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					November 2003




Calleguas Creek Watershed
Sampling and Analysis Plan
for Historic Pesticides & PCBs
- DRAFT




Submitted to:
Calleguas Creek Watershed Management Plan
TABLE OF CONTENTS

STUDY OBJECTIVE ........................................................................................................................ 1
BACKGROUND ............................................................................................................................... 1
CONTACTS ..................................................................................................................................... 4
APPROACH ..................................................................................................................................... 4
DESCRIPTION OF PLANNED USE OF DATA ................................................................................ 5
PARAMETERS TO BE MONITORED .............................................................................................. 8
SAMPLING STATIONS...................................................................................................................10
SAMPLING EVENT PREPARATION ..............................................................................................13
  Sampling Event Summary ..........................................................................................................14
  Sample Container Order/Preparation .........................................................................................14
  Sample Bottle Labeling ...............................................................................................................14
  Sample ID Conventions ..............................................................................................................15
SAMPLE COLLECTION ..................................................................................................................15
  Clean Sampling Techniques .......................................................................................................15
  Water Sample Collection ............................................................................................................16
  Sediment Sample Collection .......................................................................................................18
  Fish Tissue Sample Collection....................................................................................................19
  Field Measurements and Observations ......................................................................................20
  Chain-of-Custody ........................................................................................................................21
  Transport to Lab .........................................................................................................................21
FIELD PROTOCOLS ......................................................................................................................22
QUALITY ASSURANCE/QUALITY CONTROL ...............................................................................23
  Field Blank ..................................................................................................................................23
  Equipment Blank.........................................................................................................................23
  Field Duplicates ..........................................................................................................................23
  Method Blanks ............................................................................................................................24
  Laboratory Control Samples .......................................................................................................24
  Laboratory Duplicates .................................................................................................................24
  Matrix Spike/Matrix Spike Duplicates ..........................................................................................25
  Surrogate Spikes ........................................................................................................................25




Calleguas Creek Watershed                                               i                                                     November 2003
Pesticides/PCBs Sampling and Analysis Plan - DRAFT
APPENDICES                                                                                                                          ______

Appendix 1:      Sampling Stations ......................................................................................................27
Appendix 2:      Example Event Summary Sheet.................................................................................29
Appendix 3:      Field Log ....................................................................................................................30
Appendix 4:      Blank Chain of Custody Form.....................................................................................31
Appendix 5:      Fish Tissue Sample Collection and Preparation Protocols for Pollutant Analyses .....32


LIST OF TABLES

Table 1.    2002 303(d) Listings for Pesticides & PCBs in the Calleguas Creek Watershed............... 3
Table 2.    Project Contacts ................................................................................................................ 4
Table 3.    Constituents, Methods, Detection Limits, Holding Times .................................................. 8
Table 4.    Sampling Station Locations ..............................................................................................10
Table 5.    Estimated Monitoring Dates .............................................................................................12
Table 6.    Field Equipment Checklist ................................................................................................13
Table 7.    Sampling Requirements ...................................................................................................15
Table 8.    Analytical Laboratory ........................................................................................................21
Table 9.    Quality Control Sample Collection Schedule ....................................................................26


LIST OF FIGURES

Figure 1. Calleguas Creek Watershed– 2002 303(d) Listings for Historic Pesticides & PCBs ......... 2
Figure 2. Calleguas Creek Watershed – Sampling Locations for the Historic Pesticides & PCBs
          Sampling and Analysis Plan ............................................................................................11




Calleguas Creek Watershed                                             ii                                                     November 2003
Pesticides/PCBs Sampling and Analysis Plan - DRAFT
STUDY OBJECTIVE
The primary objective of the Sampling and Analysis Plan for Historic Pesticides and PCBs is to
collect additional ambient water quality data, sediment quality data, fish tissue data, and related
information necessary to identify the extent and magnitude of pesticide/PCB contamination in the
Calleguas Creek Watershed. Data collected will be used in support of the development of the
Pesticide/PCB TMDL. If the data collected through this SAP in combination with historical data are
not sufficient to complete a source analysis, a source identification and assessment plan will be
developed.


BACKGROUND
Eleven out of the fourteen reaches within the Calleguas Creek Watershed, in southern Ventura
County, California, appear on the 2002 Clean Water Act (CWA) Section 303(d) list of water quality
limited segments as impaired due to the presence of historic pesticides and/or PCBs in water,
sediment, and/or fish tissue (Figure 1). In response to these listings, local stakeholders, organized
through the Calleguas Creek Watershed Management Plan, developed this Pesticides/PCBs
Sampling and Analysis Plan (PSAP).

The historic pesticides and PCBs addressed in this SAP possess unique physical and chemical
properties that contribute to their ability to concentrate in biota, magnify in the food chain and
persist in soils and sediment. In addition to their toxicity to aquatic organisms, organochlorine
pesticides and PCBs bioaccumulate in fish tissue and other aquatic life, posing cancer risks to
humans consuming these organisms as food and potentially impairing wildlife reproduction.
Although organochlorine pesticides and PCBs have been banned from use in the United States,
concentrations of these chemicals have been detected in the water column, sediment, and fish
tissue in various reaches within the Calleguas Creek Watershed. The primary sources are
assumed to be sediment loading associated with watershed runoff and resuspension and transport
of previously deposited in-stream sediments. The 303(d) listings require the State to develop Total
Maximum Daily Loads (TMDLs), which establish the maximum amount of pollution a water body
can receive without exceeding established water quality criteria. The data collected through this
SAP will be used in support of the development of the TMDL for historic pesticides and PCBs.

Reaches listed on the 2002 303(d) list and associated pollutants causing impairments are
summarized in Table 1.




Calleguas Creek Watershed                            1                                 November 2003
Pesticides/PCBs Sampling and Analysis Plan - DRAFT
Figure 1. Calleguas Creek Watershed– 2002 303(d) Listings for Historic Pesticides & PCBs




Calleguas Creek Watershed                            2                                     November 2003
Pesticides/PCBs Sampling and Analysis Plan - DRAFT
Table 1. 2002 303(d) Listings for Pesticides & PCBs in the Calleguas Creek Watershed
                                                     California                                             Potential      Estimated
                     Name                                                     Pollutant [1]
                                                     Watershed                                               Source           Size
Calleguas Creek Reach 1                                           Chlordane(t), DDT(t,s),                  nonpoint/
                                                     40311000                                                              344 acres
(was Mugu Lagoon on 1998 303(d) list)                             endosulfan(t), PCBs(t)                   point source
Calleguas Creek Reach 2                                           Chem A(t), chlordane(t), DDT(t,s,w),
                                                                                                           nonpoint/
(estuary to Potrero Rd – was Calleguas Creek         40312000     endosulfan(t), PCBs(t),                                  4.3 miles
                                                                                                           point source
Reaches 1 & 2 on 1998 303(d) list)                                toxaphene(t,s),
Calleguas Creek Reach 4                                           Chem A(t), chlordane(t,s), DDT(t,s),
                                                                                                           nonpoint
(was Revolon Slough Main Branch: Mugu                40311000     dieldrin(t), endosulfan(t,s), PCBs(t),                   7.2 miles
                                                                                                           source
Lagoon to Central Avenue on 1998 303(d) list)                     toxaphene(t,s)
                                                                  Chem A(t), chlordane(t,s),
Calleguas Creek Reach 5                                           dacthal(s), DDT(t,s), dieldrin(t),       nonpoint
                                                     40311000                                                              4.3 miles
(was Beardsley Channel on 1998 303(d) list)                       endosulfan(t,s), PCBs(t),                source
                                                                  toxaphene(t,s)
Calleguas Creek Reach 6
                                                                                                           nonpoint
(was Arroyo Las Posas Reaches 1 and 2 on             40362000     DDT(s)                                                   15 miles
                                                                                                           source
1998 303(d) list)
Calleguas Creek Reach 9A                                          Chem A(t), chlordane(t), DDT(t),
                                                                                                           nonpoint
(was lower part of Conejo Creek Reach 1 on           40312000     dieldrin(t), endosulfan(t), HCH(t),                      1.7 miles
                                                                                                           source
1998 303(d) list)                                                 PCBs(t), toxaphene(t,s)
Calleguas Creek Reach 9B
                                                                  Chem A(t), DDT(t), endosulfan(t),        nonpoint
(was part of Conejo Creek Reaches 1 and 2 on         40363000                                                              6.2 miles
                                                                  toxaphene(t,s)                           source
1998 303(d) list)
Calleguas Creek Reach 10
(Conejo Creek (Hill Canyon) – was part of
                                                                  Chem A(t), DDT(t), endosulfan(t),        nonpoint
Conejo Creek Reaches 2 & 3, and lower                40364000                                                               3 miles
                                                                  toxaphene(t,s)                           source
Conejo Creek/Arroyo Conejo N. Fork on 1998
303(d) list)
Calleguas Creek Reach 11
                                                                  Chem A(t), DDT(t), endosulfan(t),        nonpoint/poi
(Arroyo Santa Rosa, was part of Conejo Creek         40365000                                                              8.7 miles
                                                                  toxaphene(t,s)                           nt source
Reach 3 on 1998 303(d) list)
Calleguas Creek Reach 12
                                                                                                           nonpoint
(was Conejo Creek/Arroyo Conejo North Fork           40364000     Chlordane(t), DDT(t)                                     5.5 miles
                                                                                                           source
on 1998 303(d) list)
Calleguas Creek Reach 13
(Conejo Creek South Fork, was Conejo Creek                        Chem A(t), DDT(t), endosulfan(t),        nonpoint
                                                     40368000                                                              17 miles
Reach 4 and part of Reach 3 on 1998 303(d)                        toxaphene(t,s)                           source
list)

           [1] t = tissue; s = sediment; w = water




           Calleguas Creek Watershed                              3                                        November 2003
           Pesticides/PCBs Sampling and Analysis Plan - DRAFT
CONTACTS
This PSAP is administered by the Flood Protection/Sedimentation Subcommittee of the Calleguas
Creek Watershed Management Plan (WMP). The members of the WMP provide funding for the
PSAP. Larry Walker Associates, Inc. (LWA) provides technical consulting services. Table 2 lists
project contact names and phone numbers for sampling team members, laboratory personnel, and
other important contacts.

 Table 2. Project Contacts
        Name                       Agency                      Phone                   E-mail
 Gil Wheeler                                                                   GilW@lwa.com
 Shelli St.Clair                                                               ShelliS@lwa.com
                          Larry Walker Associates          (805) 449-0011
 Chris Minton                                                                  ChrisM@lwa.com
 Greg Reide                                                                    GregR@lwa.com
 Steve Granade            Naval Base Ventura               (805) 989-1011      Steve.Granade@navy.mil
                          County
 Damon Wing               Ventura Coastkeeper              (805) 382-4540      vck@wishtoyo.org
 Rick Alexander           The Rick Alexander               (619) 220-8825      trac@connectnet.com
                          Company
 Mark Carpenter           KTU+A                          (619) 294-4477 x124   markc@ktua.com
 Rich Gossett             CRG Laboratories, Inc.            (310) 533-5190     rgosset@crglabs.com




APPROACH
Beginning in December 2003, water column and sediment samples will be collected monthly over
approximately an 8-month period for analysis of organochlorine pesticides/PCBs and total organic
carbon (TOC). One wet weather monitoring event and seven dry weather events will be conducted
for water column and sediment sample collection. Three fish tissue monitoring events will be
conducted between December 2003 and August 2004, all of which will be dry weather events. The
initial approach will be geared toward collecting more recent data at all listed reaches to determine
whether concentrations continue to exceed water quality criteria and sediment and fish tissue
guidelines. Data will be evaluated after each sampling event to determine whether listed reaches
are still impaired, in which case monitoring efforts will be shifted to focus on source identification.
Approximate monitoring dates, as well as wet weather sampling protocols, are discussed in the
Error! Reference source not found.SAMPLING SCHEDULE section of this plan.




Calleguas Creek Watershed                            4                                    November 2003
Pesticides/PCBs Sampling and Analysis Plan - DRAFT
DESCRIPTION OF PLANNED USE OF DATA
The following discussion regarding the planned use of data collected through this SAP is based on
the data requirements for each TMDL element:

TMDL-1: Problem Statement
Eleven out of fourteen reaches in the Calleguas Creek Watershed appear on the 2002 303(d) list of
impaired water bodies due to elevated concentrations of historic (chlorinated) pesticides and PCBs.
Because reach boundaries in the Watershed were revised during the 1996, 1998, and 2002 Water
Quality Assessment, several reaches were listed that appear to have no supporting data. In
addition, the newest data in the existing data set were collected nearly 6 years ago. The PSAP,
therefore, focuses on characterizing the extent and magnitude of pesticide/PCB contamination in
the Calleguas Creek Watershed. Data collected through the PSAP, in conjunction with historic
data, will be used to develop a clear and concise Problem Statement describing the nature of the
impairments and the regulatory context for developing a TMDL.

TMDL-2: Numeric Target
Basin Plan objectives (Los Angeles Region), CTR criteria, and sediment and fish tissue guidelines
will be used to develop numeric targets.

TMDL-3: Source Analysis
The PSAP is designed to update the existing pesticide & PCB data set with current data. The
PSAP is not specifically designed to guide the conduct of a source assessment. However, historic
data as well as data generated through the PSAP will provide information necessary to develop a
source assessment if existing data are insufficient to identify pollutant sources.

TMDL-4: Linkage Analysis
TMDL-5: Waste Load Allocations – Point Sources
TMDL-6: Load Allocations – Non-point Sources
Known environmental processes, previous studies, and results from the PSAP will be used in a
Linkage Analysis to develop a Conceptual Model (CM) describing the fate and transport of
pesticides and PCBs from sources to reaches in the Watershed. In addition, a hydrologic and
water quality model will be developed to assist in gaining an understanding of the Watershed and
to complete a TMDL. The data generated through the PSAP will provide input into this modeling
effort, which will use the USEPA-developed Hydrologic Simulation Program – FORTRAN (HSPF).
A discussion of HSPF and its use to develop loading capacities, linkage analyses, waste load
allocations, and load allocations is presented below in the Modeling portion of this summary.

TMDL-7: Margin of Safety
Regional Board and EPA guidelines will be used to incorporate an explicit and/or implicit margin of
safety (MOS). An implicit MOS may be incorporated through making and documenting any
conservative assumptions used in the development of the TMDL, including model development.
An explicit MOS may be incorporated by reserving a portion of the reach’s loading capacity for
pesticides & PCBs.


Calleguas Creek Watershed                            5                                November 2003
Pesticides/PCBs Sampling and Analysis Plan - DRAFT
TMDL-8: Seasonal Variations
The PSAP contains dry and wet weather components to provide information on seasonal variations
(low, high, and storm flow conditions) on pesticide/PCB concentrations in the Watershed. Although
the PSAP is constrained by the Consent Decree deadline, a minimum of eight monitoring events
for water and sediment and three for fish tissue will occur over an 8-month time period. In addition,
these newly collected data will be used in conjunction with historic data to provide information on
temporal variations.

Modeling
The Modeling component of the TMDL process will be used to conduct the following analyses:

   Estimate the current loading of a pollutant in a reach of concern.
   Estimate the loading capacity for each reach, which is an estimation of the maximum amount
    of pollutant loading a reach can receive over time without exceeding water quality standards.
   Estimate how various waste load allocations (point sources) and load allocations (nonpoint
    sources) will affect loading to a reach and its ability to meet water quality standards.
   Estimate how various best management practices or best available technologies will affect
    loading to a reach and its ability to meet water quality standards.
   Estimate how future growth and land use changes may affect loading in each reach.

The USEPA Hydrologic Simulation Program – FORTRAN (HSPF) will be used to develop a
hydrologic and water quality model of the Watershed. As described by the USEPA, “HSPF is a
comprehensive package for simulation of watershed hydrology and water quality for both
conventional and toxic organic pollutants. It is the only comprehensive model of watershed
hydrology and water quality that allows the integrated simulation of land and soil contaminant
runoff processes with in-stream hydraulic and sediment-chemical interactions. The result of this
simulation is a time history of the runoff flow rate, sediment load, and nutrient and pesticide
concentrations, along with a time history of water quantity and quality at any point in a watershed.”
(USEPA website visited 10/15/03, http://www.epa.gov/ceampubl/swater/hspf/).

Existing data and data developed through the various sampling and analysis plans will be used to
update databases required by the model. The model will then combine a probability distribution of
a particular constituent with the simulated flows provided by the hydrologic aspect of the HSPF
model to provide estimations of concentrations and loadings under different conditions. After
running a sufficiently large number of continuous simulation/Monte Carol simulations, the collective
output will provide a probability distribution of concentrations of various constituents in-stream
across the watershed.

The model can be used in the decision support role to investigate the changes to water flow and
quality given a set of proposed management practices. The effort and cost of implementation of
proposed management practices may then be evaluated against the environmental benefit of each
alternative.

TMDL-2: Numeric Targets
Numeric Targets are identified for each TMDL group. For water quality targets, the models may be
directly applied to determine baseline loads to and the additional capacity of the waterbodies.


Calleguas Creek Watershed                            6                                  November 2003
Pesticides/PCBs Sampling and Analysis Plan - DRAFT
TMDL-3: Source Analysis
A Source Analysis will be performed for each of the developed TMDLs. The source information will
be used as input to the numerical simulation models. Source data will be used to construct
statistical distributions for use in the models. Using the distribution of source loads as input
incorporates the frequency and duration of loading to the waterbodies. Following through the
model calculations allows estimates of the frequency and duration of the in-stream magnitude of
constituents allowing direct comparison to water quality objectives.

TMDL-4: Linkage Analysis
The portion of HSPF modeling being completed by AQUA TERRA Consultants will provide the
hydrologic basis for water quality modeling. As each TMDL focuses on water quality, simulation of
the watershed hydrology is undoubtedly a component in the linkage analysis. The water quality
portion of the HSPF modeling will be assigned to a consultant in January or February 2004. The
water quality modeling will use the water quality modules that are included in the HSPF model and
other modeling approaches, as needed, to build upon the HSPF model hydrology. The data
generated in the various SAPs discussed above along with historical data will provide input into the
water quality predictive model.

A conceptual model describing the linkage from the sources of a pollutant of interest to the affected
beneficial uses for each of the separate TMDLs will be used as a blueprint to evaluate the
calculation procedures used by the predictive model (for example HSPF) to estimate the fate and
transport of the pollutant of interest. Every predictive model is based on mass (and energy)
balances. The conceptual model identifies the process by which mass (a pollutant) enters and
leaves the system based on sources, hydrology, and pollutant specific degradation and generation
characteristics. The predictive model will provide a linkage between the processes within the
system affecting a pollutant, using the mass balance identified in the conceptual model, and the
potential affects on beneficial uses.

TMDL-5: Waste Load Allocations – Point Sources and
TMDL-6: Load Allocations – Non-point Sources
Using the models as decision support tools allows the evaluation of watershed management.
Adjusting the model inputs to reflect the effects of management alternatives will be used to
determine the most appropriate balance of waste-load and load allocations.

TMDL-7: Margin of Safety
Regional Board and EPA guidelines will be used to incorporate an explicit and/or implicit margin of
safety (MOS). An implicit MOS may be incorporated through making and documenting any
conservative assumptions used in the development of the TMDL, including model development.
An explicit MOS may be incorporated by reserving a portion of the reach’s loading capacity as a
reserve. Statistical estimates developed as part of the simulations may be used to qualitatively
assess an appropriate size of an explicit MOS.

TMDL-8: Seasonal Variations
Model simulations will be conducted for year-round or wet and dry season conditions as
appropriate. Seasonal variations will be directly assessed by the model simulations.



Calleguas Creek Watershed                            7                                 November 2003
Pesticides/PCBs Sampling and Analysis Plan - DRAFT
         PARAMETERS TO BE MONITORED
         Table 3 lists the specific constituents for which analyses will be conducted and includes analytical
         methods, expected detection limits, and holding times for each constituent.

Table 3. Constituents, Methods, Detection Limits, Holding Times
                                                                            Water                     Sediment (s)/Tissue (t)
         Constituent               Analytical Method                                                 MDL [1]
                                                                  MDL [1]           Holding
                                                                                                 (s: ng/dry g;      Holding Time
                                                                  (ng/L)             Time
                                                                                                  t: ng/wet g)
Chlorinated Pesticides & PCBs:      608 / 8080 / 8081             1 – 10            7 days [2]        1 – 10       1 year if frozen
 2,4’-DDD
 4,4’-DDD
 2,4’-DDE
 4,4’-DDE
 2,4’-DDT
 4,4’-DDT
 Aldrin
 alpha-BHC
 beta-BHC
 gamma-BHC (Lindane)
 delta-BHC
 alpha-Chlordane
 gamma-Chlordane
 Dieldrin
 Endosfan I
 Endosulfan II
 Endosulfan Sulfate
 Endrin
 Endrin Aldehyde
 Heptachlor
 Heptachlor Epoxide
 Methoxychlor
 Mirex
 trans-Nonachlor
 Toxaphene
 Aroclors (1016 through1260)
 PCBs by Congener
 Dacthal
TOC                                   5310B / 415.1           10 g/L                7 days       10 ng/g (s)      1 year if frozen
         [1] Method Detection Limit, established based on 40 CFR Part 136, Appendix B.
         [2] 7 days from sample collection to extraction; 40 days from extraction to analysis.




         Calleguas Creek Watershed                            8                                          November 2003
         Pesticides/PCBs Sampling and Analysis Plan - DRAFT
Selection of appropriate analytical methods and laboratory selection are fundamentally important
steps in constructing a monitoring program. All analyses shall meet data quality objectives, as
stated in the method, in the Draft Quality Assurance Project Plan (QAPP) for Calleguas Creek
TMDL Work Plan Monitoring (LWA August 2003), and be otherwise qualified in conformity with
EPA QA/QC guidance. The choice of analytical method may change during the study if a different
method is found to give better results (better QA/QC results and/or a more suitable detection limit).
All analyses identified in this SAP (with the exception of field measurements) will be performed by
CRG Laboratories in Torrance, California. CRG performs all analyses in conformance with EPA
and California (DHS-ELAP) requirements.




Calleguas Creek Watershed                            9                                  November 2003
Pesticides/PCBs Sampling and Analysis Plan - DRAFT
        SAMPLING STATIONS
        Table 4 lists the sampling stations and identifies the sample matrix to be collected. Figure 2
        shows the general locations of the sampling stations. Selection of the sampling stations was
        primarily based on previous and current sampling programs in the Watershed. Current or
        previously used sampling stations were selected whenever practical to save time and resources,
        and to provide continuity with historical data. Appendix 1 presents detailed descriptions of and
        driving directions to selected sampling stations.


Table 4. Sampling Station Locations

                                                                                    Sample Matrix
      Reach                       Station Location                                                                                Station ID
                                                                      Water                                   Fish
                                                                                        Sediment
                                                                     Column                                  Tissue
 1    Mugu Lagoon                         TBD 1                           √                  √                   √                   1-P
     Calleguas Creek
                            Calleguas Creek Northeastern
 2     Lower Main                                                         √                  √                   √                   2-P
                              Side of Highway 1 Bridge
          Stem
                             Revolon Slough East Side of
 4    Revolon Slough                                                      √                  √                   √                   4-P
                                     Wood Road
                              Beardsley Wash at Wright
 5   Beardsley Wash                                                       √                  √                   √                   5-P
                                         Road
                               Arroyo Las Posas Below
        Arroyo Las               Moorpark Wastewater
 6                                                                                           √                                       6-P
          Posas               Treatment Plant off Somis
                                         Road
                            Conejo Creek below Camarillo
9A     Conejo Creek          Wastewater Treatment Plant                   √                  √                   √                  9A-P
                               at Howard Road Bridge
       Conejo Creek          Conejo Creek Main Stem at
9B                                                                        √                  √                   √                  9B-P
        Main Stem               the end of Adolfo Road
                              Conejo Creek Hill Canyon
       Conejo Creek
10                           Below North Fork of Conejo                   √                  √                   √                  10-P
        Hill Canyon
                                        Creek
       Arroyo Santa           Arroyo Santa Rosa at Las
11                                                                        √                  √                   √                  11-P
           Rosa                      Posas Road
                              Conejo Creek North Fork
       Conejo Creek
12                                Above Hill Canyon                       √                                      √                  12-P
        North Fork
                             Wastewater Treatment Plant
       Conejo Creek         Above Confluence with Conejo
13                                                                        √                  √                   √                  13-P
        South Fork                 Creek North Fork
        [1] The results of previous studies in Mugu Lagoon are currently being investigated. These studies may provide
        sufficient data to identify the extent and magnitude of historic pesticide/PCBs, and eliminate the need to conduct
        additional monitoring. If additional monitoring is required, these studies will help to identify and fill data gaps and
        identify potential future sampling stations.


        Calleguas Creek Watershed                                    10                                              November 2003
        Pesticides/PCBs Sampling and Analysis Plan - DRAFT
Figure 2. Calleguas Creek Watershed – Sampling Locations for the Historic Pesticides & PCBs Sampling and
Analysis Plan




            Calleguas Creek Watershed                            11                                        November 2003
            Pesticides/PCBs Sampling and Analysis Plan - DRAFT
SAMPLING SCHEDULE
The objective of the sampling schedule for the PSAP is to obtain data representative of current
conditions in the Calleguas Creek Watershed. Table 5 presents estimated monitoring dates.
Dates will be finalized during coordination with other monitoring efforts in order to minimize
duplication of effort and to develop a representative data set.

     Table 5. Estimated Monitoring Dates
                                      Medium                                       Medium
     Event            Date                                Event       Date
                                     Sampled [1]                                  Sampled [1]
        1       December 2003             w,s,t             5      April 2004         w,s,t
        2       January 2004              w,s               6      May 2004           w,s
        3       February 2004             w,s               7      June 2004          w,s
        4       March 2004                w,s               8      July 2004          w,s,t
    [1] w = water; s = sediment; t = tissue

Only one sampling event will be a wet weather event; all other sampling events will be dry weather
events. Should measurable precipitation occur during the seven days prior to a scheduled dry
weather event, the sampling event will be rescheduled to allow for at least seven days without
measurable precipitation prior to sampling. Wet weather water samples will be collected after a
targeted storm event, defined as a storm that produces at least 0.5 inches of precipitation. 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. Should
measurable precipitation occur in the three days prior to a wet event, the sampling event will be
rescheduled to allow for at least three days without measurable precipitation prior to sampling.
Wet weather sediment samples will be collected when the effects of the precipitation on stream
flow have subsided.




Calleguas Creek Watershed                            12                               November 2003
Pesticides/PCBs Sampling and Analysis Plan - DRAFT
SAMPLING EVENT PREPARATION
Sample event preparation includes preparation of field equipment, placing orders for sample
containers, and contacting the necessary personnel regarding site access and scheduling. The
following steps should be completed two weeks prior to each sampling event:

    1. Contract laboratories to order sample containers and to coordinate sample delivery
       logistics.
    2. Confirm scheduled sampling date with field crew and set-up sampling day itinerary,
       including sample drop-off.
    3. Prepare equipment.
    4. Prepare sample labels.
    5. Prepare the sampling event summary and field log sheet to indicate the type of field
       measurements, field observations and samples to be collected at each of the stations.
    6. Calibrate field measurement equipment.

Table 6 provides a field equipment checklist of equipment to mobilize prior to each sampling event.

  Table 6. Field Equipment Checklist
                All Events                     Water Specific            Sediment Specific
                                                                        Sampling and Mixing
       Sampling and Analysis Plan              Peristaltic Pump   
                                                                        Spoons
        Sample Containers w/ Pre-                Extra Pump
                                                                     4-mil Poly Bags
        Printed and Extra Labels                 Batteries
       Event Summary Sheets                    Clean Tubing          Munsell Color Chart
       Field Log Forms
       Chain of Custody Forms
       Bubble Wrap
       Coolers w/ Ice
       New Powder-Free Nitrile Gloves
       Pens
       Watch
       Field Measurement Equipment
       Camera
       Tape Measure
       Hip Waders
       Safety Equipment
       First Aid Kit
       Cellular Telephone
       Gate Keys (if necessary)
       Paper Towels or Rags in a Box
       Plastic Trash Bags
       Distilled/DI Wash Bottles
       Distilled/DI Water for Blanks
       Sealable Plastic Bags
       Grab Pole


Calleguas Creek Watershed                            13                                   November 2003
Pesticides/PCBs Sampling and Analysis Plan - DRAFT
Sampling Event Summary

A sampling event summary sheet will be produced for the sampling crew prior to each sampling
event. Appendix 2 presents an example of a sampling event summary. The event summary
sheet will 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. Additionally, the sheet will show container,
processing and storage requirements.


Sample Container 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 and sediment samples,
including quality control samples. The containers must be the proper size and material, and
contain preservatives as appropriate for the specified laboratory analytical methods. Table 7
presents the proper container material and volume, sample type, and immediate processing and
storage needs. The field crew must inventory sample containers upon receipt from the laboratory
to assure that adequate bottles have been provided to meet analytical requirements for each
sampling event. After each monitoring event, the tubing and other equipment used to collect
samples will be cleaned by the laboratory and either picked up by or shipped to the sampling crew
in advance of the next event.


Sample Bottle Labeling

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,
sample number, 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 will be applied to the appropriate containers in a dry environment, as labels typically do not
adhere to wet surfaces. The labels shall be applied to the sides of containers rather than to the
caps. Field labels shall contain the following information:

     Program Name                       Sampling Personnel
     Station ID                         Sample ID (see next section for ID conventions)
     Event Number                       Analysis to be Performed
     Date                               Preservatives
     Time                               Laboratory Conducting the Analysis




Calleguas Creek Watershed                            14                                 November 2003
Pesticides/PCBs Sampling and Analysis Plan - DRAFT
Sample ID Conventions

Sample containers submitted to laboratories for analysis will be labeled with the following sample
ID format:

                    STATION- XX

          Where: STATION                 = Station ID
                 XX                      = Event number (i.e., 01, 02, 03, …)

For example, 4-P-01 would be the sample ID for a sample collected at station 4 (Revolon Slough)
to be analyzed for pesticides & PCBs/TOC during the first sampling event.


SAMPLE COLLECTION
Table 7 lists specific constituents for which samples will be analyzed, sample volume required, and
immediate processing and storage requirements.


Table 7. Sampling Requirements
                                                                  Sample             Immediate Processing and
          Parameter                  Sample Container
                                                                   Size                      Storage
Organic Constituents in Water
Chlorinated Pesticides/PCBs               Amber Glass               1L           Store at 40C
Total Organic Carbon (TOC)                  Glass                 250 mL         pH<2 w/H2SO4; Store at 40C
Organic Constituents in Sediment
Chlorinated Pesticides/PCBs                Glass Jar                4 oz         Store at 40C / freeze at laboratory
Total Organic Carbon (TOC)                 Glass Jar                4 oz         Store at 40C / freeze at laboratory
Organic Constituents in Fish Tissue
                                         Teflon sheet/Ziploc
Chlorinated Pesticides/PCBs                                       200 g [1]      Store at 40C / freeze at laboratory
                                                 bag
1 Discussed in detail in the section titled “Fish Tissue Sample Collection”, below.

All water samples will be grab samples
All sediment samples will be composite samples


Clean Sampling Techniques

Samples will be collected using “clean sampling techniques” to minimize the possibility of sample
contamination. For this program, clean techniques must be employed whenever handling sample
containers, lids, suction tubing, or grab sample bottles for organics analysis. Clean 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.

Calleguas Creek Watershed                                   15                                            November 2003
Pesticides/PCBs Sampling and Analysis Plan - DRAFT
   One person (“dirty hands”) touches and opens only the outer bag of all double bagged items
    (such as Teflon® or silicone tubing and Teflon® lined bottle lids), avoiding touching the inside
    of the bag.
   The other person (“clean hands”) reaches into the outer bag, opens the inner bag, and
    removes the clean item (sample bottle, tubing, lid, etc.).
   After a sample is collected, or when a clean item must be re-bagged, it is done in the opposite
    order from which it was removed.
   Clean, powder-free nitrile gloves are changed whenever something not known to be clean has
    been touched.
   For this program, clean techniques must be employed whenever handling suction tubing, or
    grab sample bottles.
   To reduce the potential for contamination, sample collection personnel must adhere to the
    following rules while collecting samples:
    1. No smoking.
    2. Never collect samples near a running vehicle. Do not park vehicles in the immediate
         sample collection area, even non-running vehicles.
    3. During wet weather events avoid allowing rainwater to drip from rain gear or any other
         surface into sample containers.
    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

All water samples will be collected as grab samples. At most stations, 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 sampling station configurations and safety concerns, direct filling of sample bottles
may not always be feasible. Sampling station configuration will dictate grab sample collection
technique. Grab samples will be collected directly into the appropriate bottles (containing the
required preservatives) as outlined in Table 7.

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 to mid-stream, mid-depth
using the following procedures.

    1. Wear clean powder-free nitrile gloves when handling bottles and caps. Change gloves if
       soiled or if the potential for cross-contamination occurs from handling sampling materials
       or samples;
    2. Pre-label sample containers as described in Sample Bottle Labeling and Sample ID
       Conventions;
    3. Submerge bottle to mid-stream/mid-depth, remove lid, let bottle fill, and replace lid;
    4. Place sample on ice;


Calleguas Creek Watershed                            16                                November 2003
Pesticides/PCBs Sampling and Analysis Plan - DRAFT
    5. Collect remaining samples including control samples, if needed, using the same protocols
       described above;
    6. Fill out the Chain-of-Custody form, note sample collection information on the field log, 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 (either acid washed Pyrex® pitcher or HDPE container) following the steps listed below.

    1. Wear clean powder-free nitrile gloves when handling bottles and caps. Change gloves if
       soiled or if the potential for cross-contamination occurs from handling sampling materials
       or samples;
    2. Pre-label sample containers as described in Sample Bottle Labeling and Sample ID
       Conventions;
    3. Submerge specially cleaned intermediate container (Pyrex® pitcher) 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 control samples, if needed, using the same protocols
       described above;
    6. Fill out the Chain-of-Custody form, note sample collection information on the field log, 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.

    1. Wear clean powder-free nitrile gloves when handling bottles and caps. Change gloves if
       soiled or if the potential for cross-contamination occurs from handling sampling materials
       or samples;
    2. Pre-label sample containers as described in Sample Bottle Labeling and Sample ID
       Conventions;
    3. Insert pre-cleaned silicone 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.
    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 control samples, if needed, using the same protocols
       described above;


Calleguas Creek Watershed                            17                               November 2003
Pesticides/PCBs Sampling and Analysis Plan - DRAFT
    9. Fill out the Chain-of-Custody form, note sample collection information on the field log, and
       deliver to appropriate lab.


Sediment Sample Collection

Collection of sediment samples for chemical analysis will 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, Open-File Report 94-458, 1994. Sediment sampling stations
will encompass a section of the reach approximately 100 meters in length upstream from a water-
column sampling station. 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
sediment sample from each reach. Each depositional zone identified at a sampling station will be
sub-sampled several times and composited in the field for chemical analysis. The number of sub-
samples 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.

All sediment samples to be analyzed for organic constituents shall be collected as composite
samples. Sediment samples will be collected using pre-cleaned stainless steel trowels to remove
the top 3 cm of sediment. In areas where water is too deep such that no wadeable zones exist, an
Ekman dredge or similar coring device should be used. Composite samples shall be collected
directly into a clean polyethylene bag, mixed, and then placed into the appropriate jars as outlined
in Table 7. Sediment sampling techniques that may be employed are described below.

Sediment Sample Collection for Chemical Analysis

    1. Wear clean powder-free nitrile gloves when handling bottles and caps. Change gloves if
       soiled or if the potential for cross-contamination occurs from handling sampling materials
       or samples;
    2. Pre-label sample containers as described in Sample Bottle Labeling and Sample ID
       Conventions;
    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;


Calleguas Creek Watershed                            18                                November 2003
Pesticides/PCBs Sampling and Analysis Plan - DRAFT
    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 poly bag and fill sample containers used for chemical analysis;
    9. Place sample on ice;
    10. Fill out the Chain-of-Custody form, note sample collection information on the field log, and
        deliver to appropriate lab;


Fish Tissue Sample Collection

Target Fish Species

Species collected in the past in the Watershed through the Toxic Substances Monitoring Program
(TSMP) and the State Mussel Watch Program (SWMP) include goldfish, fathead minnow, black
and brown bullhead, Arroyo Chub, transplanted freshwater clams, mosquito fish, mussels, green
sunfish, and red swamp crayfish. According to USEPA guidance,1 the target fish species for
sample collection should be the largest individual fish captured from 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 Watershed, 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.

Sampling Protocols

Either the California Department of Fish and Game 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 chlorinated pesticides and PCBs, using protocols
detailed in Appendix 5. These protocols are summarized below.

Collection of fish for analysis of trace levels of chlorinated pesticides and PCBs in tissue may be
accomplished by a variety of methods, including hook and line, seines, gill nets, and
electroshocking. 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.



1USEPA. 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.

Calleguas Creek Watershed                             19                                       November 2003
Pesticides/PCBs Sampling and Analysis Plan - DRAFT
Individual fish will be wrapped in trace metal- and organic-free Teflon™ 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 (see Appendix 5). 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™) 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 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, DFG staff or
the sampling contractor will contact LWA / members of the WMP to discuss whether sampling should
continue at that location.

If the performance requirements documented in this SAP are not met, the tissue sample will be re-
collected. Sample collection will be conducted during three monitoring events between December
2003 and July 2004. Samples will be distributed to the analytical laboratories as soon as possible
following field collection, and stored frozen until analytical testing is performed.



Field Measurements and Observations

In addition to the constituents listed in Table 7, field measurements will be taken and observations
made at each sampling station after a sample is collected. Field measurements will include flow,
pH, temperature, dissolved oxygen, salinity, and conductivity. Temperature, pH, dissolved oxygen,
salinity, and conductivity measurements will be taken at approximately mid-stream, mid-depth at
the location of greatest flow (if feasible). Field probes shall be lowered to mid-depth, readings

Calleguas Creek Watershed                            20                                    November 2003
Pesticides/PCBs Sampling and Analysis Plan - DRAFT
taken and recorded on the field log for that station. Field measurements for sediment samples
shall be collected from within one meter of the sediment. All field measurement results and
comments on field observations will be recorded in the field log presented in Appendix 3.

Flow measurements will be taken using a flow meter or estimated at each sampling station after a
sample is collected. When a flow meter is unavailable or flow is not sufficiently deep to use a flow
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, mid-stream, mid-
depth measurements will not be collected. If in-stream field measurement is not safe, field
measurements will be collected from a stable, unobstructed area at the reach’s edge or an
expandable pole and intermediate container will be used to obtain sample for field measurements.

In addition to field measurements, observations will be made at each sampling station, including
water color, odor, floating materials as well as observations of contact and non-contact recreation
and wildlife. All comments on field observations will be recorded in the field log presented in
Appendix 3.


Chain-of-Custody

Chain-of-custody (COC) forms shall be filled out for all field samples submitted to each laboratory.
Sample data, sample location, sample collection crew names, and analyses requested shall be
noted on each COC form. An example COC form is presented in Appendix 4.


Transport to Lab

Samples shall be stored in coolers with ice, packed in bubble wrap and delivered to the laboratory
listed in Table 8. Samples will be analyzed according to the methods listed in Table 3, which also
lists reporting limits and holding times.




Table 8. Analytical Laboratory
             Lab                              Analysis                         Shipping Method
                                Chlorinated pesticides and PCBs in
CRG Laboratories                water, sediment, and fish tissue; TOC   Same day or overnight delivery
                                in water and sediment




Calleguas Creek Watershed                            21                                   November 2003
Pesticides/PCBs Sampling and Analysis Plan - DRAFT
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. 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 station.
    3. Fill out the general information on the field log sheet.
    4. Collect field measurements and observations, and record on the field log sheet.
    5. Collect the samples indicated on the field log sheet in the manner described in this study
       plan. Collect additional volume and blank samples for field-initiated QA/QC samples, if
       necessary. Place filled sample containers in the coolers; carefully pack and ice samples.
       Double check against the log sheet that all appropriate containers were filled.
    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 notes recorded in the field log.
    8. After sample collection is completed, deliver and/or ship samples to CRG Laboratories on
       the same day as sample collection:

                           CRG Laboratories
                           2020 Del Amo Boulevard, Suite 200
                           Torrance, CA 90501
                           (310) 533-5190




Calleguas Creek Watershed                            22                              November 2003
Pesticides/PCBs Sampling and Analysis Plan - DRAFT
QUALITY ASSURANCE/QUALITY CONTROL
Quality control samples for water, sediment and fish tissue analyses will be collected according to
the schedule shown in Table 9. Specific collection methods for each type of quality control sample
type are described below.


Field Blank
The purpose of analyzing field blanks is to demonstrate that sampling procedures do not result in
contamination of the environmental samples. One set of field blanks will be prepared and analyzed
for all analytes of interest, along with the associated environmental samples for each event. Field
blanks will consist of laboratory-prepared blank water decanted directly into the appropriate sample
containers in the field. If any analytes of interest are detected at levels greater than the Reporting
Limit (RL) for the parameter, the sampling crew should be notified so that the source of
contamination can be identified (if possible). If the concentration in the associated samples is less
than five times the value in the field blank, the results for the environmental samples may be
unacceptably affected by contamination and should be qualified as an upper limit (UL) at the
reported value. Field blanks will be submitted “blind” to the laboratory in containers labeled
“Station 20-P”.


Equipment Blank
The purpose of analyzing equipment blanks is to demonstrate that sampling equipment is free from
contamination. Prior to using sampling equipment for the collection of environmental samples, the
field crew will generate equipment blanks using water provided by the laboratory responsible for
cleaning and preparation of the equipment. 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 should be identified and corrected (if
possible), the affected batch of bottles or equipment should be re-cleaned, and new equipment
blanks should be prepared and analyzed.

Sampler blanks will consist of laboratory-prepared blank water processed through the sampling
equipment using the same procedures used for environmental samples. Equipment blanks will be
collected for pesticides/PCBs and TOC. For water sampling equipment, blank water will be
collected from the laboratory water provided using each of the water sampling techniques. For
sediment sampling equipment, blank water will be poured over pre-cleaned sampling trowel into a
clean polyethylene bag and then poured into sample containers. Equipment blanks should be
submitted “blind” to the laboratory as Station 21-P.


Field Duplicates
The purpose of analyzing field duplicates is to demonstrate the precision of sampling and analytical
processes. One set of field duplicates will be prepared and analyzed along with the associated
environmental samples for each event. Field duplicates will consist of two grab samples collected
in rapid succession. If the Relative Percent Difference (RPD) of field duplicate results is greater

Calleguas Creek Watershed                            23                                 November 2003
Pesticides/PCBs Sampling and Analysis Plan - DRAFT
than 25% and the absolute difference is greater than the RL, both samples should be reanalyzed.
If an RPD greater than 25% is confirmed by reanalysis, environmental results will be qualified as
estimated. Field duplicate water and sediment samples shall be collected and analyzed for
pesticides/PCBs and TOC. Field duplicates for water samples shall be collected immediately
following the collection of normal samples. In cases where multiple intermediate bottles are used
for a single analysis, field duplicates and original sample containers shall be filled in an alternating
sequence (i.e., original-duplicate-original-duplicate). Field duplicates for sediment samples shall
be produced with the same composite sample as the original sample. Field duplicates shall be
submitted “blind” to the laboratory as Station 22-P.


Method Blanks
The purpose of analyzing method blanks is to demonstrate that the 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. The
method blank should be prepared and analyzed before analysis of the associated 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.
If reanalysis is not possible, the associated sample results should be qualified as an upper limit
(UL) at the reported value.


Laboratory Control Samples
The purpose of analyzing laboratory control samples is to demonstrate the accuracy of the
analytical method. Laboratory control samples will be analyzed at the rate of one per sample
batch. Laboratory control samples will consist of laboratory fortified method blanks. If recovery of
any analyte is outside the acceptable range for accuracy, 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. If reanalysis is not possible, the
associated sample results should be qualified as low or high biased.


Laboratory Duplicates
The purpose of analyzing laboratory duplicates is to demonstrate the precision of the analytical
method. 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 the precision criterion 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. If reanalysis is not possible, the associated sample
results should be qualified as not reproducible due to analytical variability. Laboratory duplicates
will be analyzed for water, sediment and fish tissue samples.




Calleguas Creek Watershed                            24                                    November 2003
Pesticides/PCBs Sampling and Analysis Plan - DRAFT
Matrix Spike/Matrix Spike Duplicates
The purpose of analyzing matrix spikes/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 matrix spike recovery of any analyte is outside the acceptable range (80-120%), the results for
that analyte have failed the 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. Attempt to correct the problem (i.e., by dilution, concentration,
etc.) and re-analyze the samples and the matrix spikes. If the matrix problem cannot be corrected,
qualify the results for that analyte as appropriate (low or high biased) due to matrix interference.

If the matrix spike duplicate RPD for any analyte is greater than 20%, the results for that analyte
have failed the 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. Attempt to correct the problem (by dilution, concentration, etc.) and re-analyze
the samples and the matrix spike duplicates. If the matrix problem can’t be corrected, qualify the
results for that analyte as not reproducible, due to matrix interference. Matrix spike/matrix spike
duplicates analyses will be requested for water, sediment, and fish tissue samples analyzed for
pesticides/PCBs TOC. No special sampling considerations are required. However, triple the
sample volume must be collected for each water sample to be used for MS/MSD analysis.


Surrogate Spikes
Surrogate recovery results are used to evaluate the accuracy of sample preparation and 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 chlorinated pesticides & PCBs and organophosphate pesticides
analyses

The acceptable range for recovery of surrogate compounds is between 30% and 150%. If
surrogate recoveries are outside this range, the sample batch should be prepared again and
reanalyzed. If reanalysis is not possible, the associated environmental data for all analytes by the
specific method should be qualified as low or high biased, consistent with the surrogate recovery
bias. If surrogate recovery bias is inconsistent for different surrogate compounds, qualify the
associated environmental data as biased due to indeterminate surrogate recovery bias.




Calleguas Creek Watershed                            25                                  November 2003
Pesticides/PCBs Sampling and Analysis Plan - DRAFT
Table 9. Quality Control Sample Collection Schedule
                               Station                                     Event Number
         Reach
                                  ID          1          2         3         4      5              6         7            8
 1     Mugu    Lagoon1           1-P
      Calleguas Creek
 2                               2-P         MS                                        FD         FB
      Lower Main Stem
 4     Revolon Slough            4-P                    FB                                                  FD
 5    Beardsley Wash             5-P         FB         LD
         Arroyo Las
 6                               6-P         FD                   MS                                                      FB
            Posas
9A      Conejo Creek            9A-P         EB                   FB                   MS         LD
        Conejo Creek
9B                              9B-P                              FD                                        FB
         Main Stem
        Conejo Creek                                                                                                      LD,
10                              10-P                                         FB
                                                                                                                          MS
         Hill Canyon
        Arroyo Santa
11                              11-P                    FB                   LD
             Rosa
        Conejo Creek
12                              12-P                                         FB        EB
         North Fork
        Conejo Creek
13                              13-P                                                   FB
         South Fork
[1] The results of previous studies in Mugu Lagoon are currently being investigated. These studies may provide
sufficient data to identify the extent and magnitude of historic pesticide/PCBs, and eliminate the need to conduct
additional monitoring. If additional monitoring is required, these studies will help to identify and fill data gaps and
identify potential future sampling stations.
FB = Field Blank, analyzed for pesticides/PCBs and TOC in water and sediment samples.
FD = Field Duplicate, analyzed for pesticides/PCBs and TOC in water, sediment and tissue samples.
LD = Lab Duplicate, analyzed for pesticides/PCBs and TOC in water, sediment and tissue samples.
MS = Matrix Spike/Matrix Spike Duplicate, analyzed for pesticides/PCBs and TOC in water, sediment and tissue
        samples.




Calleguas Creek Watershed                                    26                                              November 2003
Pesticides/PCBs Sampling and Analysis Plan - DRAFT
Appendix 1: Sampling Stations

Station ID: 1-P
Reach 1: Mugu Lagoon - TBD
The results of previous studies in Mugu Lagoon are currently being investigated. These studies
may provide sufficient data to identify the extent and magnitude of historic pesticide/PCBs, and
eliminate the need to conduct additional monitoring. If additional monitoring is required, these
studies will help to identify and fill data gaps and identify potential future sampling stations.

Station ID: 2-P
Reach 2: Calleguas Creek Lower Main Stem - Northeastern side of Highway 1
Directions: From Oxnard, heading south on Hwy 1, turn left, across northbound Hwy 1 traffic, just
south of Los Posas Rd intersect, onto Deer Path. Make way north to Calleguas Creek. Collect
sample at midstream. Thomas Guide p. 584-J4.

Station ID: 4-P
Reach 4: Revolon Slough - East Side of Wood Road
Directions: Access slough on east side of Wood Rd. Collect samples at midstream. Thomas
Guide p. 553-H3.

Station ID: 5-P
Reach 5: Beardsley Wash – at Wright Road
Directions: From US 101 in Camarillo, head north on Central Ave to Beardsley Rd. Turn right on
Beardsley Road and park near the Wright Road intersection. Use county gate access key.
Thomas Guide p. 493-G7.

Station ID: 6-P
Reach 6: Arroyo Las Posas - Below Moorpark Waste Water Treatment Plant off Somis Road
Directions: From Somis Rd turn east onto road at Hagel Tree Farm, between Ag Rx and Paty’s
Farm stand. Cross railroad tracks and follow road until you reach Arroyo Las Posas. Sample at
midstream, upstream of bridge. Thomas Guide p. 495-A5.

Station ID: 9A-P
Reach 9A: Conejo Creek - Below Camarillo Waste Water Treatment Plant at Howard Road Bridge
Directions: From US 101 in Camarillo exit Pleasant Valley Rd, and head south to Pancho Rd.
Turn left (south) on Pancho Rd. Turn left (east) on Howard Rd. Sample downstream of Howard
Road Bridge. Collect samples at midstream. Thomas Guide p. 524-J7.

Station ID: 9B-P
Reach 9B: Conejo Creek Main Stem - At the end of Adolfo Road
Directions: From the US 101 in Camarillo head north on Santa Rosa Rd. Turn right (headed
east) on Adolfo Rd and continue to the end. Pass through a locked VCWPD gate and sample as
close as a sampling pole will permit to midstream. Thomas Guide p. 525-B4.

Station ID: 10-P
Reach 10: Conejo Creek Hill Canyon - Below North Fork of Conejo Creek

Calleguas Creek Watershed                            27                                November 2003
Pesticides/PCBs Sampling and Analysis Plan - DRAFT
Directions: From Santa Rosa Rd head south on Hill Canyon Rd. Follow dirt access road to Creek.
Thomas Guide p. 525-J2.

Station ID: 11-P
Reach 11: Arroyo Santa Rosa – E. Las Posas Road
Directions: From Santa Rosa Rd head north on East Las Posas Rd. Access to creek is through
locked VCWPD gate on downstream side of road. Thomas Guide p. 496-C7.

Station ID: 12-P
Reach 12: Conejo Creek North Fork
Directions: From Santa Rosa Rd head south on Hill Canyon Rd. Follow dirt access road to the
treatment plant. Access to creek is behind the new belt press building at the treatment plant.
Thomas Guide p. 526-A4.

Station ID: 13-P
Reach 13: Conejo Creek South Fork - South of Confluence with Conejo Creek North Fork
Directions: From Santa Rosa Rd head south on Hill Canyon Rd. Access creek through locked
gate on south side of treatment plant. Sample at midstream of south fork. Thomas Guide p. 526-
A4.




Calleguas Creek Watershed                            28                             November 2003
Pesticides/PCBs Sampling and Analysis Plan - DRAFT
         Appendix 2: Example Event Summary Sheet
    Station                     Analyses                      Containers/Preservatives         Laboratory
1-P-01
Water                Chlorinated Pesticides/PCBs         1-L Amber Glass                 CRG
                     TOC                                 250-mL glass / H2SO4 to pH<2    CRG
1-P-01
Sediment             Chlorinated Pesticides/PCBs         4-oz. Glass jar                 CRG
                     TOC                                 4-oz. Glass jar                 CRG
1-P-01
Tissue               Chlorinated Pesticides/PCBs         Teflon Sheet/Ziploc Bag         CRG
2-P-01
Water                Chlorinated Pesticides/PCBs 3 x 1-L Amber Glass                CRG
                     TOC                         3 x 250-mL glass / H2SO4 to pH<2 CRG
                     QC Samples: Matrix Spike/Matrix Spike Duplicate (extra containers indicated above)
2-P-01
Sediment             Chlorinated Pesticides/PCBs 4-oz. Glass jar                   CRG
                     TOC                         4-oz. Glass jar                   CRG
                     QC Samples: Matrix Spike/Matrix Spike Duplicate (no extra sample needed)
2-P-01
Tissue               Chlorinated Pesticides/PCBs Teflon Sheet/Ziploc Bag           CRG
                     QC Samples: Matrix Spike/Matrix Spike Duplicate (no extra sample needed)
5-P-01
Water                Chlorinated Pesticides/PCBs  1-L Amber Glass                        CRG
                     TOC                          250-mL glass / H2SO4 to pH<2           CRG
                     QC Samples: Field Blank – Label as 20-P-01
                     Chlorinated Pesticides/PCBs  1-L Amber Glass                        CRG
                     (use blank water provided by
                     the laboratory)
                     TOC (use blank water         250-mL glass / H2SO4 to pH<2           CRG
                     provided by the laboratory
5-P-01
Sediment             Chlorinated Pesticides/PCBs  4-oz. Glass jar                        CRG
                     TOC                          4-oz. Glass jar                        CRG
                     QC Samples: Field Blank – Label as 20-P-01
                     Chlorinated Pesticides/PCBs  1-L Amber Glass                        CRG
                     (use blank water provided by
                     the laboratory)
                     TOC (use blank water         250-mL glass / H2SO4 to pH<2           CRG
                     provided by the laboratory
5-P-01
Tissue               Chlorinated Pesticides/PCBs         Teflon Sheet/Ziploc Bag         CRG




         Calleguas Creek Watershed                            29                           November 2003
         Pesticides/PCBs Sampling and Analysis Plan - DRAFT
  Appendix 3: Field Log

GENERAL INFORMATION

Station ID:                                 Date:                             Time: Arrival
                                                                                    Departure
Sampler’s Name(s):

OBSERVATIONS
Weather:
Floating material or debris:
Oil (extent):                                          Water color or odor:
Photograph No. (if taken):
Recreation uses observed:
Other Notes (presence of algae, wildlife observations, etc.):




FLOW MEASUREMENTS / ESTIMATES

Measured Flow:

Estimated Flow:

Mid-stream depth                            Width of flow                      Velocity


WATER QUALITY MEASUREMENTS

DO (mg/L):              pH:             Temp (oC):               EC (umhos/cm):           Salinity:

SAMPLE COLLECTION
Pesticides in Water                     Time:                                 Volume:

TOC in Water                            Time:                                 Volume:

Pesticides in Sediment                  Time:                                 Volume:

TOC in Sediment                         Time:                                 Volume:

Pesticides in Fish Tissue               Time:                                 Volume:

Other                                   Time:                                 Volume:



  Calleguas Creek Watershed                             30                                 November 2003
  Pesticides/PCBs Sampling and Analysis Plan - DRAFT
                                                              CRG        Marine Laboratories, Inc.                                              CHAIN-OF-CUSTODY RECORD
                                                                   2020 Del Amo Blvd., Suite 200, Torrance, CA 90501-1206
                                                                 (310) 533-5190 FAX (310) 533-5003

                                                             Client Name:             Larry Walker Associates                                                                                                    REQUESTED ANALYSIS
                                                            Client Address:           100 E. Thousand Oaks Blvd, Suite 124
                                                                                      Thousand Oaks, CA 91360
                                                             Sampled By:              G. Reide C. Minton
                                                                Phone:                (805) 449-0011




Calleguas Creek Watershed
                                                                 FAX:                 (805) 449-0095
                                                           Project Manager:           Shelli St Clair
                                                            Project Name:             Calleguas Creek Pest and PCBs Monitoring
                                                             PO Number:               257.06 Task 2

                                                                                       Sample        Sample        Sample        Container
                                                           Client Sample ID




                                                                                                                                                   Chlorinated Pesticides & PCBs
                                                                                                                                                                                   TOC
                                                                                                                                                                                         MS/MSD - CHPs & PCBs
                                                                                                                                                                                                                  MS/MSD - TOC
                                                                                        Date          Time         Matrix*   Number     Type




Pesticides/PCBs Sampling and Analysis Plan - DRAFT
                                                                                                                                                                                                                                         Appendix 4: Blank Chain of Custody Form




                         31
                                                         Correct Containers:            Yes       No                                                                                       RELINQUISHED BY
                                                        Sample Temperature:            Ambient   Cold               Warm
                                                                                                                                     Signature:
                                                        Sample Preservative:            Yes       No
                                                          Turnaround Time:              STD    Specify:                                Print:
                                                     Comments:
                                                                                                                                     Company:     Larry Walker Associates
                                                                                                                                       DATE:                                                                                     TIME:
                                                                                                                                                                                                                RECEIVED BY
                                                                                                                                     Signature:
                                                                                                                                       Print:
                                                                                                                                     Company:     CRG Marine Laboratories, Inc.
                                                                                                                                  DATE:                               TIME:
                                                     *MATRIX CODES: (SED = Sediment); (TISS = Tissue); (SW = Seawater, Saltwater); (FW = Freshwater); (WW = Wastewater); (STRMW = Stormwater)




                         November 2003
Appendix 5: Fish Tissue Sample Collection and Preparation Protocols for Pollutant
Analyses




           STANDARD OPERATING PROCEDURES

    FOR FISH TISSUE SAMPLE COLLECTION AND
                  PREPARATION

 SAMPLING AND PROCESSING TRACE METAL AND
 SYNTHETIC ORGANIC SAMPLES OF MARINE AND
             FRESHWATER FISH



                THIS APPENDIX CONTAINS EXCERPTS TAKEN DIRECTLY FROM:

                    CALIFORNIA DEPARTMENT OF FISH AND GAME

                                        METHOD 102


                                                     BY:

                    CALIFORNIA DEPARTMENT OF FISH AND GAME

                      MARINE POLLUTION STUDIES LABORATORY



                                              JULY 20, 200




Calleguas Creek Watershed                            32                      November 2003
Pesticides/PCBs Sampling and Analysis Plan - DRAFT
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING

             In the field, sources of contamination include sampling gear, dirty hands,
             grease from ship winches or cables, ship and truck engine exhaust, dust, and
             ice used for cooling. Efforts are made to minimize handling and to avoid
             sources of contamination. All sampling equipment will be made of non-
             contaminating materials and will be inspected prior to entering the field. Nets
             will be inspected for holes and repaired prior to being used. Boats (including
             the electroshocking boat) will be visually checked for safety equipment and
             damage prior to being taken into the field for sample collection. Samples are
             handled with polyethylene-gloved hands only. The samples are sealed in
             appropriate containers immediately. Fish are wrapped in part or whole in
             Teflon and subsequently placed into Ziplocs™. Teflon sheet used to wrap
             fish is cleaned by soaking in micro™, acid and rinsed with petroleum ether.
             Samples are frozen as soon as possible. In the field, dry ice is ideal, but
             regular ice may be used if it is sealed in watertight plastic bags.

         6.1 A chain of custody form (Appendix A-1) will accompany all samples that are
             brought to the lab. All samples that are processed in the lab WILL receive a
             unique lab number for identification. This number is recorded in the Lab
             Number Log book, and is used to identify the sample while it is processed
             through the lab.

         6.2 To avoid contamination, all equipment used in sample collection are
             thoroughly cleaned before each sample is processed. Ideally, instruments are
             made of a material that can be easily cleaned (e.g. Stainless steel, anodized
             aluminum, or borosilicate glass). Before the next sample is processed,
             instruments are washed with a detergent solution, rinsed with ambient water,
             rinsed with MilliQ and finally rinsed with a high-purity solvent (methanol or
             petroleum ether). Solvent solutions are collected and taken back to the
             laboratory.

         6.3 Tissue dissections are carried out by or under the supervision of a competent
             laboratory manager. Samples are handled with polyethylene gloves and
             changed between samples. Each organism is rinsed free of dirt with deionized
             water and handled with clean stainless steel, quartz, or Teflon instruments.
             The SO specimens come in contact with pre-cleaned glass, aluminum foil or
             Teflon surfaces only.

         6.4 The tissue and sediment samples are placed in a clean glass (SO) or
             polyethylene (TM) container which has been cleaned appropriately. See
             section on cleaning for the description of appropriate methods in detail.



Calleguas Creek Watershed                            33                         November 2003
Pesticides/PCBs Sampling and Analysis Plan - DRAFT
         6.5 Tissue and sediment samples are maintained at -20°c and extracted or digested
             as soon as possible. Complete analyses are performed within 40 days of
             digestion or extraction.

7.0 PROCEDURE FOR SAMPLE COLLECTION AND PREPARATION

                  7.4.2    As a general rule, five fish of medium size or three fish of larger
                           size are collected as composites for analysis. The smallest fish
                           length cannot be any smaller than 75% of the largest fish length.
                           Five fish usually provides sufficient quantities of tissue for the
                           dissection of 100 grams of fish flesh for organic and inorganic
                           analysis. The medium size is more desirable to enable similar
                           samples to be collected in succeeding collections.

                  7.4.3    When only small fish are available, sufficient numbers are
                           collected to provide 100 grams of fish flesh for analysis. If the fish
                           are too small to excise flesh, the whole fish, minus the head, tail,
                           and guts are analyzed as composites.

                  7.4.4    Fish collected, to large to fit in our clean bags (>500 mm) are
                           initially dissected in the field. At the dock, the fish are laid out on
                           a clean plastic bag and a large cross section from behind the
                           pectoral fins to the gut is cut with a cleaned bone saw. The bone
                           saw is cleaned (micro, DI, methanol) between fish and a new
                           plastic bag is used. The internal organs are not cut into, to prevent
                           contamination. For bat rays, a section of the wing is cut and saved.
                           These sections are wrapped in Teflon ®, double bagged and packed
                           in dry ice before transfer to the freezer. During lab dissection, a
                           subsection of the cross section is removed, discarding any tissue
                           exposed by field dissection.

                  7.4.5    Field data (Appendix A-2) recorded include, but are not limited to
                           site name, sample identification number, site location (GPS), date
                           of collection, time of collection, names of collectors, method of
                           collection, type of sample, water depth, water and atmospheric
                           conditions, fish total lengths (fork lengths where appropriate),
                           photo number and a note of other fish caught.

                  7.4.6    The fish are then wrapped in cleaned Teflon sheets. The wrapped
                           fish are then double-bagged in Ziploc™ bags with the inner bag
                           labeled. The fish are put on dry ice and transported to the
                           laboratory where they are kept frozen until they are processed for
                           chemical analysis.


Calleguas Creek Watershed                            34                              November 2003
Pesticides/PCBs Sampling and Analysis Plan - DRAFT
         7.5    Sample Dissection – Fish

                  7.5.1    Large fish requiring dissection are partially thawed, then washed
                           with DI water. You may need to rub more vigorously in order to
                           remove mucous. Place the rinsed fish in a clean, Teflon lined bin.

                  7.5.2    Total fish length and fork length is measured on the measuring
                           board to the nearest millimeter. The fish is then placed on a clean
                           Teflon sheet on the balance and weighed. All lengths and weights
                           are recorded on standard lab forms (Appendix A-3).

                  7.5.3    The list of species that are prepared skin on or skin off is
                           dependent upon that specific study’s procedure. Generally, scaly
                           fish (largemouth bass, perch, etc.) are de-scaled from the tail to the
                           operculum above the lateral line with the titanium rod, and are
                           dissected “skin-on”. The skin is removed from scaleless fish in the
                           same section as above, and the fish are dissected “skin-off” (EPA,
                           1995). If the contract requires aging, scales are taken at this time
                           from just behind the dorsal fin and placed in coin envelopes for
                           later age determination.

                  7.5.4    For “skin-off” fish, a "U" shaped incision is made with a scalpel
                           just posterior to the operculum; the upper leg running the length of
                           the fish just ventrally of the dorsal fin and the lower just below the
                           midline; cutting just through the epidermis. The skin is peeled
                           back using the "v" shaped forceps and the flesh exposed.

                  7.5.5    With a fresh scalpel (cutting approximately 1 cm inside the
                           original cut to avoid contamination, providing the size of the fish
                           allows) a fillet is cut from the entire length of the fish.

                  7.5.6    The fillet is removed with Teflon forceps. Equal weight fillets are
                           taken from each fish of the sample to composite. Ideally, 30-40g
                           from each of 5 fish makes up the total weight.

                  7.5.7    The beginning bottle weight, each fillet weight and end bottle
                           weight are recorded on the fish dissection sheet.

                  7.5.8    If the contract requires liver analysis, the livers are removed from
                           the predator species by opening the body cavity with the incision
                           scalpel. The liver is freed by cutting with a fresh dissection scalpel
                           and removed with a clean forceps. The livers are rinsed with
                           MilliQ and placed in a clean sample jar. Beginning bottle weight,
                           individual liver weights and end bottle weights are recorded.



Calleguas Creek Watershed                            35                              November 2003
Pesticides/PCBs Sampling and Analysis Plan - DRAFT
                  7.5.9    If the contract requires gut content analysis, the gut is removed by
                           opening the body cavity with the incision scalpel. The stomach
                           and intestines are separated from the visceral cavity and placed in a
                           125ml polypropylene jar and covered with 50% isopropanol.

                  7.5.10 At this time vertebra or scales may be taken from for aging. The
                         first unfused vertebra is removed and placed in a 25mL beaker,
                         covered with water and placed in the refrigerator until the flesh has
                         broken down enough to be cleaned away.

                  7.5.11 The vertebrae or scales are placed in a labeled coin envelope and
                         may later be used for age determination.
                  7.5.12 Whole-bodied fish are thawed under MilliQ. They may be
                         stripped of mucous by using a forceps. At no time may the whole
                         body fish touch any unclean surface or instrument.

                  7.5.13 They are measured to the nearest 1mm with a plastic ruler. The
                         whole fish, minus the head, tail, and guts are rinsed in MilliQ and
                         composited with the other fish. The individual fish are cut as
                         necessary to ensure similar size fish in the composite.

                  7.5.14 The beginning bottle weight, individual fish weights to the nearest
                         0.01g and end bottle weight are recorded.

                  7.5.15 All samples are refrozen after dissection and maintained at -20°C
                         until homogenization and/or analysis.


         7.6 Sample Homogenization – Fish/Crab

                  7.6.1    Ideally samples are homogenized directly after dissection. If they
                           were frozen fish/crab samples are removed from the freezer and
                           are allowed to thaw long enough to be transferred to clean Büchi
                           sample jar.

                  7.6.2    Prior to and after homogenization the blades and drive shaft of the
                           Büchi are scrubbed with Micro, and rinsed 3 times each in tap and
                           DI.

                  7.6.3    To TM clean the titanium blades, rinse 3 times in MilliQ.

                  7.6.4    To SO clean the steel blades, rinse 3 times in MilliQ, followed by
                           3 rinses in methanol and 3 rinses with. Air dry.

                  7.6.5    To split clean titanium blades, rinse 3 times in 6% HNO3, followed
                           by 3 rinses in MilliQ. Follow up with 3 rinses each in methanol


Calleguas Creek Watershed                            36                            November 2003
Pesticides/PCBs Sampling and Analysis Plan - DRAFT
                           and PE. Air dry.

                  7.6.6    Reassemble the cutting unit. Support the screw with your left hand
                           while turning with your right. To lock into position, press the
                           white button at the top of the machine while turning the cutter
                           screw.

                  7.6.7    To homogenize the sample, close the door and secure. Raise the
                           sample jar by pressing the toggle on the front of the machine. The
                           blades will automatically turn. If there is too much tissue in the
                           jar, the machine will not be able to function. Make sure the motor
                           does not overwork.

                  7.6.8    Remove homogenized sample from Buchi by pressing the other
                           side of the toggle. Open door and gently remove sample jar.

                  7.6.9    Aliquot sample to SO jar and/or TM cup with pre-cleaned titanium
                           rod. Record weights aliquoted to each.

                  7.6.10 Dissasemble cutting unit and diaphragm seal; clean for next
                         sample.


8.0 QUALITY CONTROL

         8.1 Equipment Blanks: All equipment used in collection and preparation of
             samples is periodically checked for contamination. Before any new or
             different equipment is used it must be checked for contamination.

         8.2 Sample Archive: All remaining sample homogenates and extracts are archived
             at     -20C for future analysis. A few of the more important original mussel
             and clam samples are also archived for future analysis.

         8.3 Field Blanks: Field blanks are taken according to the specific study.

         8.4 Field Replicates: Field replicates are taken according to the specific study.
             Generally, one field replicate is taken for every twenty stations and is
             analyzed for both TM and SO.

         8.5 A record of sample transport, receipt and storage is maintained and available
             for easy reference.

         8.6 All samples are prepared in a clean room to avoid airborne contamination.




Calleguas Creek Watershed                            37                           November 2003
Pesticides/PCBs Sampling and Analysis Plan - DRAFT

				
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