B 20% 75% 125% Se 200.9;270.3;200.8 20% 75% 125% Hg 1 1631 21% 79% 121% Total Petroleum Hydrocarbons TPH (gasoline) 21% 45% 129% TPH(diesel) 8015b 21% 45% 129% TPH(motor oil) 21% 45% 129% Oil&Grease 1664 18% 79% 114% Pesticides and Herbicides Glyphosate 547 30% 70% 130% OP Pesticides (esp.diazinon 8141;ELISA 25% and chlor rifos) OC Pesticides 8081 25% see method for constituent Chlorinated 8150;8151 25% specific Herbicides Carbamate 8321 25% Pesticides Miscellaneous Organic Constituents Base/Neutrals 625;8270 30%to 50% and Acids (analyte see method for constituent PAHs 8310 dependent) specific Purgeables 624;8260 20% Purgeable 601 30% see method, Table 2 Halocarbons Purgeable 602 20% see method for constituent Aromatics specific Miscellaneous Constituents Cyanide 335.2 20% 75 125 Bacteriological Fecal Coliform SM 9221 E Total Coliform SM 9221 B Implementing the Monitoring Plan 13-11 May 2000 QA/QC Data Evaluation (Revised May 2002) • • Is I Qualify results as estimated if holding time variance allowed,or reject 11 031111111111%'„ '„'__, ,_• results. Proceed to next step. • • • � . � . - � ' ' • No qualification. a- - • ' ' Proceed to next step. No qualification. Qualify associated detected Proceed to next step. environmental sample results as"U". Proceed to next step. • �. _ _ _ _ Qualify sample results as estimate due to analytical variability. • • ' �' Proceed to next step. If MS result is>UL, No qualification. qualify detected associated environmental sample results as Proceed to next stop estimates due to matrix interference. ® ' If MS result is<LL, qualify associated environmental sample results as estimates due to matrix interference and consider rejecting associated environmental sample data below detection based on other supporting QA/QC data. "U D Qualify sample results as estimates � _ •_ < ,., � �;� �„�,, ;� W"' due to matrix interfernce. Proceed to next step. If spike recovery result is>UL, qualify associated environmental sample results above detection levels as estimates due to high analytical bias. ' If spike recovery result is<LL or more than half of recoveries are outside acceptability limits, "' x qualify associated detected environmental sample results as estimates due to low analytical bias and reject associated environmental sample data below detection. No qualification. Proceed to field-initiated QA/QC data evaluation Are sample results p 7. Are field blanks ND? • Are sample <10x(phthalates&common contaminants)o results ND? -' � <5x(semi-&non-volatiles&metals*) ' , ,•• : • blank concentration? report No qualification. Qualify associated detected environmental sample results as"U". Proceed to next step. Report patterns in data $ Are field duplicate RPD Are measured differences between samples ' ' lab within project specs? less than the Reporting Limit? protocols Qualify results if deemed necessary. jai Y Proceed to next step. Do overall QC results Make additional 9• indicate systematic ;- necessary matrix,method,etc. problems? d Qualified No limitation on use of unqualified data. noted and reported. *Environmental results between 5x and 1 Ox the blank concentration are qualified as"an upper limit on the true concentration"and the data user should be cautioned. Figure 13-2. Technical Data Evaluation for Field-Initiated QA/QC Samples Implementing the Monitoring Plan 13-13 May 2000 QA/QC Data Evaluation Appendix I April 24, 2007 Comment Letter from the Los Angeles Regional Water Quality Control Board and Response to Comments California Regional Water Quality Control Board Los Angeles Region Recipient of the 2001 Environmental Leadership Award from Keep California Beautiful Linda S.Adams 320 W.4th Street,Suite 200,Los Angeles,California 90013 Arnold Schwarzenegger Agency Secretary Phone(213)576-6600 FAX(213)576-6640 - Internet Address: http://www.waterboards.ca.gov/losangeles Governor April 24, 2007 Richard Hajas Calleguas Creek Watershed Management Plan Water Quality/Water Resources Subcommittee 2100 Olsen Road Thousand Oaks, California Monitoring and Reporting Program Plan and Quality Assurance Project Plan,for the Nitrogen, OC and PCBs, and Toxicity TMDLs Dear Mr. Hajas, Thank you for the submission of the Monitoring and Reporting Program Plan (MRP) and Quality Assurance Project Plan (QAPP) for the Nitrogen, OC and PCBs; and Toxicity TMDLs on September 26, 2006 in compliance with the Calleguas Creek Watershed Nitrogen, OC and PCBs, and Toxicity TMDLs. Regional Board staff has reviewed these documents and generally agrees with the approach outlined in the MRP and the QAPP. However, please revise and or provide a response to the following comments: • Sediment testing for selenium should be added to the list of metals to be tested in Mugu Lagoon (Table 2,-page 11) • The underlined language below should be added to.the Special Studies section on page 13: "...No specific special studies are incorporated into the QAPP at this time; however, a summary of special studies that may be incorporated at a later date are provided below. Work plan for specific special study shall be submitted to the Regional Board for approval Additional special studies may be added as other TMDLs are completed (e.g., metals, salts, and bacteria) or developed through other processes." ■ Include the CAS No. for each sample as part of the analytical data reports (page 15). ■ Two addition wet weather sampling event should be done at all sites except for POTWs' discharges as they were not identified as major sources of constituents identified in the TMDLs. If the changes can not be made please provide an explanation why additional wet weather sampling event are not included for these specific sites. • Toxicity testing should be monitored for Beardsley Wash (Reach 5) as it is impaired for toxicity. • Reaches 9A and 10 have various tissue impairments. Therefore, tissue testing should be included for Reaches 9A and 10. California Environmental Protection Agency Q1, Recycled Paper Calleguas Creek Watershed Management Plan April 24, 2007 Water Quality/Water Resources Subcommittee Page 2 of 3 • Under bullet one on page 45, it is suggested to put the bubbled wrapped bottles and or containers into re-sealable bags before placing them in the-ice chest. • The project reporting limits listed in Table 13 for total suspended solids, and Nitrate— N are higher than those Listed in the SWAMP QAPP. Please provide an explanation and or change the reporting limits to reflect those listed in the SWAMP QAPP template of: ❑ Total Suspended Solids - 0.5 mg/L ❑ Nitrate-N- 0.01 mg/L • The analytical methods for pyrethroid pesticides are not listed in Table 13 on pages 49 and 51. Please specify these methods and or provide detailed information the GCMS alternate test procedure. • The following pesticides listed in Table 9 Aldrin, alpha-BHC, Chlordane-alpha, Chlordane-gamma, 4,4'-DDD,.4,4'-DDE, 4;4'-DDT,;Dieldrin and Toxaphene have the MDL or RL higher than the assigned WLAs and LAs, please provide an explanation for this. • Paragraph 6 on page 68 of the Assessments and Response Action should be revised to read as follow: 'If a coordinated and comprehensive monitoring plan that address multiple regulatory requirements (i.e., TMDL, NPDES, Ag Waiver, etc.) is developed, aad meet the goals of this monitoring plan,and approved by the Executive Officer, that plan should be considered as a replacement for the CCWTMP. • In reviewing the Toxicity Testing and Toxicity Identification Evaluations section of the QAPP it was noted that the procedures described differ from the procedures proposed in the Conditional Waiver for Agricultural Dischargers. Please provide rationale demonstrating that the procedures proposed in the CCWMP QAPP are equivalent to the procedures specified in the Conditional Waiver. • Regional Board staff is specifically concerned that the 50% mortality endpoint for TIE initiation, which is based on acute toxicity methods, does not reflect the same endpoint sensitivity as established in the waiver by the use of TU, units. This unit of the toxicity water quality benchmark set in the Conditional Waiver integrates chronic toxicity endpoints; it is important that the sensitivity of this endpoint be conserved. • The approach section of the MRP states an effort to coordinate monitoring between the Calleguas Creek Watershed TMDL monitoring and the Conditional Waiver monitoring in the Calleguas Creek Watershed. Please clarify how data will be used and/or shared between these two monitoring programs and specifically identify sites that correspond between the two programs. California Environmental Protection Agency Ott Recycled Paper Calleguas Creek Watershed Management Plan April 24, 2007 Water Quality/Water Resources Subcommittee Page 3 of 3 ■ Paragraph six on page 53 discusses the decision to initiate TIE procedures. Please state that Regional Board staff will participate in consultation with the Project Manager and the toxicity laboratory on the decision to initiate TIE procedures. Your consideration of these comments is appreciated. Please contact me (213)567-6622, or Thanhloan Nguyen (213)576-6690 if you have any questions or would like to schedule a meeting to discuss these comments. Sincerely, ' 1 Samuel Unger, P.E. Section Chief—Regional Programs California Environmental Protection Agency VJ Recycled Paper Our mission is to preserve and enhance the quality of California's water resources for the benefit ofpresent and future eenerations. Responses to Regional Board Comments on the Draft Calleguas Creek Watershed Monitoring and Reporting Plan and Quality Assurance Project Plan for the Nitrogen, OC and PCBs, and Toxicity TMDLs dated September 26, 2006 Prepared by Larry Walker Associates June 18, 2007 Comment Response Los An eles Regional Water Quality Control Board-Letter dated April 24,2007 RB-1 Table 2, Page 11 -Sediment testing for selenium should be added to the list of metals to be tested The current version of the QAPP is not intended to address the Metals and in Mugu Lagoon. Selenium TMDLs. The metals presented in Table 2 were selected as they have been found in previous sediment studies conducted in Mugu Lagoon to exceed guideline values used to interpret the relationship between sediment chemistry and biological impacts(e.g.,toxicity). Selenium was not found to exceed SQUIRT guideline values and as such is not included. Additional metals and/or selenium may be added in the future to address the needs of the Metals and Selenium TMDLs. Language was added to the footnote in Table 2 to clarify why the metals resented were selected for analysis. RB-2 Special Studies section, Page 13-The underlined language below should be added: "...No Revised per comment. specific special studies are incorporated into the QAPP at this time; however,a summary of special studies that may be incorporated at a later date are provided below.Work plan for specific special study shall be submitted to the Regional Board for approval.Additional special studies may be added as other TMDLs are completed(e.g.,metals,salts,and bacteria)or developed through other ,processes 11 RB-3 Page 15-Include the CAS No.for each sample as part of the analytical data reports Revised per comment. Responses to Comments/CCW TMDL Monitoring Program QAPP September 26,2006 1 of 5 June 2007 Comment Response RB-4 Two additional wet weather sampling events should be done at all sites except for POTW's A primary goal of the CCWTMP is to determine compliance with targets and discharges as they were not identified as major sources of constituents identified in the TMDLs. If allocations. A total of six events,which includes two wet weather events,over the the changes cannot be made please provide an explanation why additional wet weather samples course of the year is sufficient,at this time,to evaluate compliance with targets and events are not included for these specific sites allocations. Given the implementation schedules for the Nutrients,Toxicity,and OCs TMDLs are 7, 10,and 20 years, respectively,the frequency of monitoring outlined in the CCWTMP,and the additional monitoring conducted by other programs in the watershed, it is expected that a range of wet weather conditions will be evaluated and sufficient data will be available to answer the monitoring questions posed in Element 5(Problem Definition/Background)without collection of two additional wet weather samples at this time. If the wet weather data generated through the two wet weather events conducted by this program each year and the two and four conducted annually by the Irrigated Lands Group and the County Stormwater Program, respectively,are determined to be insufficient to attain the goals of the monitoring program additional wet events can be added. Additional sites were added as part of a Nutrient Investigation component of the CCWTMP. Sampling in support of nutrient investigation monitoring will focus on evaluating urban land use and open space contributions of nutrients and nutrient loads in receiving waters during wet weather. The urban land use component of nutrient investigation monitoring is addressed through the land use discharge investigation discussed above. An open space site was selected at a location in the watershed where flows are present throughout the year from a drainage that is open space. Evaluation of nutrient loading during wet weather will be addressed through collecting samples at compliance monitoring sites and urban,agricultural,and open space land use monitoring sites. Nutrient investigation monitoring is intended to occur during the first year of the CCWTMP, unless results suggest continuing at one or more sites. Several changes were made to the QAPP regarding sites and frequency to address nutrient investigation monitoring. Site 07T_LL_RC replaced 08_WALNU as a representative open space site to evaluate loads from this land use. Additionally,two wet weather events were added to evaluate nutrient loadings to the following sites: 05_CENTR, 10_GATE,and 07 MADER. Nutrient sampling will also occur during wet weather at the following sites: 01_RR_BR, 03_UNVI,04_WOOD, 9B_ADOLF,06_SOMIS,and 07 HITCH. Responses to Comments/CCW TMDL Monitoring Program QAPP September 26,2006 2 of 5 June 2007 Comment Response RB-5 Toxicity testing should be monitored for Beardsley Wash(Reach 5)as it is impaired for toxicity. As discussed in the QAPP,the process for selection of sites was based on including sites on reaches or in a subwatershed for which waste loads and loads were allocated, not necessarily where impairments are listed. Allocations were assigned to each 303(d)listed reach in the Nutrients TMDL. Accordingly, at least one Nutrients TMDL compliance monitoring site is located in each 303(d)listed reach. Allocations were assigned by modeling subwatersheds in the Toxicity and OCs TMDLs. Accordingly,at least one compliance monitoring site is located in each modeling subwatershed that received an allocation. The compliance monitoring site for the Revolon Slough/Beardsley Wash subwatershed was established on Revolon Slough at Wood Rd(Site 04_WOOD) and is intended to address toxicity in this subwatershed. The number and location of sites may be revised if it is determined that alternative locations are needed. For example,at such a time as numeric targets are consistently met at a compliance monitoring site,an additional site or sites within the subwatershed will be considered for monitoring to ensure allocations are met throughout the subwatershed. Additionally,the Ventura County Agricultural Irrigated Lands Group(VCAILG)under the Conditional Waiver for Irrigated Agricultural Lands program(Ag Waiver)will be monitoring two locations within the Beardsley Wash area for toxicity. These data will be incorporated into the TMDL analysis conducted in the Annual Report as outlined in the QAPP. A note was added to the QAPP indicating data collected in the Beardsley Wash area are available and will be considered. RB-6 Reaches 9A and 10 have various tissue impairments.Therefore,tissue testing should be included As discussed in the previous response,the compliance monitoring site for the for Reaches 9A and 10. Calleguas subwatershed,which includes Reach 9A, is located on Calleguas Creek at University Drive(03_UNIV)and the compliance monitoring site for the Conejo subwatershed,which includes Reach 10,was set on Conejo Creek at Adolfo Road (913_ADOLF). These two sites are intended to address fish tissue concentrations in these subwatersheds, among other allocations. The number and location of sites may be revised if it is determined that alternative locations are needed. For example,at such a time as numeric targets are consistently met at a compliance monitoring site, an additional site or sites within the subwatershed will be considered for monitoring to ensure allocations are met throughout the subwatershed. Additionally,the City of Thousand Oaks Hill Canyon Wastewater Treatment Plant collects water samples for consituents with wasteload allocations identified in the OC pesticides and PCBs TMDL at receiving water locations in Conejo Creek on Reaches 10 and 12. These data will be incorporated into the TMDL analysis conducted in the Annual Report as outlined in the QAPP. A note was added to the QAPP indicating data collected in Conejo Creek are available and will be considered. RB-7 Page 45-Under bullet one, it is suggested to put the bubbled wrapped bottles and/or containers Comment noted, re-sealable bags will be used if available. into re-sealable bags before placing them in the ice chest. Responses to Comments/CCW TMDL Monitoring Program QAPP September 26,2006 3 of 5 June 2007 Comment Response RB-8 Table 13-The project reporting limits listed for total suspended solids, and Nitrate- N are higher Of the 1690 nitrate as N data available in the watershed 98%were detected data than those listed in the SWAMP QAPP. Please provide an explanation or change the reporting with less than 1%detected below the RL of 0.1 mg/L proposed in the QAPP. Of the limits to reflect those listed in the SWAMP QAPP template of*Total Suspended Solids-0.5 mg/L 15065 TSS data available in the watershed 99%were detected data with 2% and"Nitrate N-0.01 mg/L detected below the RL of 1 mg/L proposed in the QAPP. Less than 0.1%of all TSS data were non-detect at an RL of 1 mg/L. A review of the available data does not suggest that the reporting limits presented in the QAPP will lead to a significant number of non-detect values. This information was added to the QAPP. RB-9 Table 13, Pages 49-51 -The analytical methods for pyrethroid pesticides are not listed. Please The analytical method that will be used for pyrethroid pesticides will be 8270C(NCI), specify these methods and/or provide detailed information the GCMS alternate test procedure. where NCI is negative chemical ionization as allowed under the method. A footnote was added to the table. RB-10 Table 9 Aldrin-The following pesticides listed,alpha-BHC,Chlordane-alpha, Chlordane-gamma, The following explanation was added: "The MDLs and/or RLs listed for several 4,4'-DDD,4,4'-DDE,4,4'-DDT, Dieldrin and Toxaphene have the MDL or RL higher than the organochlorine pesticides in water(aldrin,alpha-BHC,chlordane, DDTs,dieldrin and assigned WLAs and Las, please provide an explanation for this. toxaphene)are higher than targets/allocations specified in the BPAs. However,the MDLs and/or RLs listed herein are significantly lower than levels currently attainable by commercial laboratories using standard analytical test methods and are consistent with the lowest detection limits reported for NPDES monitoring ro rams." RB-11 Paragraph 6, Page 68-Assessments and Response Action should be revised to read as follows: If Revised per comment as follows: "If a coordinated and comprehensive monitoring a coordinated and comprehensive monitoring plan that address multiple regulatory requirements plan that addresses multiple regulatory requirements(i.e.,TMDL, NPDES,Ag (i.e..,TMDL, NPDES,Ag Waiver,etc.)is developed,aPA meet the goals of this monitoring plan, Waiver, etc.)is developed and meets the goals of this monitoring plan,that plan and approved by the Executive Officer,that plan should be considered as replacement for the should be considered as a replacement for the CCWTMP. Any such plan would CCWTMP. re uire the approval of the Executive Officer." RB-12 In reviewing the Toxicity Testing and Toxicity Identification Evaluations section of the QAPP it was The following text was added to clarify why the test species were chosen: "The test noted that the procedures described differ from the procedures proposed in the conditional Waiver species selected are standard USEPA test species considered to be among the for Agricultural Dischargers. Please provide rationale demonstrating that the procedures proposed most sensitive species to many different types of pollutants. The test species are in the CCWMP QAPP are equivalent to the procedures specified in the Conditional Waiver. particularly sensitive to constituents previously identified as contributing to toxicity in water and/or sediment in the CCW. C.dubia is a water flea known to be extremely sensitive to organophosphate pesticides and some metals and also is used as an indicator of ammonia toxicity. H. azteca is a sediment dwelling invertebrate that is sensitive to ammonia and organochlorine pesticides. E.estuarius is a burrowing amphipod that is sensitive to organochlorine and organophosphate pesticides. A. bahia is a shrimp known to be sensitive to organophosphate pesticides.At such a time as toxicity numeric targets are consistently met,alternative species may be considered if it is determined the aforementioned species are not completely assessing toxicity in the CCW." Responses to Comments/CCW TMDL Monitoring Program QAPP September 26,2006 4 of 5 June 2007 Comment Response RB-13 Regional Board Staff is specifically concerned that the 50%mortality endpoint for TIE initiation, Chronic tests will be used to assess both survival and reproductive/growth endpoints which is based on acute toxicity methods,does not reflect the same endpoint sensitivity as for each species to allow for an evaluation of compliance with the 1 TUC endpoint in established in the waiver by the use of TUB units.This unit of the toxicity water quality benchmark water established in the TMDL BPAs and in the Conditional Waiver.Therefore,the set in the Conditional Waiver integrates chronic toxicity endpoints; it is important that the sensitivity sensitivity of this endpoint is conserved. Similar to the Conditional Waiver TIE of this endpoint be conserved. approach,the 50%mortality endpoint is for TIE initiation only not for assessing compliance with the TMDL.As discussed in the QAPP,the 50%mortality endpoint for TIE initation is based on USEPA guidance and extensive experience conducting TIEs in the CCW. TIE initiation is not based on"acute toxicity methods"as the QAPP utilizes chronic toxicity tests. For clarification,a toxic effect(mortality or reduced reproduction/growth)observed in 96 hours or less is typically considered acute. A chronic toxic effect(which can include mortality or reduced reproduction/growth),would be the effect observed over the portion of the test beyond the test duration of an acute test. The test duration for chronic tests are based on the life span of the species. In the case of Ceriodaphnia Dubia,the chronic test duration is 7 days. Text similar to the response to this comment was added to the QAPP. RB-14 The approach section of the MRP states an effort to coordinate monitoring between the Calleguas Revised text in Element 18(Non-Direct Measurements)to indicate data from other Creek Watershed TMDL monitoring and the Conditional Waiver monitoring in the Caileguas Creek programs(including the VCAILG)will be incorporated and the data from other Watershed. Please clarify how data will be used and/or shared between these two monitoring programs will be used to supplement land use data to evaluate loading to the programs and specifically identify sites that correspond between the two programs. receiving water as well as to evaluate receiving water quality. Additionally,Table 8 was revised to specifically identify sites that correspond between the two programs. RB-15 Paragraph 6, Page 53-Discusses the decision to initiate TIE procedures. Please state that Revised to state Regional Board staff will be consulted in making the determination Regional Board Staff will participate in consultation with the Project Manager and the toxicity of whether to initiate TIE procedures. laboratory on the decision to initiate TIE procedures. Responses to Comments/CCW TMDL Monitoring Program QAPP September 26,2006 5 of 5 June 2007 EXHIBIT F version 9/24/2007 CALLEGUAS CREEK TMDL PROGRAM IMPLEMENTATION FORMULA-VOTING POWER TABLE 1 %of Cost Allocations for each TMDL by Discharger Group.' (Overall) Fiscal Agent Discharger Group Nutrients OC/PCBs Toxicity Metals Svc GWQC One Time POTW 67.60% 0.90% 29.40% 14.70% 28.15% 28.15% 28.15% Urban 0.00% 26.70% 36.90% 33.40% 24.25% 24.25% 24.25% Agriculture 32.40% 72.40% 33.70% 51.90% 47.60% 47.60% 47.60% Total Budget Annual Monitoring Budget $ 1,532,000 $ 64,000 $186,000 $ 556,000 $ 163,000 $ 150,000 $ 5,000 $ 408,000 %Overall Annual Budget 4% 12% 36% 11% 10% 0.3% 27% TABLE 2 %of Allocation Discharger within Group Group: POTWs2 City of Simi Valley 36% City of Thousand Oaks 34% Camarillo Sanitary District 20% Camrosa 5% County Waterworks 5% Group: URBAN DISCHARGE' City of Simi Valley 21.3% City of Thousand Oaks 26.2% City of Camarillo 18.7% City of Moorpark 6.3% City of Oxnard 0.7% County of Ventura 17.0% Navy 3.9% Caltrans 5.8% Group: Agriculture Irrigated&Non Irrigated 100% Footnotes: Total Allocation=(Ag Allocation*Ag Annual Discharge Volume)+(Urban Allocation*Urban Annual Discharge Volume)+(POTW Allocation*POTW Annual Discharge Volume) The allowable loads for each responsible entity were then added together to determine the total allowable load. Finally the allowable load for each responsible entity was divided by the total allowable load to determine the percent of the allocation each entity was responsible for. GWQC=General Water Quality Constituents 'Cost Information and percentages based on LWA Memo dated 4/12/2006.Allocations presented in the BPAs were multiplied by the average annual discharge volume from each responsible entity to determin an allowable load for each responsible entity for each TMDL. 2 POTW cost distribution formula is based on wastewater plant design capacities per the POTWs'request. 3 Urban cost distribution based on allocations multiplied by average annual discharge volume from each entity. Open space portion was split proportionally since the contribution is minimal. 4 Costs were not split between irrigated an non-irrigated land as non-irrigated land only accounts for approximately 1%of agricultural acreage. 5 OVERALL VOTING POWER Overall Voting Discharger Power City of Simi Valley 15.4% City of Thousand Oaks 16.3% Camarillo Sanitary District 5.1% Camrosa 1.3% County Waterworks 1.3% City of Camarillo 5.5% City of Moorpark 1.8% City of Oxnard 0.2% County of Ventura 5.0% Navy 1.1% Caltrans 1.7% Agriculture/Farm Bureau 45.4% 100.0% 5 Voting Power based on Annual Monitoring Costs I - - 0 , , y w r')CD _i CD -ADD OZ 000000C 000gC -0 g -I m > CDD o iHt n C -u o = o o co c - - o ) Q) -• _ 0 o > cn Q- 0 a; D 0) -Iw � zEo• < ? 00000a = '6OO �; Oro 3 0 Z', ,-% rQ ._� O =z �' �' to .�--+ 0) m� Ca � o 0 m � 0. o o � c u) xOo . , U' � 2 o , 0' N� 0 N (D C cQ con es m � hq . o , � < � 03 � - v cn � D0 Q Q CD 0 m � o• � � av � � < CD � � � c7 n CGS D �' a � cDn � � o � °_' �' � c� 3 � oQ o 0, Q N v c aooi �`� cc0n 0 -0 c C- cD u, - sv n � O O C -U C) • r•. 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(D n •• �• p. {A V3 f1,f1,ffl EA EA EA EA EA EA EA EA EA 61, ffl `< 0 CD O 3 C N = C X __• CD 3 O = C cn• -� 3 0 -. cn "("Di 3 a) CD o, 0 CO N N -A 0) N O) CO -.4 - -, 01 CO CD (D W ES a' O C3) -A .pNNNOo0111 -, 4. 1100 - N CO CSC N 10 (D N N N_ WO_ -.1O0NN01 -p .pO01 W O OO ' O a0•) -1 0) -1 0)) -- N.) - - CO CO (0 0 (3) r. 0 O EXHIBIT H CALLEGUAS CREEK TMDL IMPLEMENTATION COST ALLOCATION-ESTIMATE FY 2007-2008` Total POTWa Urban A riculture TMDL Due�� Task Description Estimated POTW CS of Cary of Sanitary Camraee County Urban City of Thousand City of City of City of County o ivy Caltran Irrigated&Non cost Allocation Valley Oaks District Waterworks Allocation Valley Oaks Camadllo Moorpa Oxna Ventura Irrigated Tool afar CorroidertNbra %Allocation within Group 36% 34.00% 20.00% 5.00% 5.00% 21.28% 26.16% 18.74% 6.27% 0.74% 17.03% 3.95% 5.83% 100% Overall 28.15% 10.13% 9.57% 5.63% 1.41% 1.41% 24.25% 5.16% 6.34% 4.54% 1.52% 0.18% 4.13% 0.96% 1.41% 47.80% PC 0.90% .32% 1 0.18% % 26.7 .68% 99% 5.00% 1.67% 0.20% 4.55% 1. 1.56 72.40% Toxicity 29.40% 10.58% 10.00% 5.88% 1.47% 1.47% 36.90% 7.85% 9.65% 6.91% 2.31% 0.27% 6.28% 1.46% 2.15% 33.70% 14.70% 5,29% 5.00% 2,94% F74 0.74% 3 .4 7.11% 8.74% 6.26% 2.09% 0.25% .69 1,32% 1,95% 51.90% All TMDL Implementation Responsible parti X X X X X X X X X X X X X X Administration Estimated costs 11 4 32 51 11 704 11 054 6 502 1 62 28 00 5 961 7 327 5 248 1 7 208 4 769 1 1 163 54 97 $115 490 vyp-3,2008 Special Study#2- Responsible partie X X X X X X X X X X X X X X Identification of POTWs are not really impeded selenium contaminated by this study and k Is unclear Aclbrr groundwater sources Estimated costs $ 14,030 $ 2,062 $ 742 $ 701 $ 412 $ 10 $ 4,686 $ 997 $ 1,226 $ 878 $ 294 $ 35 $ 798 $ 185 $ 273 $ 7,282 $14,030 why they are listed as 312009 workplan responsible parties. WP 3121x18 Responsible parties X X X X X X X X X This study wil provide Special Study 03-Metals Metals "Hot Spot"and Natural dischargers a d other 9 Action- Soils Investigation Estimated costs $ 19,270 $ 5,192 $1,105 $ 1,358 $ 973 $ 326 $ 39 $ 884 $ 205 $ 302 $ 14,078 $19,270 dischargers of significant 312010 workplan amounts of sediment. WP-312008 Metals Optional Special Responsible parties X X X X X X X X X Study#1-Natural Action Sources Exclusion Estimated costs $ 24,050 $ 9,417 $2,004 $ 2,464 $ 1,765 $ 591 $ 70 $1,603 $ 372 $ 549 $ 14,633 $24,050 312009 workplan WP-NA Alternative Pesticide Responsible parties X X X X X X X I X X X X X X Toxicity Action Investigation Estimated costs $ 36,890 $ 16,358 $5,889 $ 5,562 $3,272 $ 818 $ 818 $ 20,532 $4,370 $ 5,371 $3,847 $1,288 $153 $3,496 $ 811 $1,196 $36,890 3/2008 WP- OC Special Study#1- Responsible partie4 X X X X X X X X X X X X X X X Work being conducted by the Sediment Completed Sedimentation and Sediment Transport VCWPD may provide Action,2014 Study Estimated costs $ 71,330 $ 642 $ 231 $ 218 $ 128 $ 32 $ 32 $ 19,045 $4,053 $ 4,983 $3,569 $1,194 $142 $3,243 $ 752 $1,109 $ 51,643 $71,330 Information for this study. 3!2014 WP- Responsible roe X X X X X X X X X X X X X X X Completed OC Special Study#2- by0this study and it really is unclear OC/PCB High Concentration why they are listed as Actlon-NA Area Study Estimated costs $ 49,770 $ 448 $ 161 $ 152 $ 90 $ 22 $ 22 $ 13,289 $2,828 $ 3,477 $2,490 $ 833 $ 99 $2,263 $ 525 $ 774 $ 36,033 $49,770 responsible parties. �- Responsible partie X X X X X X X X X X X X X X X Completed Nutrient Special Studie ACUon 7120oeExt. Estimated costs $ 39,990 $ 27,033 $9,732 $ 9,191 $5,407 $1,352 $ 1,352 $ - $ - $ - $ - $ - $- $ - $ - $ - $ 12,957 $39,990 Nutrient fe"i d' WP- Responsible par6 X X X X X X X X X X X X X X X Completed Algae Special Study 712008 7/2008 Ext. Estimated costs $ 78,300 $ 52,931 $19,055 $17,998 $10,588 $2,647 $ 2,847 $ - $ - $ - $ - $ - $- $ - $ $ - $ 25,369 $78,300 d. Totals>>>> $ 449120 $131,9851$47,515 $44 875 328,397 $6 599 8,599 S 100 186 $21 319 S 28 205 $18 788 $8,282 $744 $17 056 3,958 $5 835 $ 216,968 $449,1201 'Cost information based on LWA memoranda at 4/1 7 an 9 6/2007. CCW TMDL Implementation Cost Allocation Larry Walker Associates 1 Of 1 September 12,2007 EXHIBIT I Representatives of PARTIES Camrosa Water District Frank Royer, General Manager 7385 Santa Rosa Road Camarillo, CA 93012 Phone: 805-482-4677 Fax: 805-482-5143 Email: froyer camrosa.com Camarillo Sanitary District & City of Camarillo Lucia McGovern, Deputy Public Works Director 601 Carmen Drive Camarillo, CA 93010 Phone: 805-388-5334 Fax No: 805-388-5387 Email: Imcgovern(ab-ci.camarillo.ca.us City of Moorpark Yugal K. Lail, P.E., Public Works Director 799 Moorpark Avenue Moorpark, CA 93021 Phone: 805-517-6255 Fax: 805-532-2555 Email: ylall ci.moorpark.ca.us mailto:mlindleyna,ci.moorpark.ca.us City of Oxnard Mark Norris, WWTP Superintendent 305 West Third Street Oxnard, CA 93030 Phone: 805-385-8280 Fax: 805-385-7907 Email: ken.ortega(aD-ci.oxnard.ca.us City of Simi Valley Joe Deakin, Assistant Public Works Director 2929 Tapo Canyon Road Simi Valley, CA 93063 Phone: 805-583-6786 Fax: 805-483-6300 Email: ideakin�simivalleg City of Thousand Oaks Jay Spurgin, Deputy Public Works Director 2100 Thousand Oaks Boulevard Thousand Oaks, CA 91362 Phone No. 805-449-2444 Fax No. 805-449-2475 Email: ispurgin@toaks.org County of Ventura Public Works Agency Ronald C. Coons, Director 800 S. Victoria Ave. Ventura, CA 93009 Phone: 805-654-2074 Fax: 805-654-3952 Email: ron.coonsCa-)ventura.org Ventura County Waterworks District No. 1 Reddy Pakala, Manager 7150 Walnut Canyon Road Moorpark, CA 93021 Phone: 805-584-4830 Fax: 805-529-7542 Email: reddy.pakalaCaD-ventura.org U.S. Department of Navy Steve Granade, Environmental Engineer Naval Base Ventura County Building 632 Laguna Road Point Mugu, CA 93042 Phone No. 805-989-3806 Fax No. 805-989-1011 E-mail: steve.granade @navy.mil California Department of Transportation (Caltrans) Bob Wu, Senior Transportation Engineer 100 South Main Street, Suite 100, MS13 Los Angeles, CA 90012 Phone No. 213-897-8636 Fax No. 213-897-0205 - Email: robert—wu@dot.ca.gov Ventura County Agricultural Irrigated Lands Group A Subdivision of Farm Bureau of Ventura County Rex Laird, Chief Executive Officer 5156 McGrath St., Suite 102 Ventura, CA 93006 Phone: 805-289-0155 Fax: 805-658-0295 Email: rex a�farmbureauvc.com