[From the U.S. Government Printing Office, www.gpo.gov]



                                                               Volume 2 - Field Sampling
              Project Manual                                                   & QA/QC Plan







                         PENNSYLVANIA COASTAL ZONE MANAGEMENT PROGRAM


                                    WATER QUALITY MONITORING STUDY
                                       FOR THE LANE ERIE WATERSHED



                                                SEPTEM13ER 1996
                                                 Project: 2758-001



                                          CZM Project No.: CZI:94.06PE





                  A REPORT OF THE PENNSYLVANIA DEPARTMENT OF ENVIRONMENTAL PROTECTION
                          TO THE NATIONAL OCEANIC AND ATMOSPHERIC ADMINISTRATION
                                    PURSUANT TO NOAA AWARD NO. - NA470ZO248






                            dur







              This project was financed through a Federal Coastal Zone Management Grant from the
              Pennsylvania Department of Environmental Protection with funds provided by the National
              Oceanic and Atmospheric Administration (NOAA). The views expressed herein are those of
              the author(s) and do not necessarily reflect the view of NOAA or any of its subagencies.
                                                            A











              MALODW
                 PIRNIE                                 ENVIRONMENTAL ENGINEERS, SCIENTISTS & PLANNERS








                 MALCOW
                    PIRNIE









                       FIELD SAMPLING AND
                       QUALITY ASSURANCE/QUALITY CONTROL PLAN
                       WATER QUALITY MONITORING STUDY
                       FOR THE LAKE ERIE WATERSHED










                       REVISED JUNE 1995
                       MAY 1995


















                                                               MALCOLM PIRNEE, INC.


                                                                       40 Centre Drive
                                                                        P. 0. Box 1938
                                                                Buffalo, New York 14219



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               MALCOLM
                  PIRNIE


                                                           TABLE OF CONTENTS


                                                                                                                        Page


                      1.0  INTRODUCTION            ................................................                          1
                      1.1  DATA QUALITY OBJECTIVE                  .....................................                     1


                      2.0  SAMPLING         .....................................................                            2
                      2.1  DRY WEATHER SAMPLING                  ......................................                      2
                      2.2  WET WEATHER SAMPLING                  ......................................                      2
                      2.3  DEPTH AND VELOCITY MEASUREMENTS                           .........................               3
                      2.4  INITIAL SAMPLING             .............................................                        3
                      2.5  INITIAL SELECT[ON OF PARAMETERS-OF-INTEREST                              ...............          4
                      2.6  INTERMEDIATE REDUCED PARAMETER SAMPLING                                  ...............          4
                      2.7  FINAL SELECTION OF PARAMETERS-OF-INTEREST                             .................           4
                      2.8  REDUCED PARAMETER SAMPLING                       ...............................                  5


                      3.0  SAMPLING AND SAMPLE CUSTODY PROCEDURES                                .................           6
                      3.1  GENERAL SAMPLING PLAN                 ......................................                      6
                           3.1.1 Sampling Methods         ...........................................                        6
                      3.2  SAMPLE CONTAINERS AND PREPARATION                           ........................              6
                           3.2.1 General       ...................................................                           6
                           3.2.2 Bacteriological Samples        .......................................                      6
                      3.3  SAMPLE ACQUISITION - GENERAL                     ..............................                   7
                           3.3.1   ..........................................................                                7
                           3.3.2   ..........................................................                                7
                           3.3.3   ..........................................................                                7
                           3.3.4   .........................................................                                 7
                      3.4  ACQUISITION OF LIQUID SAMPLES                    ...............................                  7
                           3.4.1 For General Chemical/Physical Analyses            ..........................                7
                      3.5  CHAIN-OF-CUSTODY              ............................................                        8
                      3.6  SAMPLE LABELS            ...............................................                          8
                      3.7  RECORD KEEPING PROCEDURES                       ................................                  8
                      3.8  SAMPLE PRESERVATION                 ........................................                      9
                      3.9  SAMPLE HOLDING             ..............................................                         9
                      3.10 SAMPLE LOG-IN AND ANALYTICAL SPECIFICATIONS                              ...............          9
                      3.11 SAMPLE AND DATA MOVEMENT IN THE LABORATORY                                   ...........       10
                           3.11.1 Sample Storage and Movement            ................................                 10
                           3.11.2 Data Movement          ...........................................                      10


                      4.0 ANALYTICAL PROCEDURES                    ....................................                   11
                      4.1 ANALYTICAL METHODS/PROCEDURES                           ..........................              11










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            MALCOLM
             PIRNIE


                                           TABLE OF CONTENTS (Continued)


                                                    LIST OF TABLES


                  Table                                                                           Follows
                   No.       Description                                                             Page

                  2-1        Sampling Approach   ..........................................            3

                  2-2        Analytical Parameters - PADER Chapter 16     ........................     3
                             Analytical Parameters - PADER Chapter 93     ........................     3

                  2-3        Analytical Methods and Detection Limits for Inorganics  ...............   3

                  3-1        Containers, Preservatives and Holding Times -
                             Water Samples    ..............................................           9




                                            LIST OF FIGURES AND FORMS



                  Figure/Form                                                                     Follows
                   No.       Description                                                             Page

                   2-1       Twelvemile Creek Map     ........................................         2

                   2-2       Walnut and Elk Creek Map      ....................................        2

                   3-1       Church Laboratory, Inc. Chain of Custody Record    ...................    8

                   001       Field Log Sheet  ..............................................           9

                                                LIST OF ATTACHMENTS



                  Attachment Description

                    A        Church Laboratories, Inc. - Commonwealth of Pennsylvania Certification



                                                 LIST OF APPENDICES


                  Appendix Description

                   A         Sample Preservation




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              MAWDIM
               PIRNIE


                    1.0    INTRODUCTION


                           The Erie County Department of Planning (ECDP), in conjunction with the
                    Pennsylvania Department of Environmental Resources Division of Coastal Programs (DCP)
                    and the Erie County Health Department (ECHD) retained Malcolm Pirnie to conduct a
                    water quality survey of three Erie County subwatersheds. The project will be coordinated
                    by the County while technical support and review activities will be performed by the DCP
                    and ECHD. Project financing is through a federal Coastal Zone Management (CZM) grant

                    program.
                           The purpose of this plan is to identify the quality control and assurance steps for
                    sampling, field activities and laboratory analytical controls required to establish a water
                    quality baseline for the Lake Erie Watershed. The activities included in this plan focus on
                    the Elk Creek, Walnut Creek, and Twelvemile Creek subwatersheds, which together make
                    up about 44.5 percent of the entire watershed area.
                           The Lake Erie Watershed covers 330 square miles; has 14 large subwatersheds and
                    more than 500 individual drainage areas; and encompasses all or portions of 25 Erie County,
                    Pennsylvania, municipalities, including the 10 coastal municipalities.
                           The Coastal Zone Act Reauthorization Amendments, Section 6217, require that
                    states with coastal programs develop a Coastal Nonpoint Source Control Program (CNPCP).
                    Water quality information for watersheds within the federally assigned CNPCP management
                    areas is needed to help quantify the effects of nonpoint source pollutants on coastal water,
                    identify particular parameters of concern, and establish appropriate baseline conditions for
                    future effectiveness monitoring of management measure implementation.


                    1.1    DATA QUALITY OBJECTIVE


                           The data quality objective is to collect representative samples and analyze them using
                    methods that will produce accurate, precise values to be used to characterize the stations.
                    The data will further be assessed to evaluate flow characteristics and potential pollutant
                    loadings. As sampling activities progress, the objective will be to reduce the analytical
                    parameter list and concentrate on those parameters that have the greatest potential to affect
                    pollutant loading to Lake Erie.



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             MALCOW
               PIRNIE

                                                                                              2.0 SAMPLING



                            Malcolm Pirnie will subcontract laboratory analytical and sample collection activities
                    to Church Laboratories, Inc., located in Fairview, Pennsylvania. Church is a certified full
                    service laboratory that also provides sample collection services. Field and analytical data
                    will be recorded by laboratory personnel on a form similar to the one that will be
                    transmitted throughout the project from Church Laboratories to Malcolm Pirnie for review
                    and report preparation.
                            Presented on Figures 2-1 and 2-2 are maps showing approximate water quality
                    sampling station locations. Malcolm Pimie will inspect each subwatershed for precise
                    sampling locations that are near the discharge of each creek, upstream of any influences of

                    Lake Erie.
                            Malcolm Pirnie personnel will be present during the first dry weather sample
                    collection task to identify the sample collection locations for the subcontractor.
                            The subcontractor will notify Mr. Joseph Vogel of the Erie County Department of
                    Health (ECDOH) at (814) 451-6700 of pending sampling events. The ECDOH may elect
                    to split samples during dry or wet weather sampling events.



                    2.1     DRY WEATHER SAMPLING


                            Dry weather sampling activities will commence following sample location siting. A
                    minimum of 48 to 72 hours of antecedent dry weather is required prior to collection of dry
                    weather samples.


                    2.2     WET WEATHER SAMPLING


                            Wet weather sampling activities will commence following a number of conditions.
                    A minimum of 48 to 72 hours of antecedent dry weather conditions will proceed wet
                    weather sampling activities.      Malcolm Pirnie will estimate the travel time of each
                    subwatershed in an effort to determine proper wet weather sampling protocols. By
                    evaluating the travel time of each stream, we will attempt to collect samples in a timely
                    fashion that captures any "first flush" effects of a precipitation event. Rainfall intensity and



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               MALCOLM
                PIRNIE

                    duration, time of travel and estimated flows will all factor into the decision to initiate wet
                    weather sampling. We will review the developed wet weather protocol with the sampling
                    crew prior to the first wet weather sampling event.


                    23      DEPTH AND VELOCITY MEASUREMENTS


                            Procedures for collection of depth and velocity measurements will be developed
                    following the initial site visit to select the sample site. Based on an evaluation of the sample
                    collection location, the number of depth and velocity measurements that are required during
                    each "round" of sampling will be determined. Depth and velocity measurement procedures
                    and techniques will be reviewed with the sampling crew prior to the collection of the first
                    sampling event.



                    2A      INITIAL SAMPLING


                            Table 2-1 illustrates the overall sampling program approach. Initially, one dry
                    weather sampling event will be performed where all three monitoring locations will be
                    sampled. The depth of flow at each sampling location for each stream will be recorded
                    when the grab sample is collected. We estimate that the time to collect the first round of
                    samples from each stream will approach two hours. This procedure will be completed three
                    times, collecting an equal volume of sample each time. These three sets of grab samples
                    collected at each stream station will be composited by the analytical laboratory and tested
                    for the complete parameter list (see Table 2-2). This will serve as baseline or background
                    data for the study. Listed in Table 2-3 are the approved U. S. Environmental Protection
                    Agency (USEPA) methods and detection limits that the laboratory will use when analyzing
                    inorganic parameters.
                            In addition, one wet weather sampling event will be performed at the three
                    monitoring locations for the full list of parameters. Sample collection will be conducted as
                    described above during the storm events.









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                                                                  TABLE 2-1


                           WATER QUALITY MONITORING STUDY FOR THE LAKE ERIE WATERSHED


                                                           S"PLRVG APPROACH

                      Initial Monitoring (Spring and Summer Season):

                                       1 Event (dry)                   6-hour composite - Full list of parameters

                                       1 Event (wet)                   6-hour composite - Full list of parameters

                      Intermediate Reduced Parameter Sampling (Spring and Summer Season):

                                       1 Event (dry)                   6-hour composite - Initial parameters-of-interest

                                       3 Events (wet)                  6-hour composite - Initial parameters-of-interest

                      Reduced Parameter Sampling (Fall Season):

                                       4 Events (wet)                  6-hour composite - Final parameters-of-interest







































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               MALCOW
                 PIRNIE

                                                                     TABLE 2-2


                             WATER QUALITY MONITORING STUDY FOR THE LAKE ERIE WATERSHED

                                                           ANALYTICAL PARAMETERS

                            PADER Chapter 16 Test Parameters                     PADER Chapter 93 Test Parameters

                                  Antimony                                            Aluminum
                                  Arsenic                                             Alkalinity
                                  Beryllium                                           Ammonia Nitrogen

                                  Cadmium                                             Bacteria/Fecal Coliform
                                  Chromium Total                                      Hardness
                                  Chromium VI                                         Iron

                                  Copper                                              Manganese
                                  Lead                                                Nitrite - Nitrogen
                                  Mercury                                             Nitrate - Nitrogen

                                  Nickel                                              Chloride
                                  Selenium                                            Oil and Grease
                                  Silver                                              CBODs
                                  Thallium                                            Total Suspended Solids
                                  Zinc                                                Phosphorus
                                  Cyanide (free)                                      COD

                                  Pesticides:                                         Field Measurements:
                                  Aldrin                                              Dissolved Oxygen
                                  aIpha-BHC                                           pH
                                  beta-BHC                                            Temperature
                                  gamma-BHC (Lindane)                                 Conductivity

                                  delta-BHC
                                  alpha-Chlordane
                                  gamma-Chlordane

                                  4,4'-DDT
                                  4,4'-DDE
                                  4,4'-DDD

                                  Dieldrin
                                  alpha-Endosulfan

                                  beta-Endosulfan
                                  Endosulfan. Sulfate
                                  Endrin

                                  Endrin Aldehyde
                                  Heptachlor
                                  Heptachlor Epoxide
                                  Toxaphene






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                  IRNI




                                                                  TABLE 2-3


                           WATER QUALITY MONITORING STUDY FOR THE LAIKE ERIEE WATERSHED

                                  Approved USEPA Analytical Methods and Detection Limits for Inorganics

                                Parameter                          Analytical                    Method Detection
                                                                    Method                           Limit mg/1

                      Aluminum                                       202.1                               0.1

                      Antimony                                       204.2                               0.003

                      Arsenic                                        206.2                               0.001

                      Beryllium                                      210.1                               0.005

                      Cadmium                                        213.2                               0.0001

                      Chromium                                       218.1                               0.05

                      Chromium, hexavalent                           218.4                               0.01

                      Copper                                         220.2                               0.001

                      Iron                                           236.1                               0.03

                      Lead                                        239-1/239.2                        0.1/0.001

                      Manganese                                      243.1                               0.01

                      Mercury                                        245.1                               0.0002

                      Nickel                                         249.1                               0.04

                      Selenium                                       270.2                               0.002

                      Silver                                         272.2                               0.0002

                      Tballium,                                   279.1/279.2                        0.1/0.001

                      Zinc                                           289.1                               0.005























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             MALCOLM
               PIRNIE


                    2.5     INITUL SELECTION OF PARAMETERS-OF-INTEREST


                            At the conclusion of the sampling and analysis of the dry weather and wet weather
                    events, a meeting will be scheduled with ECDP and DCP. At this meeting the concentra-
                    tions of parameters from the dry weather and wet Weather events will be evaluated with

                    respect to:


                              ï¿½     Presence above detection limits.
                              ï¿½     Historical presence above detection limits.


                            Based   on these criteria, the full parameter list may be reduced for subsequent
                    sampling efforts. Each of the sampling locations will be evaluated individually which may
                    result in different parameter-of-interest lists.


                    2.6     INTERMEDIATE REDUCED PARAMETER SAMPLING


                            Once an initial parameters-of-interest list has been agreed upon by ECDP and DCP
                    for each sampling location, a second set of events will be sampled. Samples will be collected
                    for one dry weather event and three wet weather events in the same manner as described
                    in Section 2.4. The samples will be analyzed for the initial parameters-of-interest lists.



                    2.7     FINAL SELECTION OF PARAMETERS-OF-INTEREST


                            Once the data from the second dry weather and three wet weather sampling events
                    have been reviewed for adequacy in meeting the data quality objectives of the sampling
                    program, the concentrations of those parameters detected will be compared and evaluated
                    with respect to:


                              ï¿½     Frequency of presence above detection limits.
                              ï¿½     Existing water quality standards.
                              ï¿½     Potential pollutant loading to Lake Erie.


                            Based   upon these criteria, the initial parameter list may be further reduced for
                    future sampling efforts. The objective is to both reduce sampling costs and to concentrate
                    on those parameters which have the greatest potential to influence the evaluation of



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             MAW01M
               PIRNIE

                    pollutant loadings to Lake Erie. It should be noted that the parameter list again will be
                    reviewed individually for each sampling point and that each point may not have the same
                    recommended list of final parameters-of-interest.



                    2.8    REDUCED PARAMETER SAMPLING


                           Once a final parameter-of-interest list has been established for each sampling point,
                    an additional four wet weather sampling events will be performed at all three sampling
                    locations. The samples will be analyzed for the final list of parameters-of-interest.















































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              MALCOW
               PIRNIE


                                 3.0 SAMPLING AND SAMPLE CUSTODY PROCEDURES



                    3.1     GENERAL SAMPLING PLAN


                            This sampling plan addresses the procedures to be used to obtain representative
                    stream samples from Elk Creek, Walnut Creek, and Twelve Mile Creek, descriptions of
                    sampling equipment and containers to be used. Appropriate sampling procedures will be
                    utilized to collect representative samples. A description of the technique, the rationale, and
                    the criteria to be employed for selection of sampling locations and the frequency of sampling
                    is described. Specific sampling procedures to be used (USEPA), will be referenced. For
                    non-standard or modified sampling methods, detailed procedures with appropriate
                    references will be required.


                            3.1.1 Sampling Methods
                            All persons involved with the sampling program will participate in a review of
                    sampling procedures to be conducted by Malcolm Pirnie and will be technically competent
                    and familiar with the procedures employed. They will be familiar with all aspects of this
                    QA/QC Plan as well as the data quality objective of this program.


                    3.2     SAMPLE CONTAINERS AND PREPARATION



                            3.2.1. General
                            Sample containers shall be made of materials that will not contaminate the sample.
                    See Appendix A for acceptable containers.


                            3.2.2  Bacteriological Samples
                            Plastic bottles (at least 125 ml capacity), caps, and their liners must withstand
                    sterilization temperatures and impart no toxic or bacteriostatic compounds to the sample.
                            Clean containers with a phosphate-free laboratory detergent and hot water, then
                    rinse repeatedly with hot water followed by at least three rinses with laboratory deionized

                    water.






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              MALCOLM
               PIRNIE

                           Sterilize containers in an autoclave at a minimum of 121*C, 15 psi for at least 30
                    minutes. Loosen screw caps slightly to avoid rupture of container.
                           If the sample to be collected contains residual chlorine, add sodium thiosulfate in
                    an amount to provide a concentration of about 100 mg/l in the sample. Omit this addition
                    if thiosulfate interferes with subsequent examination.


                    33     SAMPLE ACQUISITION - GENERAL


                           33.1 See Appendix A for container types for each parameter or group of

                    parameters.


                           3.3.2 Label samples with information listed in Section 3.6. For each ten or
                    multiple of ten samples collected in a set, one sample shall be collected in duplicate.


                           3.3.3 A field log book will be kept for all sampling and will include the applicable
                    items listed in Section 3.7.



                           3.3A Additional sampling instructions specific for acquisition of liquids are
                    contained in subsequent Section (3.4).


                    3.4    ACQUISITION OF LIQUID SAMPLES


                           3A.1 For General Chemical/Physical Analyses
                           Grab Samples: Before taking the samples, rinse the sample container at least three
                    times by filling it to about one-fourth capacity with water to be sampled.
                           It is important to obtain the most representative sample possible. If a stream is
                    sampled avoid disturbing the sediment at the site by approaching the site from downstream.
                           Analytical parameters where composite sampling is not suitable, such as fecal
                    coliform. and oil and grease, will be collected during the second round of grab sampling
                    activities, initially. If during the sampling program it becomes apparent that collection of
                    these samples is more advantageous to be completed during Rounds 1 or 3, we will notify
                    the ECDP of this change via letter.



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             MALCOW
               PIRNIE

                           Composite Samples: Composite samples may be made by combining individual grab
                    samples taken at frequent intervals.
                           Composite samples are not suited for samples to be analyzed for dissolved gases, pH,
                    oil and grease, bacteria, temperature or other parameters with holding periods less than the
                    composite cycle or that cannot be agitated or poured from one container to another.



                    3.5    CHAIN-OF-CUSTODY


                           To establish the documentation necessary to trace sample possession from the time
                    of collection, a Chain-of-Custody Record (Figure 3-1) must be completed and accompany
                    each sample or sample set.
                           The form is signed by the sample collector and by any individual who has custody
                    of the samples until they are delivered to Church Laboratory, Inc. The Laboratory
                    Supervisor (or his representative) acknowledges receipt of the samples at the laboratory by
                    initiating the Chain-of-Custody Record.



                    3.6    SAMPLE LABELS



                           Sample labels are located on the face of each container and are to include the
                    following information as applicable:


                             ï¿½     Collector's initials.
                             ï¿½     Location.
                             ï¿½     Date sampled.
                             ï¿½     Time sampled.
                             ï¿½     Church Laboratory, Inc. I.D. Number (when received in laboratory).
                             ï¿½     Required analysis.
                             ï¿½     Field information.



                    3.7    RECORD KEEPING PROCEDURES


                           The following information shall be recorded by the sampling crew at the time of
                    sampling:


                             ï¿½     Unique sample designation, location, sketch.
                             ï¿½     Name of sampler.



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                                                                                                                          FIGURE 3-1
                         CHURCH laboratory, inc.                                                               (814) 474-2044
                                                                                           7397 0HGGTNUT STREET - P.0 00)(83
                                                                                                              FAIRVIEW. PA. 104 15








                       Malting Address:
              Name:


              Address:


              qi ty:             -ST-ZlP-

              At tn:


                                                          CNAIM OF CUSTODT RECORO

                       Sample name &/or             Date      Time          "to           No. of
                       Description                  5ampted Sampled         Matrix        Containers         Notes:




























                   SAMPLED BY:                                                        RECEIVED Sy:
              Print Name:                                                        Print kamo;
              Signature,                                                         Signature:
              Date:                                                              Date:


                 RELINQUISHED By:                                                     RECEIVED FOR LABORATORY BY.-
              Print Name:                                                        Print Name:
              ligmaturej                                            -            Signature:
              Date:                                                              Date:


              Comments-
              @9























































              NO Of S8009s;-               PO Number-              Lot Wo-.               tat) ID No.,

              Client Authorization:                                                        Date:







             MALCOLM
               PIRNIE


                             E     Weather.
                             E     Method of collection.
                             0     Time and date of sampling.
                             E     Field measurements and calibration.
                             0     Observations and remarks.


                           Malcolm Pirnie has developed and included a typical form to be used during each
                   sample event (Form 001). All data sheets will be forwarded to Malcolm Pirnie for
                   recordkeeping.


                   3.8     SAMPLE PRESERVATION


                           Samples to be analyzed for any parameter listed in Table 3-1 must be preserved
                   according to instruction given in that procedure.
                           A container of the same type used in sampling must be filled with deionized water,
                   and the same preservative used in the actual samples is added to the deionized water and
                   labeled field blank. The field blank is analyzed along with the samples to determine if there
                   is any contamination attributable to the sampling process. Field blanks will be analyzed at
                   a rate of approximately one per twenty samples.



                   3.9     SAMPLE HOLDING


                           Properly preserved samples may be held up to the holding times listed in Table 3-1.
                   Regardless, samples should be analyzed as soon as possible to ensure the minimum loss or
                   gain of the parameter of interest. Whenever an analysis has exceeded its holding time, it
                   must be noted on the final report.



                   3.10 SAMPLE LOG-IN AND ANALYTICAL SPECIFICATIONS


                           The Laboratory Supervisor (or his designate) acknowledges receipt of samples on
                   the Chain-of-Custody Record. Next the samples are assigned a Church Laboratory
                   Identification Number. This number is logged in a bound book. The Church Laboratory
                   sample number is placed on the sample bottle and the appropriate color coded work sheet
                   is completed and placed in the pending work file box.



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                                                                                                                                                                                      Form 001



                                                                                                       COUNTY OF ERIE.


                                                                                           WATER QUALITY MONITORING
                                                                                     FOR LAKE ERIE WA TERSHED STUDY




                                                                                    FIELD LOG SHEET


                                                                                                                                                                        .............-.... .
                        ..........            --------------------
                     LOCATION:
                     DATE:
                     SAMPLERS NAME:
                     WEATHER CONDITIONS:
                          ..................... ......................         ................................................................................................................................. ........................... .j




                                                               ---------- -----                           ............. ....................
                                                                                                                      0
                                                                         ROUND I                                        UND 2                            ROUND 3
                     ...............................  ..............................M. .............................. ............................. ..... ........ ................................
                                      TIME
                                       pH
                                       Do
                            CONDUCTIVITY
                                     TEMP
                                                                                                                                                               ..................................
                     DEPTH MEASUREMENTS
                     .................................................................. ............................... ............................ ................................. .......................... ...........................
                                       St 1
                                       st -2
                                       St 3
                                       St 4
                                       St 5
                                                                                    -------------------
                                                    ...............                                       .................................................... ..............
                     VELOCITY MEASUREMENTS
                     ........... .................. ... ------ - -- - ----- -- ---------------------- . ............................ .-..............  ......... ............................... .................................
                                       st 1
                                       St 2
                                       St 3
                                       St 4
                                       St 5
                     . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .




                     OTHER SITE OBSERVATIONS
                                                                                    -------------------------- ------  ----------- ---------------- -------- ----------------------------------












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                  f:\users\wier\erieco\fldlog.wkl                                                                                                                                  12-May-95












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                                                                                                                     TABLE 3-1


                                                                          WATER QUALITY MONITORING STUDY FOR THE LAKE ERIE WATERSHED



                                                                                         CONTAINERS, PRESERVATIVES AND HOLDING TIMES*
                                                                                                                 WATER SAMPLES

                                                                                                                                                                                                          Analytical          Method
                       Parameter                                                 Container                                             Preservative                        Holding Time                    Method           Reference

              Pesticides                         One (1) I-liter amber glass bottle, Teflon-lined lid.                          Cool to 4*C                      Extract within 5 days and ana-              508                  1
                                                                                                                                                                 lyze within 40 days of collec-
                                                                                                                                                                 tion

              Total Metals                       One (1) 1-liter polyethylene bottle                                            HN03 to pH     <2                28 days mercury, 6 months                200 series              2
                                                                                                                                                                 others

              Hexavalent Chromium                500 rrd polyethylene bottle                                                    Cool to 4*C                      24 hours                                    218.4                2

              Total Suspended Solids             100 n-d polyethylene bottle or glass                                           Cool to 4*C                      7 days                                      160.2                2

              Alkalinity                         500 mi plastic or glass                                                        Cool to 4'C                      14 days                                  310.1 or 2              2

              Chloride                           100 ml plastic or glass                                                        None required                    28 days                                  325.2 or 3              2

              Ammonia-Nitrogen                   500 ml plastic or glass                                                        Cool to 4*C                      14 days                                  350.1 or 2              2
                                                                                                                                H2S04 to pH    <2

              Nitrate-Nitrite                    100 mI plastic or glass                                                        Cool to 4*C                      14 days                                  353.2 or 3              2
                                                                                                                                H,SO4 to pH    <2

              Oil and Grease                     One (1) I-liter amber glass bottle                                             Cool to 4*C                      24 hours                                    413.1                2
                                                                                                                                H.IS04 to pH   <2

              CBOD,                              500 ml plastic or glass                                                        Cool to 4*C                      24 hours                                    507                  3
              Total Phosphorus                   500 ml plastic or glass                                                        Cool to 4*C                      28 days                                     365.4                2
                                                                                                                                H2SO4 to pH    <2

              Phenols                            500 n-d glass                                                                  Cool to 4*C                      28 days                                     420.2                2
                                                                                                                                H2SO4 to pH    <2
                                                                                                                                                                                                                                        _j




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                                                                                                                  TABLE 3-1


                                                                         WATER QUALITY MONITORING STUDY FOR THE LAKE ERIE WATERSHED



                                                                                       CONTAINERS, PRESERVATIVES AND HOLDING 77MES*
                                                                                                               WATER SAMPLES


                                                                                                                                                                                                     Analytical          Method
                       Parameter                                               Container                                             Preservative                      Holding Time                   Method           Reference

              Cyanide, Free                     500 in] plastic or glass                                                     Coot to 4'C                      14 days                                  00719A                5
                                                                                                                             NaOH to pH > 12

              Bacteria, Fecal Coliform           125 ml sterilized plastic or glass                                          Cool to 4*C                      6 hours                                                        4
                                                                                                                             Add NA,SO,                     I                                    I

              Hardness                          500 ml plastic or glass                                                      Cool to 4C                       24 hours                                  130.2                2

              Notes:
                         The laboratory shall achieve a Method Detection Limit which meets those limits established in PADER, Tide 25, Chapters 93 and 16 for the particular methodology listed in this table.
                         No specific numerical method available.

              Method Reference:
                     1.  USEPA, 40 CFR Part 136, "Guidelines Establishing Test Procedures for the Analysis of Pollutants Under the Clean Water Act", Friday, October 26, 1984.
                     2.  USEPA, 600/4-79-020, 'Methods for Chemical Analysis of Water and Wastes", revised March 1984.
                     3.  AWWA-WPCF, "Standard Methods for the Examination of Water and Wastewater, l6th Edition, 1985.
                     4.  USEPA, "Microbiological Methods for Monitoring the Environment", December 1978.
                     5.  DER Method.













    V






    T      2758-001-130                                                                                                                                                                                                   Page 2 of 2
    CL.







             MAW01M
               PIRNIE


                   3.11 SAMPLE AND DATA MOVEMENT IN THE LABORATORY



                           3.11.1 Sample Storage and Movement
                           When refrigeration is necessary, samples are stored at 4'C until analysis is
                   performed. Otherwise they are stored in a designated area as specified by the Laboratory
                   Supervisor. The Laboratory Supervisor or his designate will provide individual instruction
                   which specifies the parameters to be analyzed for the sample(s). As these parameters are
                   completed the analyst places the results on the appropriate work sheet.
                           Samples should be kept until holding times are exceeded or until client gives
                   approval to discard samples.



                           3.11.2 Data Movement
                           During analysis a parameter specific worksheet must be completed. This worksheet
                   must contain the following:


                            ï¿½     Church Laboratory I.D. Number.
                            ï¿½     Sampling date.
                            ï¿½     Type of sample.
                            ï¿½     Quality control data per client specifications.
                            ï¿½     Parameter name.
                            ï¿½     Results and analysis.
                            ï¿½     Procedure number (when applicable).
                            ï¿½     Dilution factors (when applicable).
                            ï¿½     Sample weight (when applicable).
                            ï¿½     Blank results (when applicable).

                           When analysis of a sample or set of samples is complete the Laboratory Supervisor
                   or his designate will review the worksheet. Any mistakes will be reviewed with the analyst
                   and corrected. The worksheet is then submitted to the secretary for transfer to the client
                   report form. This form is then reviewed and signed by the Laboratory Supervisor.












                   2758-001-130                                10



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             MALCOW
               PIRNIE


                                                                  4.0 ANALYTICAL PROCEDURES



                   4.1     ANALYTICAL METHODS/PROCEDURES


                           Analytical methods used shall be USEPA-approved standard methods wherever
                   practical. All inorganic parameters listed in Chapter 16 and all Chapter 93 parameters shall
                   be analyzed according to methodology contained in either:
                             ï¿½     USEPA, 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
                                   Analysis of Pollutants Under the Clean Water Act", Friday, October 26,
                                   1984.


                             ï¿½     USEPA, 600/4-79-020, "Methods for Chemical Analysis of Water and
                                   Wastes", revised March 1984.

                             ï¿½     AWWA-VVTCF, "Standard Methods for the Examination of Water and
                                   Wastewater, 16th Edition, 1985.

                             ï¿½     USEPA, "Microbiological Methods for Monitoring the Environment",
                                   December 1978.


                             ï¿½     DER Method.


                           Where alternate standard methods are available, the most cost-effective method shall
                   be used provided it satisfies project requirements for precision, accuracy, specificity,
                   sensitivity, and is approved by ECHD and DCP.
                           Malcolm Pirnie has received a copy of the Commonwealth of Pennsylvania
                   certification for Church Laboratory, Inc. This document (Attachment A) indicates that the
                   laboratory utilizes appropriate analytical instrumentation, methodologies, procedures and
                   calculations that conform to standard laboratory practices. We expect that the laboratory
                   analytical instrumentation and methodology accuracy are verified through proper matrix
                   spikes, method blanks and duplicates as appropriate for proper QA/QC checks and data
                   validation. We anticipate that detailed information pertaining to these practices will be
                   available upon request.









                   2758-001-130                                 11



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                  MALCOM
                     PIRNIE













                                                                           ATTACHMENT A


                                                               CHURCH LABORATORIES, INC.
                                          COMMONWEALTH OF PENNSYLVANIA CERTIFICATION

















































                          2758-001-130




                                                                                                                                                Printed on Recycled Paper










         ER-LAB-16
              DEPARTMENT OF ENVIRONMENTAL RESOURCES

           OFFICE OF MANAGEMENT AND TECHNICAL SERVICES                          BUREAU OF LABORATORIES
                                          COMMONWEALTH OF PENNSYLVANIA

                                                                           Certifies that

                                                                 CHURCH LABORATORY INC
                                                            7397 CHESTNUT STREET PO BOX 83
                                                                     FAIRVIEW, PA 16415
                                                                         I.D. #25-070

                                                                having duly met the requirements of
                                                Chapter 109, Sub chapter H, Safe Drinking Water Rules and Regulations
                                                issued under the Pennsylvania Safe Drinking Water Act of May 1,1984
                                                             (P.L. 206, No. 43),(35 P.S. SS 721.1-721.17)
                                                                      is hereby approved as a
                                                      Certified Drinking Water Laboratory

                                                                To perform the following analyses:

                                                                         Microbiology

                                                                           Inorganic
                                    Trace Metals (Groups 1-3), Nitrate/Nitrite, Fluoride, Sulfate, Cyanide, Corrosivity

                                                                            Organic
         Total Trihalomethanes, Volatile Organic Compounds(Groups 1-3), Herbicides (Groups 1-2), Pesticides (Gro
                                                                 Chemicals(Groups 1&3), PCB



                                                                     Expiration Date: 1/1/96


         Certificate not transferable
         Surender upon relocation
         to be Consperiously Displayed at the Laborator


                                                                                                                Floyd Kefford, Bureau Director
                                                                                                                   Bureau of Laboratories







                  MALCOLM
                     PIRNIE














                                                                              APPENDIX A


                                                                    SAMPLE PRESERVATION




















































                          2758-001-130



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                              CHURCH LABORATORY, INC. 814 474 2044











                                         APPENDIX A


                                     SAMPLE PRESERVATION



                Once collected, a sample must be analyzed immediately or stored in
           a container with a preservative to maintain the integrity of the
           sample.    This chapter provides guidance on preservation methods,
           holding' times, storage condition nd container materials.

                Complete preservation of samples, either domestic sewage,
           industrial wastes, or natural waters, is a practical impossibility.
           Regardless of the nature of the sample, complete stability for every
           constituent can never be acbieved. At best, preservation techniques
           can only retard the chemical and biological change that take place in
           a sample after the sample is removed from the parent source.           To
           maintain the integrity of the sample, appropriate selection of
           containers, pretreatment of containers if necessary and the holding
           times form the integral part of the sample preservation program.

           1.1 METHODS OF PRESERVATION

                Methods of preservation are relatively limited and are intended
           generally to:   1) retard biological action; 2) retard hydrolysis of
           chemical compounds and complexes; and 3) reduce volatility of
           constituents.

                Preservation methods are generally limited to chemical addition,
           P14 control, refrigeration, and freezing. Combinations of these methods
           are often used for the preservation of the samDle.

           1.1.1 ChemiCal Addition

                The most convenient preservative is a chemical wbich can be added
           to a sample bottle prior to sampling. When the sample is added, the
           preservative disperses immediately, stabilizing the parameter(s) of
           concern for long periods of time.        When the preservative added
           interferes with other parameters being measured, additional samples for
           those paranteters must be collected. For example, concentrated nitric
           acid added for the preservation of sorne of the metals would interfere
           with BOD, so an additional sample must be collected for Bov.

           1.1.1.1   nK.Control

                pH control to preserve the sample is dependent upon chemical
           addition. As an example, to keep metal ions in a dissolved state con-
           carltrated nitric acid is added to lower the pH to less than 2.




                               CHURCH LABORATORY, INC. 814 474 2044





           *Taken from US EPA, 1982.           Handbook for Sampling and Sample
           Preservation of Water and Wa5tewater (EPA-600/4-02-029).
                      Freezing

                 Freezing has been the subject of many preservation studies.         it
           is felt by some that freezing would be a method for increasing the
           holding time and allowing collection of a single. sample for all
           analysis.    However, the residue solias components (filterable and
           nonfilterable) of the sample change with freezing and thawing.
           Thereforef return to equilibrium and then high speed homogenization is
           necessary before any analyses can be run.            This method may be
           acceptable for certain analysis but not as a general preservation
           method.

           1.1.3      Refrigeratign

                 Refrigeration or icing has also been studied with various results.
           This is a common method used in field work and has no detrimental
           effect on sample composition. Although it does not maintain integrity
           for all parameters it does not interfere with any analytical me-1L'-.hods.

           1.1.4      Preseryation Guidellnes

                 For NPDES samples,      the permit holder must use specific
           preservatives if the sample cannot be aaalyzed immediately after
           collection.    If preserved, the analyses must be conducted within a
           specified time frame.      Guidance submitted for approval to the 304h
           committee, US EPA, is shown in Table I.I.           Because approval and
           subsequent publication in the Federal Register has not taken place as
           of publication of the handbook, the reader is urged to keep abreast of
           existing NPDES regulations and changes through Federal Register
           publications.    In addition, some parameter holding times differ for
           drinking water samples, for example, microbiological and nitrate
           parameters.

                 Table 1.2 provides additional references and furnishes data on
           preservation methods, storage and holding times for different
           parameters found in various literature sources.           However, f or a
           specific application of the data, reference to the original publication
           should be made.

           1.1.5      Alter"tive Pre@ervazicn JIgthods

                 Alternative preservation methods with different preservatives or
           storage conditions can be used if its effectiveness can be domonstratod
           by supporting data through preservation studies.        Such preservation
           studies  must specify:

                 1.   Type of water/wastewater used as a sample in the experiment
                 2.   Type of containers used
                 3.   Pretreatment of the container and the glassware used
                 4.   Preservation methods used
                 5.   Specific temperatures or temperature range used



                              CHURCH LABORATORY, INC. 814 -.4T4 2044






                6.    Duration of storage
                7.    Stored in light or darkness
                8.    Quality Control samples - spikes, duplicates.
                9.    Blanks - controls
                10.   Number of samples analyzed and results
                11.   Statistical analysisp precision and accuracy

           1.2 CONTAINERS
                A variety of factors affect the choice of containers and cap
           material.    These include resistance to breakage, size, weight,
           interterence with constituents, cost and availability.    There are also
           various procedures for cleaning and preparing bottles depending upon
           the analyses to be performed on the sample.

           1.2.1      Container Material,
                The two major types of container materials are plastic and glass.

           Glass                                      Plastic
           1.   Kimax or Pyrex brand -                1.   Conventional
                Borosilicate                               Polyethylene
           2.   Vycor - generally lab ware            2.   Linear polyethylene
           3.   Ray - Sorbor Low-actinic              3.   Polypropylene
                generally lab ware                    4.   Polycarbonate
           4.   Corex - generally lab ware            5.   Rigid polyvinyl chloride
                                                      6.   Teflon

                All these materials have various     advantages and disadvantages.
           Kimax or Pyrex brand borosilicate glass  is inert tc most materials and
           is reccmmended where glass containers are used.              Conventional
           polyethylene is to be used when plastic is acceptable because of
           reasonable cost and less absorption of metal ions,           The specific
           situation will determine the use of glass or plastic.        However, use
           glass containers for pesticides, oil and grease, and other organics.
           Table 1.3 summarizes the advantages and disadvantages of these
           materials.


           1.2.2      C=tainer-Caps

                There are two major types of plastic used in containers caps:
           Polyethylene and bakelite with liners.           Polyethylene caps are
           recommended for ease of cleaning unless oil and grease analyses are to
           be performed. Caps with Teflon lines should be used for pesticides and
           oil and grease samples. Silicone rubber material should be avoided for
           Trace Metals because in zinc contaminations.      There are three liner
           types available and the advantages/disadvantages are listed in Table
           1.4.


           2.2.3      Container StjMCIMZe

                Use a wide mouth container in most instances. This structure will
           permit easy filling and sample removal.        It is also easily clean,



                               CHURCH LABORATORY, INC      814 474 2044




           quickly dried, and can be stored inverted. Use a narrow neck bottle
           when interaction with the cap liner or outside environment is to be
           minimized. Use a solvent cleaned glass container for pesticide sample
           collection.







           1.2.4      L)isposablp.__Qontainer,5
                 Use disposable containers when the cost of cleaning is high.
           These containers should be precleaned and sterile. The most commonly
           used disposable container of this type is the molded polyethylene
           cubitainer shipped nested and sterile to the buyer.         However since
           their cvbic shape and flexible sides make them almost impossible to
           clean thoroughly, use these containers only once.

           1.2.5      Container Wast "n

                 The following procedure should be followed to wash containers and
           caps  for inorganic and general parameters:

                 1.   Wash containers and caps with a non-phosphate detergent and
                      scrub strongly with a brush (if possible wash liners and caps
                      separately).
                 2.   Rinse with tap water, the deionized water.
                 3.   Invert to drain and dry.
                 4.   Visually inspect for any contamination prior to storage.
                 5.   If the container requires additional cleaning, rinse with a
                      chromic acid solution (35 ml saturated sodium dichromate,
                      solution in I liter of sulfuric acid - this 5olul,,--ion can be
                      reused). Then rinse with tap water and deionized water and
                      dry as indicated above.

           1.2.6      Containeg RXeRaratioja

                 For certain parameters, a special cleaning procedure is needed to
           avoid adsorption or contamination due to interaction with container
           walls. These procedures are outlined below:

                 1.   Metals: if metals are to be analyzed, rinse the container
                      with a solution of one part nitric acid to four parts        I
                      water, then with distilled water.      If phosphorus is to be
                      analyzed, rinse the container with a solution of one part
                      hydrochloric acid to one part water, followed by distilled
                      water. Treat the caps similarly.
                      Organics: If oil and grease or pesticides are to be
                      analyzed, rinse the sample container with methylene
                      chloride, followed by acetone. For pesticide analysis, use
                      pesticide grade hexane or acetone.       The container should
                      have been previously cleaned with chromic acid solution as




                              CHURCH LABORATORY, INC. 814 474 2044







                     described in Section 17.2.5.       Treat the container Caps
                     similarly.
                3.   Sterilization: For microbiological analyses, steril-4ze the
                     container and its stopper/cap by autoclaving at 12lcC for
                     15 minutes or by dry heat at 1801C for two hours.        Heat-
                     sensitive plastic bottles may be sterilized with ethylene
                     oxide at low temperatures.    Wrap bottles in kraft paper or
                     cover with aluminum foil before sterilization to protect
                     against contaminaticn. An acceptable alternative for
                     emergency or field use is ster.1lization of containers by
                     boiling in water for 15 minutes.




           1.3 HOLDING TIME

                Holding time is the time interval between collection and anaLysis.
           In general, the shorter the time that elapses between collection of a
           sample and its analysis, the more reliable will     be the analytical
           results.

                It is impossible to state exactly how much time may be allowed to
           elapse between collection of a sample and its analysis; this depends on
           the character of the sample, particular analysis to be made, and the
           conditions of storage.

                For NPDES purposes, in accordance with Federal Register, part 136
           follow the recommendations given in Table 1.1 and keep abreast of
           revised holding times that will be published in the Federal Register.

                For information purposes, however, data relating to holding times
           for general and inorganic parameters was collected front various
           literature sources and is tabulated in Table 1.2.

           1.4 SAMPLE voixmE

                The volume of sample collgcted should be sufficient to perform all
           the -required analyses plus an additional amount to provide for and
           quality control needs, split samples or repeat examination. Although
           the volume of sample required depends on the analyses to be performed,
           the amount required for a fairly complete analysis is normally about
           eight liters, (about two gallons). The laboratory receiving the sample
           should be consulted for any specific volume requirements. Individual
           portions of a composite sample should be a least 100 mi in order to-
           minimize sampler solids bias. Depending on the sampling frequency and
           sample volume, the total coinpo5ited sample should be a minimum of 8
           liters (about 2 gallons). Refer to EPA's Methods for Chemical Analyses
           of Water and Wastes 1-9-79, EPA 600/4-79-020, for the sample volumes
           required for specific-types of pollutant analyses.



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