section 6 calibration procedures and frequency … · 2012-10-04 · pollution control agency...

BioaccumulationQA Project Plan

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TABLE OF CONTENTS

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TITLE AND SIGNATURE PAGE ...................................................................................... iTABLE OF CONTENTS .................................................................................................... iiLIST OF TABLES .............................................................................................................. vLIST OF FIGURES............................................................................................................ viLIST OF ACRONYMS/ABBREVIATIONS....................................................................vii

SECTION 1 - PROJECT DESCRIPTION ..................................................................1-11.1 INTRODUCTION.....................................................................................................1-11.2 SITE DESCRIPTION................................................................................................1-11.3 PAST DATA COLLECTION ACTIVITIES ............................................................1-31.4 CURRENT STATUS ................................................................................................1-81.5 PROJECT OBJECTIVES .........................................................................................1-91.6 SAMPLE NETWORK DESIGN AND RATIONALE ...........................................1-111.7 PROJECT SCHEDULE ..........................................................................................1-131.8 BUDGET FOR ANALYTICAL, TOXICOLOGY, AND BIOACCUMULATION WORK.............................................................................1-13

SECTION 2 PROGRAM ORGANIZATION AND RESPONSIBILITIES ............2-12.1 PROJECT ORGANIZATION CHART ....................................................................2-12.2 MPCA PERSONNEL ...............................................................................................2-12.3 GLNPO PERSONNEL..............................................................................................2-22.4 CONTRACT LABORATORY MANAGEMENT ...................................................2-2

SECTION 3 QUALITY ASSURANCE OBJECTIVES FOR MEASUREMENT DATA........................................................................3-13.1 TARGET DETECTION LIMITS FOR CHEMICALS.............................................3-13.2 PRECISION ..............................................................................................................3-13.3 ACCURACY.............................................................................................................3-23.4 COMPLETENESS....................................................................................................3-33.5 REPRESENTATIVENESS.......................................................................................3-33.6 COMPARABILITY ..................................................................................................3-43.7 LEVEL OF QUALITY CONTROL EFFORT ..........................................................3-4

SECTION 4 SAMPLING PROCEDURES .................................................................4-14.1 SUMMARY OF SAMPLING ACTIVITY ...............................................................4-1


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4.2 SAMPLING NETWORK DESIGN AND RATIONALE.........................................4-14.3 SAMPLE TRACKING PROCEDURE.....................................................................4-34.4 SAMPLE CONTAINERS, SAMPLE PRESERVATION, AND MAXIMUM HOLDING TIME.................................................................................4-54.5 SAMPLE HANDLING, PACKAGING, AND SHIPMENT ....................................4-54.6 DECONTAMINATION PROCEDURES.................................................................4-64.7 SEDIMENT SAMPLING EQUIPMENT AND PROCEDURES.............................4-74.8 QC SAMPLE PROCEDURES..................................................................................4-84.9 FIELD REPLICATE SAMPLE COLLECTION.......................................................4-84.10 FIELD MEASUREMENTS ....................................................................................4-84.11 PREVENTATIVE MAINTENANCE PROCEDURES/SCHEDULE....................4-84.12 SAMPLE DISPOSAL .............................................................................................4-9

SECTION 5 SAMPLING TRACKING PROCEDURES ..........................................5-15.1 FIELD TRACKING PROCEDURES .......................................................................5-15.2 LABORATORY CUSTODY PROCEDURES.........................................................5-25.3 DATA STORAGE ....................................................................................................5-2

SECTION 6 CALIBRATION PROCEDURES AND FREQUENCY......................6-16.1 FIELD INSTRUMENT CALIBRATION .................................................................6-16.2 LABORATORY INSTRUMENT CALIBRATION .................................................6-1

SECTION 7 TOXICITY AND BIOACCUMULATION TESTING........................7-17.1 SCREENING TOXICITY TESTS ............................................................................7-17.2 SEDIMENT BIOACCUMULATION TESTS..........................................................7-17.3 TEST ACCEPTABILITY REQUIREMENTS .........................................................7-1

SECTION 8 LABORATORY ANALYTICAL PROCEDURES..............................8-1

SECTION 9 INTERNAL QUALITY CONTROL CHECKS ...................................9-19.1 FIELD QUALITY CONTROL CHECKS.................................................................9-19.2 LABORATORY QUALITY CONTROL CHECKS ................................................9-1

SECTION 10 DATA REDUCTION, VALIDATION, AND REPORTING ..........10-110.1 DATA REDUCTION............................................................................................10-110.2 DATA VALIDATION ..........................................................................................10-210.3 DATA REPORTING ............................................................................................10-3


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SECTION 11 PERFORMANCE AND SYSTEMS AUDITS ..................................11-111.1 FIELD PERFORMANCE AND SYSTEM AUDITS ...........................................11-111.2 LABORATORY PERFORMANCE AND SYSTEMS AUDITS.........................11-1

SECTION 12 PREVENTATIVE MAINTENANCE ...............................................12-112.1 FIELD EQUIPMENT PREVENTATIVE MAINTENANCE...............................12-112.2 LABORATORY INSTRUMENT PREVENTATIVE MAINTENANCE………12-1

SECTION 13 SPECIFIC ROUTINE PROCEDURES USED TO ASSESS DATA PRECISION, ACCURACY AND COMPLETENESS.........13-113.1 ACCURACY ASSESSMENT..............................................................................13-113.2 PRECISION ASSESSMENT................................................................................13-113.3 COMPLETENESS ASSESSMENT .....................................................................13-2

SECTION 14 CORRECTIVE ACTION...................................................................14-114.1 FIELD CORRECTIVE ACTION..........................................................................14-114.2 LABORATORY CORRECTIVE ACTION..........................................................14-214.3 CORRECTIVE ACTION DURING DATA VALIDATION AND DATA ASSESSMENT................................................................................14-3

SECTION 15 QUALITY ASSURANCE REPORTS TO MANAGEMENT .........15-1

SECTION 16 REFERENCES ....................................................................................16-1

APPENDICESAppendix A: MPCA Health and Safety Policy Manual.................................................A-1Appendix B: Equipment Decontamination SOP............................................................ B-1Appendix C: AScI-DETD Quality Assurance Manual .................................................. C-1Appendix D: AScI-DETD SOPs for: PAHs, PCBs, Mercury, and TOC ......................D-1Appendix E: AScI-DETD SOPs for: Organism Handling and Culturing, L. variegatus 28-day Bioaccumulation Toxicity Tests, Basic Water Chemistry Methods, and Total Lipid Measurements ................................ E-1


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LIST OF TABLES

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Table 1-1. Time Line for Completion of Major Project Tasks .....................................1-14

Table 1-2. Per Site Budget for Analytical, Toxicology, and Bioaccumulation Testing Work to be Conducted by AScI-DETD...........................................1-15

Table 3-1. Summary of Analytical Data Quality Objectives for Sediment and Tissue Samples...............................................................................................3-2

Table 4-1. MPCA Environmental Outcomes Division Sample Tracking Form .............4-4

Table 4-2. Sediment Sample Volume, Container, Preservation, and Holding Time Requirements ..........................................................................4-6

Table 6-1. Summary of Calibration Methods for Analytes in Sediment, Tissue, and Water Column Samples...........................................................................6-2

Table 7-1. Recommended Test Conditions for Conducting a Preliminary 4-day Sediment Toxicity Screening Test with L. variegatus ....................................7-2

Table 7-2. Recommended Test Conditions for Conducting a 28-day Sediment Bioaccumulation Test with L. variegatus........................................................7-3

Table 7-3. General Activity Schedule for Conducting a 28-day Sediment Bioaccumulation Test with L. variegatus........................................................7-4

Table 7-4. Test Acceptability Requirements for a 28-day Sediment Bioaccumulation Test with L. variegatus........................................................7-6

Table 8-1. Summary of Analytical Methods for Sediments and L. variegatus Tissues ..8-2

Table 8-2. PAH Compound MDLs for L. variegatus Matrix ...........................................8-3

Table 8-3. PCB Congener MDLs for L. variegatus Matrix ..............................................8-4

Table 9-1. Summary of Analytical Quality Control Checks for Critical Measurements....................................................................................9-3


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LIST OF FIGURES Page

Figure 1-1. Location of hot spot areas in the Duluth/Superior Harbor and a reference site at Kimball’s Bay ....................................................................1-2

Figure 1-2. Location of sediment sites in Slip C for four different MPCA sediment investigations ................................................................................1-4

Figure 1-3. Map of the 1994 sediment sampling sites in Minnesota Slip .......................1-5

Figure 1-4. Map of the 1995 sediment sampling sites in Allouez Bay ...........................1-6

Figure 1-5. Map of the 1995 sediment sampling sites near Boy Scout Landing, lower St. Louis River estuary .......................................................................1-7

Figure 2-1. Project organization chart .............................................................................2-5


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LIST OF ACRONYMS/ABBREVIATIONS

3D Three DimensionalAA Atomic AbsorptionAOC Area Of ConcernAScI-DETD AScI Duluth Environmental Testing DivisionASTM American Society for Testing and MaterialsBIOACC Sample Site Code Name for this InvestigationBSAF Biota-Sediment Accumulation FactorCAC Citizen’s Action CommitteeCF Calibration Factorscm CentimeterD DarkDDT Dichloro-diphenyl-trichloroethaneDQO Data Quality ObjectiveEPA Environmental Protection Agencyg GramGC/ECD Gas Chromatography/Electron Capture DetectionGC/MS-SIM Gas Chromatography/Mass Spectrometry Selective Ion MethodologyGLNPO Great Lakes National Program OfficeGPS Global Positioning SystemIJC International Joint CommissionIL Illinoiskg KilogramL Liter (or Light in terms of toxicity testing photoperiod)LOQ Limit of Quantificationm MeterMDL Method Detection LimitMDNR Minnesota Department of Natural Resourcesmg MilligrammL MilliliterMN MinnesotaMNS Minnesota Slip Code Name for Sediment Samples Collected in 1994MPCA Minnesota Pollution Control AgencyMS/MSD Matrix Spike/Matrix Spike DuplicateN/A Not ApplicableNaCl Sodium ChlorideNBS National Bureau of Standardsng Nanogram


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LIST OF ACRONYMS/ABBREVIATIONS (Continued)

NOAA National Oceanic and Atmospheric AdministrationNRRI Natural Resources Research InstitutePAHs Polycyclic Aromatic HydrocarbonsPCBs Polychlorinated BiphenylsPDOP Position Dilution of PrecisionPPDC Post Process Differential CorrectionPQL Practical Quantitation Limitpt. PointQA Quality AssuranceQAPP Quality Assurance Project PlanQA/QC Quality Assurance/Quality ControlQC Quality ControlR-EMAP Regional Environmental Monitoring and Assessment ProgramRFP Request for ProposalRPD Relative Percent DifferenceRSD Relative Standard DeviationSA Selective AvailabilitySD Standard DeviationSETAC Society of Environmental Toxicology and ChemistrySLPC Slip C Code Name for Sediment Samples Collected in 1997SOP Standard Operating ProcedureSRM Standard Reference MaterialSUS Slip C Code Name for Sediment Samples Collected in 1994TDL Target Detection LimitTOC Total Organic Carbon µg MicrogramU.S. United StatesWDNR Wisconsin Department of Natural ResourcesWI Wisconsinwt. Weight


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SECTION 1

PROJECT DESCRIPTION

1.1 INTRODUCTION

The Great Lakes National Program Office (GLNPO) has funded a study by the MinnesotaPollution Control Agency (MPCA) to conduct 28-day bioaccumulation tests of Duluth Harborsediments. In order to ensure that high quality data are collected, it is essential that qualityassurance/quality control (QA/QC) steps be adhered to while collecting, handling, and analyzingsediment samples. This document provides the Quality Assurance Project Plan (QAPP) whichwill be followed during this investigation. As part of the QAPP, a detailed work plan is given inthis chapter for the field sampling component of this study.

1.2 SITE DESCRIPTION

The Duluth/Superior Harbor has been designated as part of the St. Louis River Area of Concern (AOC) by the International Joint Commission (IJC) (Figure 1-1). Contaminated sedimentscontribute to many of the IJC impairments identified in the Stage 1 Remedial Action Plan (RAP)(MPCA/WDNR, 1992). Much of this contamination resulted from historical point and nonpointsources during the settlement and commercial/industrial development of this AOC. Currentsources of contamination include: discharges from industrial waste and sewage, storm waterrunoff, atmospheric deposition, ground water discharges to surface water, and resuspension andadvective transport of contaminated sediments to other locations in the AOC. Contaminants thatsettle out of the water column to the sediments have resulted in a long-term reservoir ofcontaminated bed sediments. The most widespread, bioaccumulative contaminants in this AOCinclude mercury, polycyclic aromatic hydrocarbons (PAHs), and polychlorinated biphenyls(PCBs). Some sites also have elevated levels of metals, dioxins/furans, diesel range organics,pesticides (including toxaphene), and tributlytin.

The aquatic ecological risks resulting from bioaccumulative contaminants in this AOC have notbeen well-characterized for lower food-chain organisms. Decisions regarding remediation ofcontaminated waterways, or disposal of dredged material for the maintenance of harbors and shipchannels, require assessing the ecological impacts of contaminants in sediments (McFarland,1995). Bioaccumulation tests provide one piece of information to assess ecological impacts. Sediment chemistry, toxicity tests, and benthological community surveys are other tools that canbe used to assess ecological impacts through a weight-of-evidence approach.

For this study, sediment samples will be collected from Slip C and Minnesota Slip for 28-daybioaccumulation tests with the oligochaete, Lumbriculus variegatus. Both of these sites have


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been included in sediment studies in which sediment chemistry analyses, sediment toxicity tests,and benthological community surveys have been conducted (Schubauer-Berigan and Crane, 1997;Crane et al., 1997; Breneman et al., 1999; Crane, 1999). Both sites are being targeted for potentialsediment remediation. Two potential reference control sites, from Allouez Bay and the Boy ScoutLanding area, will also be included in this study.

Slip C and Minnesota Slip occupy the northern section of the Duluth Harbor Basin in Duluth, MN(Figures 1-2 and 1-3, respectively). Historical uses have changed around both slips, and thephysical appearances of both slips have been modified since the late 1800s to enhance shippingactivities. A detailed description of Slip C is given in Crane (1999). This site is currentlybordered on the southwest side by the Duluth Timber Company, a firm that removes lumber fromhistoric structures. On the northwest side, Georgia-Pacific Corporation and Cutler-MagnerCompany border the slip. Georgia-Pacific manufacture products made from the compression offine wood fibers with phenolic resin and moisture inhibitors. Cutler-Magner Company importssalt at their dock. Minnesota Slip is currently bordered by parking lots on the north and west sides,by commercial businesses on the north side, and by a grass strip on the south side that separates itfrom a side street. A small marina is located along the north side of Minnesota Slip, which isoccupied by mostly sport fishing charter boats. The SS William S. Irvin, a former ore boat, ispermanently docked along the south side of the slip as a floating museum.

Allouez Bay is located east of the Superior entry to Lake Superior (Figure 1-4). This bay featuresextensive wetlands and shallow water habitat for fish and wildlife. It is one of two primaryspawning areas in the lower estuary for northern pike (MPCA/WDNR, 1992). The 600 acre rangeof Allouez Bay has been listed in the RAP as providing critical shoreline and near-shore habitatsthat must be protected from alteration, fill, and degradation (MPCA/WDNR, 1992).

The Boy Scout Landing area of the St. Louis River is located upstream of Oliver, WI and GaryNew Duluth, MN (Figure 1-5). This area is characterized by shallow water habitats, and is locatedupstream of the USX Superfund site.

1.3 PAST DATA COLLECTION ACTIVITIES

During the past seven years, the MPCA has been conducting focused sediment investigations inthe St. Louis River AOC to assess the extent of sediment contamination and associated biologicaleffects. For Slip C and Minnesota Slip, these studies have identified elevated levels of surficialand at-depth sediment contamination, acute toxicity resulting from exposure to some surficialsediments at Slip C, and degraded benthological communities at both sites (Schubauer-Beriganand Crane, 1997; Crane et al., 1997; Crane, 1999; Breneman et al., 1999, unpublished R-EMAPdata). The most prevalent contaminants of concern at both sites include: PAHs, PCBs, mercury,cadmium, copper, lead, and zinc (Schubauer-Berigan and Crane, 1997; Crane et al., 1997). Chromium, nickel, DDT metabolites, and toxaphene have also been found at elevated levels in


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Minnesota Slip (Schubauer-Berigan and Crane, 1997; Crane et al., 1997). Additionl detail on thedistribution of PAHs, PCBs, mercury, lead, and total organic carbon (TOC) in Slip C sedimentsis given in Crane (1999).

Surficial sediment samples were collected from several sites in Allouez Bay and the Boy ScoutLanding area during June 1995. These sites were sampled as part of a Regional EnvironmentalMonitoring and Assessment Program (R-EMAP) project. The MPCA, in collaboration with theU.S. EPA and Natural Resources Research Institute in Duluth, are conducting this study toevaluate status and trends in sediment chemistry, toxicity, and benthological community structurein the St. Louis River AOC. At these sites, acid volatile sulfide generally exceededsimultaneously extractable metals (SEM), thereby implying the SEM metals were notbioavailable; in addition, mercury and total PAHs were generally low for most of the sites(Breneman et al., 1999; unpublished R-EMAP data). One sample each, from both areas, werenot found to be acutely toxic to either Hyalella azteca or Chironomus tentans (unpublished R-EMAP data).

The bioaccumulation of PCB congeners was assessed at ten channel sites in the Duluth/SuperiorHarbor during early 1996. The U.S. Army Corps of Engineers collected composited channelsediments that were sent to a toxicity testing laboratory for 28-day bioaccumulation tests with L.variegatus. The results were compared to two different reference sites. Statistically significantdifferences occurred between the two reference locations for PCB congeners 086, 101, and 187(Normandeau Associates, 1996). Significant differences occurred between some of the samplesand the two reference sites for PCB congeners 015, 086, 101, 126, and 187 (NormandeauAssociates, 1996). The results of the Corps tests will be compared to the results of this projectfor PCB congeners.

1.4 CURRENT STATUS

The interpretation and uses of bioaccumulation data have garnered increased federal interest inrecent years. The U.S. Army Corps of Engineers and U.S. Environmental Protection Agency(EPA) held a joint bioaccumulation workshop during August 1995 to determine if more effectiveregulatory guidance could be developed for interpreting the effects of bioaccumulation from datacurrently collected during evaluations of dredged material (Bridges et al., 1996). DuringSeptember 1996, the U.S. EPA held a National Sediment Bioaccumulation Conference to: 1)define the current state of the science with respect to bioaccumulation assessment andinterpretation of bioaccumulation data, and 2) clarify how bioaccumulation data can be used tomake regulatory decisions (U.S. EPA, 1998). The MPCA will use the results of this study withinthe recommendations expressed at these conferences.

Several sites in the Duluth/Superior Harbor have been characterized as hot spot sites (Figure 1-1)which may eventually require remediation. A sediment remediation scoping project has recently


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been completed at Slip C (Crane, 1999). A similar type of project is in progress at MinnesotaSlip. Bioaccumulation testing will be a useful tool at these hot spot sites to assess ecologicalimpacts to benthic invertebrates.

Based on previous sediment investigations the MPCA has conducted, the following targetcompounds have been selected for further investigation: PAHs, PCBs, mercury, and TOC. Thecollection of sediment samples from Slip C and Minnesota Slip will be limited to the moderatelycontaminated sediments in the inner half of both slips.

1.5 PROJECT OBJECTIVES

The objectives of this project are to:

• Measure the bioaccumulation of PAHs, PCBs, and mercury in L. variegatus exposed tosurficial (~0-5 cm) sediments for 28-days. Study sites will be limited to moderatelycontaminated areas in Slip C and Minnesota Slip.

• Determine site-specific biota-sediment accumulation factors (BSAFs) for L. variegatus. 1.5.1 Work Tasks The proposed work will involve conducting 28-day sediment bioaccumulation toxicity tests withL. variegatus on selected harbor sediments. The U.S. EPA and the American Society for Testingand Materials (ASTM) have developed guidance on methods for evaluating bioaccumulation ofcontaminants associated with freshwater sediments using L. variegatus. This organism met anumber of criteria for bioaccumulation model development, including the ability to accuratelyreflect concentrations of contaminants in field-exposed organisms (Ingersoll, 1996). The testswill be conducted with five replicates per site, and both the sediments and tissues will beanalyzed for bioaccumulative contaminants (i.e., PAHs, PCBs, and mercury). Approximately 1-5g of tissue per replicate will be needed for residue analysis. Specific work tasks (and the responsible group) include the following: • Develop and distribute Request for Proposals (RFPs) for soliciting toxicity testing and

analytical laboratory proposals (MPCA) • Select toxicity testing/analytical laboratory for project and prepare contract for technical

services (MPCA; this work was awarded to AScI Corporation in Duluth, MN). • Prepare detailed Work Plan and Quality Assurance Project Plan (MPCA)


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• Collect sediment samples in the Duluth/Superior Harbor and lower St. Louis River estuary;deliver samples to AScI’s Duluth Environmental Testing Division (DETD) laboratory(MPCA)

• Run 4-day screening toxicity tests with L. variegatus on ten sediment samples (AScI-DETD) • Run 28-day sediment bioaccumulation tests with L. variegatus on six sediment samples,

including the reference control samples (AScI-DETD)

• Analyze sediment and tissue samples for contaminants of concern and for percent lipids intissue samples (AScI-DETD)

• Prepare toxicity test report and submit to MPCA (AScI-DETD) • Review toxicity test report (at MPCA) and submit to GLNPO • Calculate BSAFs (MPCA) • Present the results at a national conference (e.g., SETAC) and through other public forums • Prepare a manuscript for peer-review publication in a scientific journal (MPCA). 1.5.2 Project Target Parameters and Intended Data Usages The target parameters for this project include: 26 PCB congeners, 18 PAH compounds, andmercury. TOC will be measured in the associated sediment samples. Percent lipidmeasurements will be made of the test organisms. Intended data usages are to provide information that can be used by others for conducting foodchain modeling, ecological risk assessment, assessments of sediment quality, and for determiningdisposal options for dredged material from sites of interest. The results of this project will assistin identifying BSAFs for benthic invertebrates that may be used for restoring healthybenthological habitats. Expected data users for the results of this project are the MPCA, Minnesota Department ofNatural Resources (MDNR), Wisconsin Department of Natural Resources (WDNR), GLNPO,and potentially responsible parties. Other expected data users are the members of the St. LouisRiver Citizen’s Action Committee (CAC) and CAC Sediment Contamination Work Group interms of developing recommendations for sediment management alternatives at Slip C andMinnesota Slip. University and federal researchers, as well as consultants may also use thesedata. The bioaccumulation data will be added to GLNPO’s sediment database for the St. Louis


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River AOC, as well as to the Corps of Engineers sediment database for the Duluth/SuperiorHarbor. 1.5.3 Quality Objectives and Criteria for Measurement Data The Data Quality Objective (DQO) Process is a series of planning steps based on the ScientificMethod that is designed to ensure that the type, quality, and quantity of environmental data usedin decision making are appropriate for intended application. DQOs are qualitative andquantitative statements derived from outputs of each step of the DQO Process that: • Clarify the study objective • Define the most appropriate type of data to collect • Determine the most appropriate conditions from which to collect the data. The DQOs are then used to develop a scientific and resource-effective sampling design. TheDQO Process allows decision makers to define their data requirements and acceptable levels ofdecision during planning before any data are collected. 1.6 SAMPLE NETWORK DESIGN AND RATIONALE Since the MPCA has already conducted several sediment surveys in Slip C and Minnesota Slip,the contaminant data gained from these studies were used to refine the present sampling effort. The following sections will discuss in more detail the sampling design and rationale for selectingsites. 1.6.1 Sample Network by Task and Matrix Sediment and Lumbriculus tissue samples are the only matrices of concern for this investigation.Sediment samples will be collected during the week of May 25-28, 1999 for toxicity tests(screening and bioaccumulation) and chemical analyses. The field crew will consist of staff fromthe MPCA (Judy Crane and Harold Wiegner). The MPCA’s research vessel, the Naiad, will beused to collect sediment samples via a Shipek grab sampler attached to a winch at the back of theboat. Immediately following collection, the approximate upper 5 cm layer of sediment will be removedand composited into clean, 4-L Pyrex bowls. Due to the large volume (~ 9-10 L) of sedimentsto be collected at each site, the entire sediment volume will not be homogenized in the field. Instead, this will be done by the contract laboratory just prior to setting up the 4-day screeningtoxicity tests.


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Sediment samples will be stored on ice in either 4-L, 2-L, or 1-L pre-cleaned glass jars while onboard the Naiad. At the end of each day, the sediment samples will be delivered, via MPCAvehicle, to AScI-DETD’s laboratory. 1.6.2 Site Map of Sampling Locations The intended sediment sampling locations are shown in Figures 1-2 to 1-5. A total of 10 siteswere selected for screening toxicity tests, of which six of these sites were to be used for thebioaccumulation tests. It is possible, however, that depending on the nature of the encounteredfield conditions, that some of these locations will be changed. This is most likely to happen atMinnesota Slip where the sediments are quite sandy. This makes it difficult to obtain a cohesivesediment sample. The MPCA Principal Investigator, in consultation with the MPCA Field TeamLeader, will decide if site locations will be changed. 1.6.3 Rationale of Selected Sampling Locations The U.S. EPA Region 5 document on “Statistical Techniques Applied to Sediment Sampling(STATSS)” (Lubin et al., 1995) was referred to when designing this study. Based on the budgetavailable for this project, a nonrandom sampling plan was used to select sites where previouslycollected sediment chemistry data were available. Some of these sites also had toxicity andbenthological community data established for them. A total of ten sites were selected for screening toxicity tests, of which six of these sites were tobe used for the bioaccumulation tests. In Slip C, previously sampled sites at R-EMAP 51, SLPC13, SLPC 14, and SUS 3 were selected for this study (Figure 1-2). Site SUS 3 had previouslyshown significant acute toxicity to Chironomus tentans as a result of 10-day exposure to theupper 15 cm sediment segment (Crane et al., 1997). This site was included to assess whether theupper 5 cm segment of sediment would be acutely toxic to L. variegatus. In Minnesota Slip, previously sampled sites at MNS 01, MNS 02, MNS 04, and 98-MNS-03were selected for this study (Crane et al., 1997; unpublished data collected in 1998) (Figure 1-3).In Allouez Bay, site 41 from the 1995 R-EMAP field sampling schedule was selected for thisstudy (Figure 1-4). Similarly, site 88 from the 1995 R-EMAP sites was selected to represent thearea downstream from Boy Scout Landing (Figure 1-5). Both of these R-EMAP sites were fairlyclean in terms of mercury and PAH contamination, although PCBs were not measured at thesesites (unpublished R-EMAP data). R-EMAP site 41 had an elevated TOC content in thesediments (9.9 %) and contained fibrous organic matter; this site was selected as a referencecontrol sample for some of the high TOC and fibrous sediments in Slip C. R-EMAP site 88 wasselected as a more representative reference control sediment for the Minnesota Slip sediments. Itis anticipated that two acceptable sites, each, would emerge at both Slip C and Minnesota Slip


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after the 4-day screening toxicity tests are conducted. If this does not happen, then some newsediments may need to be re-sampled prior to setting up the 28-day bioaccumulation tests. 1.7 PROJECT SCHEDULE 1.7.1 Anticipated Date of Project Mobilization The earliest date for sediment sampling is May 25, 1999. It is anticipated that most of thesediment sampling will be completed within three to four days. 1.7.2 Task Bar Chart and Associated Time Frames The dates of projected milestones are indicated in Table 1-1. Although the grant was awardedOctober 1, 1997, work was delayed until higher priority sediment projects in the St. Louis RiverAOC were completed. The tasks listed in Table 1-1 are beginning with a time period of February1998. 1.8 BUDGET FOR ANALYTICAL, TOXICOLOGY, and BIOACCUMULATION WORK Table 1-2 contains the budget for this project. All contracted work will be completed by AScICorporation. The contractual costs include the following: running one negative control samplewith the 4-day screening toxicity tests, running one reference control sample (excludinganalytical costs) with the 28-day bioaccumulation tests, conducting a 4-day reference toxicant(NaCl) test with L. variegatus, and preparing a summary report. The second reference controlsample for the bioaccumulation tests will be charged as a separate sample. The total cost of AScI’s contract with the MPCA will not exceed $35,000.00. Costs will bebroken up as follows: • 4-day sediment toxicity tests with L. variegatus (ten samples): $1,500.00• 28-day sediment bioaccumulation toxicity tests with L. variegatus (five samples plus one no-

cost reference control sample): $8,200.00• Analytical analyses of sediments and tissues for selected parameters: $21,800.00• Ten percent holdback (payable upon approval of final report): $3,500.00


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Table 1-2. Per Site Budget for Analytical, Toxicology, and Bioaccumulation Testing Work to be

Conducted by AScI-DETD

Test Quantity Cost

4-Day Sediment Toxicity Screening Test 1 $150.00

28-Day Sediment Bioaccumulation Test 1 $1,640.00

Sediment PAH Compound Analysis 1 $250.00

Sediment PCB Congener Analysis 1 $350.00

Sediment Mercury Analysis 1 $40.00

Sediment TOC Analysis 1 $30.00

L. variegatus PAH Compound Analysis 5 @ $250.00 $1,250.00

L. variegatus PCB Congener Analysis 5 @ $350.00 $1,750.00

L. variegatus Mercury Analysis 5 @ $40.00 $200.00

L. variegatus Lipid Analysis 5 @ $35.00 $175.00

TOTAL PER SITE $5,835.00

Bioaccumulation QA Project Plan

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SECTION 2

PROGRAM ORGANIZATION AND RESPONSIBILITIES

The MPCA Principal Investigator will have overall responsibility for all phases of this project. Thevarious quality assurance and management responsibilities of key project personnel are definedbelow. 2.1 PROJECT ORGANIZATION CHART The lines of authority for this specific project can be found in Figure 2-1. This chart includes all theindividuals discussed in the following sections. 2.2 MPCA PERSONNEL The MPCA staff associated with this project can be reached at the following address: Environmental Outcomes Division Minnesota Pollution Control Agency 520 Lafayette Road St. Paul, MN 55155-4194 General Phone: 1-800-657-3864 Fax: 651-297-7709 Person: Responsibilities: Lanny Peissig, Supervisor Supervise Principal Investigator Standards Development & Application Unit Approve contract for technical services Environmental Research & Reporting Section Approve QAPP Phone: 651-297-1781 Email: [email protected] Judy Crane, Principal Investigator Develop request for proposals (RFPs) Standards Development & Application Unit Review responder proposals Environmental Research & ReportingSection Contract out toxicology and analytical work Phone: 651-297-4068 Develop work plan and QAPP E-mail: [email protected] Order supplies Conduct field work Analyze data and write report Perform project and grant management tasks


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Person: Responsibilities: Harold Wiegner, Field Team Leader Assemble supplies Ground Water & Toxics Unit Coordinate field sampling Environmental Monitoring & Analysis Section Coordinate sending samples to AScI-DETD Phone: 651-296-9315 Email: [email protected] Kim Sandrock, QA Coordinator Review and approve QAPP Biological Monitoring Unit Conduct field and laboratory audits, as needed Environmental Monitoring & Analysis Section Respond to QA/QC questions Phone: 651-296-7387 Email: [email protected] 2.3 GLNPO PERSONNEL The GLNPO staff associated with this project are as follows: Person: Responsibilities: Kathleen O’Connor, Project Officer Coordinate grant requests U.S. EPA GLNPO Review work plan and QAPP 17G Provide technical assistance, as needed 77 West Jackson Boulevard Review quarterly progress reports Chicago, IL 60604 Review draft and final reports Phone: 312-353-3490 Fax: 312-353-2018 Email: [email protected] Louis Blume, QA Officer Review and approve QAPP Same address as K. O’Connor Conduct field and lab audits, as needed Phone: 312-353-2317 Provide technical assistance for QA/QC Fax: 312-353-2018 questions Email: [email protected] 2.4 CONTRACT LABORATORY MANAGEMENT AScI-DETD will have their own provision for conducting an internal QA/QC review of the databefore it is released to the MPCA. The contract supervisor will contact the MPCA PrincipalInvestigator with any data concerns.


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A QA/QC section will be included in the bioaccumulation report submitted to the MPCA. Corrective actions will be reported to the MPCA Principal Investigator with the QA/QC section. AScI-DETD may be contacted by the GLNPO Project Officer, GLNPO QA Officer, or MPCA QACoordinator at any time to discuss QA/QC concerns. The AScI-DETD staff associated with this project can be reached at the following address: AScI Corporation Duluth Environmental Testing Division (DETD) 4444 Airpark Boulevard Duluth, MN 55811 Phone: 218-722-4040 Fax: 218-722-2592 Email: [email protected] The TOC analysis of sediment samples will be subcontracted to the Natural Resources ResearchInstitute (NRRI) in Duluth, MN. Person: Responsibilities:

Joe Amato, Deputy Director

Ensure laboratory resources are available on an as-required basis

Interpret data and prepare report

Randy Helander, Chemist Conduct PAH and PCB analyses of sediment and tissue samples

Oversee data review and preparation of analytical section of report

Elaine Ruzycki, Chemist NRRI, University of Minnesota-Duluth 5013 Miller Trunk Highway Duluth, MN 55811 Phone: 218-720-4389 Fax: 218-720-9412 Email: [email protected]

Conduct TOC analyses of sediment samples

Provide data to AScI-DETD


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Person:

Responsibilities:

Tim Harold, Chemist Conduct mercury analyses of sediment and tissue samples

Determine lipid content of L. variegatus tissue

Oversee data review and preparation of analytical section of report

Joe Dierkes and Todd McGuire, Biologists Coordinate set-up, maintenance, and tear

down of 4-day screening toxicity tests and 28-day bioaccumulation tests

Conduct routine monitoring of physico- chemical conditions during the tests

Conduct statistical comparisons of sample results with the negative control orreference control sample

Oversee data review and preparation of toxicity testing and bioaccumulation testing sections of report

Todd McGuire, Biologist Maintain Lumbriculus culture

Alan Mozol, QA Officer Provide information for QAPP

Conduct internal laboratory audits, as needed

Ensure proper implementation of applicable standard operating procedures (SOPs)

Review and validate laboratory data Prepare QA/QC section of AScI-DETD’s report

to the MPCA


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L. Peissig MPCA Supervisor

K. Sandrock MPCA QA Coordinator

J. Crane MPCA Principal

Investigator

K. O’Connor GLNPO Project

Officer

L. Blume GLNPO

QA Officer

AScI-DETD Contacts

J. Amato, Deputy Director A. Mozol, QA Officer R. Helander, Chemist T. Harold, Chemist J. Dierkes, Biologist T. McGuire, Biologist

H. Wiegner MPCA Field Team Leader

Figure 2-1. Project organization chart.

E. Ruzycki NRRI Chemist


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SECTION 3

QUALITY ASSURANCE OBJECTIVES FOR MEASUREMENT DATA The overall QA objectives for this project are to develop and implement procedures for fieldsampling, sample tracking, laboratory analysis, and reporting that will provide high quality results. Specific procedures for sampling, sample tracking, laboratory instrument calibration, laboratoryanalysis, toxicity and bioaccumulation testing, reporting of data, internal quality control, audits,preventive maintenance of field equipment, and corrective actions are described in other sections ofthis QAPP. 3.1 TARGET DETECTION LIMITS FOR CHEMICALS 3.1.1 Definition The target detection limit (TDL) for a specific chemical is a performance goal set between thelowest, technically feasible detection limit for routine analytical methods and available regulatorycriteria or guidelines for evaluating dredged material (USEPA, 1995). This TDL definition is beingused for this project since Minnesota does not have any sediment quality or tissue guidelines of itsown yet. The TDL is equal to, or greater than, the lowest amount of a chemical that can be reliablydetected based on the variability of the blank response of routine analytical methods. 3.1.2 Laboratory TDL Objectives The laboratory TDLs for sediment and tissue samples are given in Table 3-1. The TDL valuesgiven in U.S. EPA (1995) were used as a guide for selecting the TDLs for this project. Formercury, though, a stricter TDL was set based on the limit of quantification (LOQ) of mercury for alarge Regional Environmental Monitoring and Assessment Program (R-EMAP) project conductedin the St. Louis River AOC. The tissue TDLs for PCB congeners, individual PAHs, and mercurywere based on the Lumbriculus tissue method detection limits (MDLs) developed by AScI-DETD. 3.2 PRECISION 3.2.1 Definition Precision is a measure of the degree to which two or more measurements are in agreement.


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3.2.2 Field Precision Objectives Field precision is assessed through the collection and measurement of field replicates at a rate ofone replicate per ten analytical samples. No field replicates will be needed for this project since lessthan ten samples will be collected. 3.2.3 Laboratory Precision Objectives Precision in the laboratory is assessed through the calculation of relative percent difference (RPD)for two replicates and relative standard deviation (RSD) for three or more replicate samples. Theequations to be used for precision in this project can be found in Section 13.2 of this QAPP. Precision control limits are given in Table 3-1. 3.3 ACCURACY 3.3.1 Definition Accuracy is the degree of agreement between an observed value and an accepted reference value. Table 3-1. Summary of Analytical Data Quality Objectives for Sediment and Tissue Samples

Sediment TDL

Tissue TDL

Analyte (dry wt.) (wet wt.) Precision Accuracy Completeness PCB Congeners

1 µg/kg

30 µg/kg

50% RPD

50-120%

95%

Individual PAHs

20 µg/kg

50 µg/kg

50% RPD

50-130%

95%

Mercury 5 µg/kg 53 µg/kg 20% RPD 80-120% 95% TOC 0.1% N/A 20% RPD 80-120% 95% N/A = Not Applicable RPD = Relative Percent Difference TDL = Target Detection Limit


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3.3.2 Field Accuracy Objectives Accuracy in the field is assessed through the adherence to all sample handling, preservation, andholding times. 3.3.3 Laboratory Accuracy Objectives Laboratory accuracy is assessed through the analysis of matrix spikes (MS), or standard referencematerials (SRM), and the determination of percent recoveries. The equation to be used for accuracyin this project can be found in Section 13.1 of this QAPP. Accuracy control limits are given inTable 3-1. 3.4 COMPLETENESS 3.4.1 Definition Completeness is a measure of the amount of valid data obtained from a measurement systemcompared to the amount that was expected to be obtained under normal conditions. 3.4.2 Field Completeness Objectives Field completeness is a measure of the amount of valid measurements obtained from all themeasurements taken in the project. The equation for completeness is presented in Section 13.3 ofthis QAPP. Field completeness for this project will be greater than 90%. 3.4.3 Laboratory Completeness Objectives Laboratory completeness is a measure of the amount of valid measurements obtained from all themeasurements taken in the project. The equation for completeness is presented in Section 13.3 ofthis QAPP. Laboratory completeness for this project will be equal to or greater than 95% of thetotal number of samples submitted to AScI-DETD (Table 3-1). 3.5 REPRESENTATIVENESS 3.5.1 Definition Representativeness expresses the degree to which data accurately and precisely represent acharacteristic of a population, parameter variations at a sampling point, a process condition, or anenvironmental condition.


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3.5.2 Measures to Ensure Representativeness of Field Data Representativeness is dependent upon the proper design of the sampling program and will besatisfied by ensuring that the field sampling plan is followed and that proper sampling techniquesare used. The sampling design of this project is representative of moderately contaminatedsediments in Slip C and Minnesota Slip. In addition, the reference control sites will berepresentative of “clean” areas for the Duluth Harbor. 3.5.3 Measures to Ensure Representativeness of Laboratory Data Representativeness in the laboratory is ensured by using the proper analytical, toxicity, andbioaccumulation procedures; meeting sample holding times; and analyzing and assessing laboratoryduplicates for the chemistry samples. 3.6 COMPARABILITY 3.6.1 Definition Comparability is an expression of the confidence with which one data set can be compared withanother. Comparability is also dependent on similar QA objectives. 3.6.2 Measures to Ensure Comparability of Field Data Comparability is dependent upon the proper design of the sampling program and will be satisfiedby ensuring that the field sampling plan is followed and that proper sampling techniques are used. 3.6.3 Measures to Ensure Comparability of Laboratory Data Planned analytical data will be comparable when similar sampling and analytical methods are usedand documented in the QAPP. Comparability is also dependent on similar QA objectives. Theanalytical data obtained from sediment samples in this study will be as comparable, as possible, todata collected from previous MPCA sediment investigations at these sites. 3.7 LEVEL OF QUALITY CONTROL EFFORT Method blanks, standard reference materials (SRM), and matrix spike samples will be analyzed toassess the quality of the data resulting from the analytical programs.


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Method blank samples are generated within the laboratory and used to assess contaminationresulting from laboratory procedures. Matrix spikes provide information about the effect of thesample matrix on the digestion and measurement methodology. All matrix spikes are performed induplicate and are hereinafter referred to as MS/MSD samples. One MS/MSD will be collected forevery 20 or fewer investigative samples. MS/MSD samples are designated/collected for organicanalyses only.


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SECTION 4

SAMPLING PROCEDURES 4.1 SUMMARY OF SAMPLING ACTIVITY Sediment samples will be collected during May 25-28, 1999. Field sampling will be conducted byMPCA staff using their research vessel, the Naiad. All field activities will be in accordance withthis QAPP and with the MPCA Health and Safety Policy Manual given in Appendix A. The sites will be located in the field by interpolation from the NOAA navigational charts and fromaerial photographs of Slip C and Minnesota Slip. The geographic coordinates of the sites will beobtained with a GPS unit. However, the field GPS measurements may be adversely affected by thepresence of the SS William A. Irvin, a former ore carrier, in Minnesota Slip. Therefore, the marinaboat slip markers in Minnesota Slip will be used to provide an additional geographic reference tothe position of field samples. The field sites will be sampled from the expected “least” contaminated to the “most” contaminatedsites. The Naiad will be anchored at each sampling site. Surficial sediment samples will becollected with a Shipek grab sampler extended from a winch at the stern end of the boat. Thesamples will be processed on-board the Naiad immediately after collection. The approximate upper5 cm of sediment will be scraped off and put into pre-cleaned glass jars with Teflon -lined lids. Approximately nine to ten grab samples will need to be obtained at each site to composite enoughsediments (~9-10 L) for this project. The winch and/or the boat will be repositioned for each grabsample. A physical description of the sediment samples will be made. Any twigs, wood chunks, or rockswill be removed from the samples prior to compositing them. All field data will be recorded in a water-proof, bound field notebook, and a label of identifyinginformation will be attached to each sample jar. Although strict chain-of-custody procedures willnot be followed for this investigation, a sample tracking system will be in place to reduce thepossibility of losing sample jars. The following sections provide additional details on the sampling procedures to be used for thisinvestigation. 4.2 SAMPLING NETWORK DESIGN AND RATIONALE The sampling network design and rationale was previously discussed in Section 1.6. The sedimentsampling for this study will take advantage of previous sediment investigations that pinpointed


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Section 4 Page 4-2 areas of moderately contaminated sediments in Slip C and Minnesota Slip, as well as “clean”sediments in Allouez Bay and downstream of Boy Scout Landing. The U.S. EPA Region 5 document on “Statistical Techniques Applied to Sediment Sampling(STATSS)” (Lubin et al., 1995) was referred to when designing this study. The project budget($35,000) was the limiting factor for determining how many samples would be collected. Anonrandom sampling plan was designed to target areas in Slip C and Minnesota Slip that containedelevated levels of mercury, PAHs, and PCBs. Similarly, relatively clean areas of Allouez Bay anddownstream of Boy Scout Landing were targeted for the reference sites. A total of ten sampling sites were selected for this study. The sites will be located in the field byinterpolation from the NOAA navigational charts and from physical markers in the boat slips. Thegeographic coordinates of the sites will be obtained with a GPS unit. Sediment soundings and thedepth of the water column will be taken at each site. The sediment soundings will determine thedepth of soft sediments at each site. Multiple sediment samples will be collected at each site, usinga Shipek grab sampler, and they will be composited until 9-10 L of sediment are obtained. Sediment samples will be collected at the reference site near Boy Scout Landing first, followed byAllouez Bay, Slip C, and then Minnesota Slip. This will generally progress from leastcontaminated to most contaminated sites. The Shipek grab sampler is able to obtain a fairly cohesive sediment sample, although someslumping of the sample is expected. Subsections of the sediment sample will be obtained when thesampler is rotated open; it will not be necessary to empty the sample into a pan. The approximateupper 5 cm layer of sediment will be removed, using a Teflon -coated spatula, and placed into aclean Pyrex bowl. Physical observations of the sediment samples will be made, and any largeobstructions (e.g., twigs, wood chunks, rocks) will be removed prior to compositing subsamples. The subsamples will be transferred into pre-cleaned glass jars (i.e., 4-L, 2-L, or 1-L) with Teflon -lined lids. It is anticipated the sediment chemistry analyses for mercury, PAHs, PCBs, TOC, and percentmoisture will be run on each composite sample. In addition, 4-day screening toxicity tests withL. variegatus will be run on all ten samples. Based on the results of the screening toxicity tests, four sample sites and the two reference controlsediments will be used in 28-day bioaccumulation tests with L. variegatus. Any other sample sitesthat had acceptable screening toxicity results, but were not selected for bioaccumulation testing willbe stored at 4°C (in the dark) at AScI-DETD’s laboratory until the successful completion of thebioaccumulation tests. After that time, the extra samples will be discarded.


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Section 4 Page 4-3 4.3 SAMPLE TRACKING PROCEDURE Sample tracking will be an important component of this project to ensure that samples are notmisplaced or lost during field collection and transport to AScI-DETD. Legal chain-of-custodyprocedures will not be followed for this project because the data will not be used for enforcementpurposes. A sample tracking system will be in place using modified chain-of-custody proceduresand forms (Table 4-1). 4.3.1 Sample Identification System All samples will be assigned a unique identifying code that identifies the project sample site(BIOACC), year of sampling (1999) and sample number (01 through 10). Since all of the sampleswill be of a sediment matrix, a matrix identifier will not be included in the sample code. Also,since sampling will occur during one temporal time period, the entire date will not be included inthe code. In order to facilitate the ease with which sample identifiers are written on the jar labels,the code will be as such: BIOACC-99-01 through BIOACC-99-10. 4.3.2 Initiation of Field Tracking Procedure Field tracking procedures will begin as soon as samples are collected. A sample tracking form willbe filled out for each sample as they are collected (Table 4-1). Although this form contains a chain-of-custody record, it will not be legally binding. The field tracking forms will accompany thesamples during transport to AScI-DETD. 4.3.3 Field Activity Documentation/Logbook A waterproof field notebook will be used to document information as specified in Section 5.1 ofthis QAPP. 4.3.4 Sample Shipment and Transfer of Samples The shipment and transfer of samples is discussed in more detail in Section 5.1. During eachsampling day, samples will be stored on ice in a cooler. The samples will be transported to AScI-DETD at the end of each day. In case the samples cannot be immediately transferred to AScI-DETD’s laboratory, the samples will be stored temporarily in a refrigerator at the MPCA’s Duluthregional office. The integrity of the sample jars will be inspected upon arrival at AScI-DETD’s laboratory. Eachsample will be logged in according to AScI-DETD standard operating procedures. Sample log-inwill include measurement of arrival temperature, completion of sample tracking forms, and visualobservation of sediment characteristics including appearance, general pore water content, and


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Section 4 Page 4-5 overlying water. All information pertaining to individual sample labeling will be transcribed toAScI-DETD’s sample receipt logbook. The MPCA will be notified immediately if any difficultiesin sample identification, or concerns of sample integrity, are encountered during sample log-in. Thesamples will be stored in darkness and refrigerated between 1 and 4°C until they are prepared fortesting. 4.4 SAMPLE CONTAINERS, SAMPLE PRESERVATION, AND MAXIMUM HOLDING TIME 4.4.1 Sediment Samples As mentioned in Section 4.6.2, composited sediment samples from each site will be collected in acombination of 4-L, 2-L, and 1-L pre-cleaned glass jars. The MPCA did not want to collect thesediment samples in large plastic buckets with lids, as some agencies do, due to concerns about theabsorption of PCBs and PAHs into the plastic. In addition, plastic can leach phthalates into thesamples. Due to the large volume of sediment to be collected at each site, it will not be feasible to allocatesubsamples for chemical analysis in the field. Instead, the jars of samples from each site will bemixed and composited in a clean aquarium at AScI-DETD’s laboratory. Uniform subsamples willbe collected per the requirements specified in Table 4-2. The sample containers for organics will be solvent-rinsed glass jars with Teflon -lined lids.Mercury, TOC, and percent moisture will all be run on the same sample jar that will be a 125-mLpre-cleaned polyethylene jar. The sample integrity will be preserved by keeping the samples cold at4 °C; organic samples will be kept in the dark. Standard holding times for sediments are not as welldeveloped as for water samples. The maximum holding times given in Table 4-2 will be used as ageneral guideline. 4.4.2 Bioaccumulation Tissue Samples The sample containers for tissue samples will be solvent rinsed brown glass bottles. Approximately4-5 g masses of L. variegatus tissue from each test replicate will be added to a separate samplecontainer. The tissue samples will be frozen, for up to 30 days, before they are analyzed formercury, PAHs, PCBs, and percent lipids. 4.5 SAMPLE HANDLING, PACKAGING, AND SHIPMENT As discussed in Section 4.3.4, sediment samples will be hand delivered to AScI-DETD’slaboratory. Care will be taken with transporting the samples so that they stay cold (i.e., through useof ice) in the coolers. The sample tracking forms will accompany the samples (Table 4-1).


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Section 4 Page 4-6 Table 4-2. Sediment Sample Volume, Container, Preservation, and Holding Time Requirements Size/Type of Analyte Amount Required Jar Preservation Holding Time PAHs 100 g 250 mL, glass Cool/dark, 4°C 42 days

PCBs 100 g 250 mL, glass Cool/dark, 4°C 42 days

Mercury 100 g 125 mL, plastic Cool, 4°C 30 days TOC 30 g 125 mL, plastic Cool, 4°C 40 days Percent Moisture 30 g 125 mL, plastic Cool, 4°C 40 days The samples are not anticipated to be classified as hazardous waste; therefore, Department ofTransportation regulations will not apply to the transport of samples, via MPCA vehicle, to AScI-DETD’s laboratory. 4.6 DECONTAMINATION PROCEDURES 4.6.1 Personnel and Equipment All field sampling personnel will be required to wear steel-shoed shoes and gloves; this shouldprotect most staff against contamination of their extremities. Tyvex suits will be available on theboat, but will not be required to be worn. Equipment (e.g., Pyrex mixing bowls, spatulas, spoons) will be decontaminated with 10% HCl,hexane, acetone, and distilled water following the general Equipment Decontamination SOP givenin Appendix B. This SOP was obtained from U.S. EPA (1995) and has not been adopted as anofficial MPCA SOP yet. Acid rinsate will be collected in a one gallon Nalgene plastic bottle. Thesolvent rinsate will be stored in a one gallon screw top empty solvent jug held in a Nalgene plasticsafety bottle carrier. At the end of each sample day, the acid and solvent wastes will be transferredto similar containment in the MPCA vehicle. The wastes will be transported to the MPCA office inSt. Paul for disposal. One deviation from the Equipment Decontamination SOP is that equipmentblanks will not be collected for this study.


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Section 4 Page 4-7 4.6.2 Sampling Bottles The sediment samples will be collected in a combination of 4-L, 2-L, and 1-L pre-cleaned glass jarswith Teflon®-lined lids. These jars have been quality assured to meet U.S. EPA “Specifications andGuidelines for Contaminant-Free Sample Containers.” Other pre-cleaned glass and plastic jars, asnoted in Table 4-2, will be used for transferring representative subsample of sediments for chemicalanalysis. 4.6.3 Sampling Devices Sediment samples will be collected using a Shipek grab sampler. The Shipek sampler will bedecontaminated by rinsing it in harbor water to remove gross amounts of sediments. Next, it willbe scrubbed with phosphate-free soap followed by rinses of distilled water, hexane, acetone, anddistilled water. This full procedure will be done between sites. Within each site, only grossamounts of sediment will be removed from the sampler after each composite sample is collected. The depth of the soft sediments at each site will be measured by using sediment sounding poles(WDNR, 1995). The sounding poles will not need to be decontaminated, except for a water rinse toremove gross amounts of sediment. These poles will only be used to measure the depth to refusalin the sediments, and thus constitute a physical measurement. 4.7 SEDIMENT SAMPLING EQUIPMENT AND PROCEDURES 4.7.1 Sampling Devices Sediment samples will be collected using a Shipek grab sampler. The depth of the soft sedimentsat each site will be measured by using sediment sounding poles. These poles will also be used todetermine the depth of the water column at each site. 4.7.2 Sampling Procedures For each site, multiple grab samples will be collected from a relatively homogeneous sedimentdeposit (i.e., all grabs should be of similar sand/silt content). Each grab sample will be collectedfrom an undisturbed area of sediment. A winch, with a rotating arm, will be used to lower and raisethe Shipek grab sampler out of the water. Since this sampler is very heavy, it will be lowered into a“cradle” onboard the boat prior to opening it to reveal the sediments. Although some slumping ofthe sediments may occur, the MPCA Principal Investigator and Field Team Leader have determinedthat this sampler works better than a Ponar grab sampler in terms of collecting a more cohesivesediment sample.


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Section 4 Page 4-8 The approximate upper 5 cm layer of sediment will be removed using a Teflon®-lined spatula. Thesample will be placed into a 4-L acid and solvent-rinsed Pyrex® measuring cup. Any large objectssuch as twigs, wood chunks, or stones will removed, and observations about the sediments (e.g.,color, odor, appearance of oil sheens, sand/silt/clay content) will be recorded. The sediments willbe briefly mixed and transferred into a pre-cleaned sample jar. The jar will be labeled with thesample site code, date and time period of sampling, approximate depth of the sediment sample,name(s) of collector(s), and the project name (i.e., sediment bioaccumulation). Additional grabsamples will be collected and processed, as mentioned above, and composited together in thesample jars until a total volume of 9-10 L is obtained. 4.8 QC SAMPLE PROCEDURES Good QC sample procedures will be followed to reduce the risk of cross-contaminating samples ormislabeling samples. The MPCA Principal Investigator will ensure that data are being recordedappropriately on the sample labels and in the field notebook. For other QC measures, it is notanticipated that field equipment blanks will be taken since this study will not deal with low levels ofcontaminants. 4.9 FIELD REPLICATE SAMPLE COLLECTION Field replicates will not be collected due to the low number of samples included in this study. 4.10 FIELD MEASUREMENTS Sediment soundings will be taken at each site to determine the approximate depth of the softsediment layer. This will be done using a long metal rod of known length. This sediment soundingpole will be lowered into the sediment and pushed in until the point of refusal (WDNR, 1995). A global positioning system (GPS) will be used to determine station positions by receiving at least100 digital codes from four or more satellite systems (3D Mode), computing time and distance, andthen calculating an earth-based position. This will be done with a position dilution of precision(PDOP) value of less than six. Recorded data will be downloaded on a personal computer, and theerror caused by selective availability (SA) will be eliminated utilizing post process differentialcorrection (PPDC). This process will be carried out using Pfinder software and base files from theMinnesota Power Base Station in Duluth. The final coordinates will be accurate to within 2-5 m. 4.11 PREVENTATIVE MAINTENANCE PROCEDURES/SCHEDULE Preventative maintenance of the sampling equipment, GPS, and boat will be done prior to samplingto ensure everything is in good working order. A tool kit, duct tape, some extra supplies, and acellular phone will be brought along in case any impromptu repairs or adjustments are needed.


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Section 4 Page 4-9 The R/V Naiad will be moored at the Minnesota Boat Basin, a commercial marina, each evening. Normal maintenance of the boat will be conducted at that time to secure the boat and to implementany corrective actions. 4.12 SAMPLE DISPOSAL Extra sediment samples will be disposed of in the field by release into the water after all samplinghas been completed at that site.


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SECTION 5

SAMPLE TRACKING PROCEDURES 5.1 FIELD TRACKING PROCEDURES Field logbooks will be used to record data collection activities. As such, entries will be described inas much detail as possible. The field logbooks will be bound notebooks with waterproof paper. For this survey, one field notebook will be sufficient. The notebook will be assigned to the MPCAPrincipal Investigator and will be used by both her and the Field Crew Leader to recordinformation. The title page of the field notebook will contain the following information: • Person to whom the notebook is assigned• Project name• Project start date and end date. Entries into the notebook will contain a variety of information. At the beginning of each entry, thedate, start time, weather, names of all sampling team members present, level of personal protectionbeing used, and the signature of the person making the entry will be entered. The names of visitorsto the site will also be recorded in the field notebook. The types of measurements made (e.g., GPS coordinates) and samples collected will be recorded. All entries will be made using permanent ink, signed, and dated, and no erasures will be made. Ifan incorrect entry is made, the information will be crossed out with a single strike mark that issigned and dated by the sampler. Whenever a sample is collected, or a measurement is made, adetailed description of the location of the station, which includes GPS coordinates, will berecorded. The number of photographs taken of the station, if any, will also be noted. Allequipment used to make measurements will be identified. A site-specific identification number(e.g., BIOACC-99-01) will be assigned to sampling sites prior to sample collection. The sample packaging and shipment procedures summarized below will ensure that the sampleswill arrive at AScI-DETD’s laboratory intact. • The Field Team Leader is personally responsible for the care and custody of the samples until

they are transferred or properly dispatched. As few people as possible will handle the samples. • All sample jars will be identified by labels that contain the following information: sample

identification number, sampling location, date/time of collection, sampler initials, and type ofanalysis.


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• Sample labels are to be completed for each sample using waterproof ink unless prohibited byweather conditions. For example, a logbook notation would explain that a pencil was used tofill out the sample label because the pen would not function.

• Samples are accompanied by a properly completed sample tracking form. The sample numbers

and locations will be listed on the sample tracking form. When transferring the possession ofsamples, the individuals relinquishing and receiving the samples will sign, date, and note thetime of the record. Although not legally binding, this record documents the transfer of custodyof samples from the sampler to another person or laboratory.

• Samples will be stored in coolers packed with ice (4 °C) before transporting them to AScI-

DETD at the end of each sampling day. In case the samples cannot be immediately transferredto AScI-DETD’s laboratory, the samples will be stored temporarily in a refrigerator at theMPCA’s Duluth regional office.

• All shipments will be accompanied by the Sample Tracking form identifying the contents. A

copy of the Sample Tracking form will be retained on file at the MPCA 5.2 LABORATORY CUSTODY PROCEDURES Laboratory custody procedures for sample receiving and log-in, sample storage and numbering,tracking during sample preparation and analysis, and storage of data will follow AScI-DETD’s internal procedures (Appendix C). All samples will be assigned an unique MPCA sample number. These numbers are to be used fortracking the sample throughout the analyses, although the laboratory may assign a separate samplecontrol number based on their individual tracking system. When reporting analytical results, AScI-DETD will report to the MPCA both sample control numbers to facilitate data control andinteragency communication regarding samples. 5.3 DATA STORAGE All original field and laboratory processing notes will be stored by the MPCA PrincipalInvestigator. These files will contain field notes, processing information for sediments, and theoriginal copies of data and reports sent from AScI-DETD. All sample tracking forms (field, and in-lab) will be delivered to the Principal Investigator along with the final data, where they will becomepart of the official file on these samples. Samples will be collected following the sampling procedures documented in Section 4.7 of thisQAPP. The equipment used to collect samples will be noted, along with the time of sampling,


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sample description, depth at which the sample was collected, volume of sample, and number ofcontainers. Modified, non-legal "chain-of-custody" procedures will be used to track the samples. All sedimentsamples will be collected by MPCA personnel who will label them using unique numbers.Sampling data and observations will be recorded, and the original notes archived in the project fileby the MPCA Principal Investigator. The sediment samples will be transported by MPCA personnelto AScI-DETD. Upon receipt by the laboratory, samples will be checked against the sample tracking forms toensure sample integrity and completeness of shipment. Composite sediment samples will behomogenized in a pre-cleaned aquarium by AScI-DETD staff; the samples will then be split forchemical analyses, 4-day toxicity tests, and 28-day bioaccumulation tests. Samples will be trackedinternally, at AScI-DETD, using forms for sample handling at each phase of the project. The"paper trail" thus formed will include the steps performed on each sample, as well as the personhandling the sample.


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SECTION 6

CALIBRATION PROCEDURES AND FREQUENCY This section describes the calibration procedures and the frequency at which these procedures willbe performed for both field and laboratory instruments. 6.1 FIELD INSTRUMENT CALIBRATION Field instrumentation for this survey will consist of a GPS unit, operated by MPCA staff. A SOPfor the calibration and use of the GPS unit is not available. Instead, the operating manual for theGPS Pathfinder Basic Receivers will be used to calibrate the GPS unit (Trimble Navigation,1992). No other equipment used in the field requires calibration. 6.2 LABORATORY INSTRUMENT CALIBRATION Calibration of analytical instruments is essential because it is the means by which instrumentresponses are properly translated into chemical concentrations. Instrument calibration is performedbefore sample analysis begins and is continued during sample analysis at the intervals specified inTable 6-1 to ensure that the data quality objectives are met. Initial calibration is performed prior tosample analysis to determine whether the response of the instrument is linear across a range oftarget analyte concentrations (i.e., the working linear range). It is also critical that the stability ofthe instrument response be verified during the course of ongoing sample analyses. The verificationof instrument stability is assessed by analyzing continuing calibration standards at regular intervalsduring the period that sample analyses are performed. It is recommended that, at a minimum,calibration standards be analyzed at the beginning of each analytical sequence, after every tenthsample, and at the end of the analytical sequence for all organic and inorganic compound analysesperformed. The concentration of the continuing calibration standard should be equivalent to theconcentration of the midpoint established during initial calibration of the working linear range ofthe instrument. The working linear range of an instrument should be established prior to performing sampleanalyses. A minimum of five calibration standards for the analysis of organic compounds, andthree calibration standards for the analysis of inorganic compounds, should be used whenestablishing the working linear range for all target analytes of concern. Generally, the workinglinear range of an instrument for a specific analysis should bracket the expected concentrations ofthe target analyte in the samples to be analyzed. The calibration standards used to establish theworking linear range should encompass a factor of 20 (i.e., 1 to 20, with the lowest concentrationequal to 1 and the highest concentration equal to 20 times the concentration of the lowestconcentration used).


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For this study, instrument calibration procedures are described in Table 6-1 and in the analyticalSOPs (Appendix D). All ongoing calibration measurements must be within 20% of the initialcalibration measurement to be considered adequate. Equipment logbooks will be maintained at AScI-DETD, in which will be recorded the usage,maintenance, calibration, and repair of instrumentation. These logbooks will be available to theMPCA or GLNPO during any audits that may be conducted. Table 6-1. Summary of Calibration Methods for Analytes in Sediment, Tissue, and Water Column Samples Matrix Analyte Initial Calibration Ongoing Calibration Sediment/Tissue PCBs 5 pt. curve of 26 congeners Every 5 samples Sediment/Tissue PAHs 6 pt. curve Every 12 samples Sediment/Tissue Mercury 4 pt. curve Every 20 samples Sediment TOC % of SRM Every 20 samples Water Ammonia 3 pt. curve Daily Water Conductivity 2 calibration standards Daily Water DO saturated oxygen reading Daily Water pH standard pH 7.0 Every 3 hours with a and 10.0 buffers pH 7.0 buffer Water Residual Chlorine 2 pt. curve Daily


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SECTION 7

TOXICITY AND BIOACCUMULATION TESTING

The toxicity screening and bioaccumulation exposures will be performed by AScI-DETD’slaboratory following methods given in U.S. EPA (1994). AScI-DETD’s laboratory willimplement the project required SOPs (Appendix E). These SOPs provide sufficient details onculturing of test organisms, QA/QC, screening toxicity test and bioaccumulation testmethodologies, and data analysis and interpretation procedures. 7.1 SCREENING TOXICITY TESTS Sediment screening toxicity tests will be conducted before any 28-day sediment bioaccumulationtests are initiated. These preliminary screening tests are required to determine if sedimenttoxicity is great enough to prevent survival of L. variegatus over a 28-day period. For thescreening tests, a toxicity exposure of four days will be conducted following the procedures givenin Table 7-1. 7.2 SEDIMENT BIOACCUMULATION TESTS Of the sediments with acceptable screening toxicity test results, four sediment samples fromMinnesota Slip and Slip C will be selected for bioaccumulation tests. Provided the reference sitesediments pass the screening toxicity tests, these sediment samples will be set-up along side theother bioaccumulation tests. The recommended test conditions for conducting the 28-daysediment bioaccumulation tests with L. variegatus are provided in Table 7-2. The generalactivity schedule for conducting these tests, after the 4-day screening toxicity tests, is given inTable 7-3. 7.3 TEST ACCEPTABILITY REQUIREMENTS The test acceptability requirements for the 4-day screening toxicity tests and bioaccumulationtests are given in Table 7-4. Any variances from these requirements will be described in the finalreport to the MPCA.


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Table 7-1. Recommended Test Conditions for Conducting a Preliminary 4-day Sediment Toxicity Screening Test with L. variegatus [adapted from U.S. EPA (1994)] Parameter Conditions 1. Test type: 4-day whole-sediment toxicity test with renewal of overlying water 2. Temperature: 23 ± 1°C 3. Light quality: Wide-spectrum fluorescent lights 4. Illuminance: about 500 to 1000 lux 5. Photoperiod: 16L:8D 6. Test chamber: 300-mL high-form lipless beaker 7. Sediment volume: 100 mL 8. Overlying water volume: 175 mL 9. Renewal of overlying water: 2 volume additions/day; continuous or intermittent (e.g.,

one volume addition every 12 hours) 10. Age of test organisms: Adults 11. Number of organisms/chamber: 10 12. Number of replicate chambers/ 4 treatment: 13. Feeding: None 14. Aeration: None, unless dissolved oxygen in overlying water drops below 40% of saturation 15. Overlying water: Dechlorinated City of Duluth tap water 16. Test chamber cleaning: If screens become clogged during the test, gently brush the outside of the screen. 17. Overlying water quality: Hardness, alkalinity, conductivity, pH, and

ammonia at the beginning and end of a test. Temperature and dissolved oxygen daily.

18. Test duration: 4 days 19. Endpoints: Number of organisms and behavior. There should

be no significant reduction in number of organisms in a test sediment relative to the control.

20. Test acceptability: Performance-based criteria specifications outlined in Table 7-4.


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Table 7-2. Recommended Test Conditions for Conducting a 28-day Sediment Bioaccumulation Test with L. variegatus [adapted from U.S. EPA (1994)]

Parameter Conditions

1. Test type: Whole-sediment bioaccumulation test with renewal of overlying water

2. Temperature 23 ± 1°C 3. Light quality: Wide-spectrum fluorescent lights 4. Illuminance: About 500 to 1000 lux 5. Photoperiod: 16L:8D 6. Test chamber: 6-L aquaria with stainless steel screens or glass

standpipes 7. Sediment volume: 1.6 L 8. Overlying water volume: 3.2 L 9. Renewal of overlying water: 2 volume additions/day; continuous or intermittent (e.g.,

one volume addition every 12 hours) 10. Age of test organisms: Adults 11. Loading of organisms in

chamber: Ratio of TOC in sediment to organism dry weight should be no less than 50:1. Preferably 5 g/replicate.

12. Number of replicatechambers/treatment:

Five

13. Feeding: None 14. Aeration: None, unless dissolved oxygen in overlying water drops

below 40% of saturation. 15. Overlying water: Dechlorinated City of Duluth tap water 16. Test chamber cleaning: If screens become clogged during the test, gently brush the

outside of the screen. 17. Overlying water quality: Hardness, alkalinity, conductivity, pH, and ammonia at

the beginning and end of a test (i.e., day 0 and 28). Temperature and dissolved oxygen daily.

18. Test duration 28 days 19. Endpoint: Bioaccumulation 20. Test acceptability: Performance-based criteria specifications outlined in

Table 7-4.


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Table 7-3. General Activity Schedule for Conducting a 28-day Sediment Bioaccumulation Test with L. variegatus [adapted from U.S. EPA (1994)] A. Conducting a 4-day Toxicity Screening Test (conducted before the 28-day bioaccumulation

test)

Day Activity

-1 Isolate worms for conducting toxicity screening test. Add sediment intoeach test chamber, place chambers into exposure system, and startrenewing overlying water.

0 Measure total water quality (i.e., pH, temperature, dissolved oxygen,

hardness, alkalinity, conductivity, ammonia). Transfer 10 worms intoeach test chamber. Measure weight of a subset of 20 organisms used tostart the test. Observe behavior of test organisms.

1-2 Measure temperature and dissolved oxygen. Observe behavior of test

organisms.

3 Same as Day 1. Measure total water quality.

4 Measure temperature and dissolved oxygen. End the test by collectingthe oligochaetes with a sieve and determine weight of survivors. Bioaccumulation tests should not be conducted with L. variegatus if atest sediment significantly reduces number of oligochaetes relative to thecontrol sediment or if oligochaetes avoid the sediment.

B. Conducting a 28-day Bioaccumulation Test

Day Activity

-1 Isolate worms for conducting bioaccumulation test. Add sediment intoeach test chamber, place chambers into exposure system, and startrenewing overlying water.


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Table 7-3. Continued B. Conducting a 28-day Bioaccumulation Test (Continued)

Day Activity

0 Measure total water quality (i.e., pH, temperature, dissolved oxygen,hardness, alkalinity, conductivity, ammonia). Transfer appropriateamount of worms (based on weight) into each test chamber. Sample asubset of worms used to start the test for residue analyses. Observebehavior of test organisms.

1-27 Measure temperature and dissolved oxygen. Observe behavior of test

organisms.

28 Measure total water quality (i.e., pH, temperature, dissolved oxygen,hardness, alkalinity, conductivity, ammonia). End uptake by collectingthe worms with a sieve. Separate any indigenous organisms fromL. variegatus. Eliminate gut contents of surviving worms in water for 24hours. Determine weight of survivors.

29 Sample surviving worms after 24 hours of elimination for chemical

analysis.


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Table 7-4. Test Acceptability Requirements for a 28-day Sediment Bioaccumulation Test with L. variegatus [adapted from U.S. EPA (1994)] A. It is recommended for conducting a 28-day test with L. variegatus that the following

performance criteria be met:

1. Numbers of L. variegatus in a 4-day toxicity screening test should not be significantlyreduced in the test sediment relative to the control sediment.

2. Test organisms should burrow into test sediment. Avoidance of test sediment by

L. variegatus may decrease bioaccumulation. 3. Hardness, alkalinity, pH, and ammonia in the overlying water within a treatment

should not vary by more than 50% during the test.

B. Performance-based criteria for culturing L. variegatus include:

1. Laboratories must perform monthly 96-hour water-only reference-toxicity tests toassess the sensitivity of culture organisms. Moderately hard reconstructed water willbe used as the diluent.

2. Laboratories should monitor the frequency with which the population is doubling in

the culture (number of organisms) and record this information using control charts(doubling rate would need to be estimated on a subset of animals from a massculture). Records should also be kept on the frequency of restarting cultures.

3. Food used to culture organisms should be analyzed before the start of a test for

compounds to be evaluated in the bioaccumulation test. 4. Laboratories should record the following water quality characteristics of the cultures

at least quarterly and the day before the start of a sediment test: pH, hardness,alkalinity, and ammonia. Dissolved oxygen should be measured weekly. Temperature should be recorded daily.

5. Laboratories should characterize and monitor background contamination and nutrient

quality of food if problems are observed in culturing or testing organisms. 6. Physiological measurements such as lipid content might provide useful information

regarding the health of the cultures.


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Table 7-4. Continued C. Additional requirements:

1. All organisms in a test must be from the same source. 2. It is desirable to start tests soon after collection of sediment from the field. 3. All test chambers (and compartments) should be identical and should contain the

same amount of sediment and overlying water. 4. Negative-control sediment and appropriate solvent controls must be included in a test.

The concentration of solvent used must not adversely affect test organisms. 5. Test organisms must be cultured and tested at 23°C. 6. The daily mean test temperature must be within ± 1°C of the desired temperature.

The instantaneous temperature must always be within ± 3°C of the desiredtemperature.

7. Natural physico-chemical characteristics of test sediment collected from the field

should be within the tolerance limits of the test organisms.


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SECTION 8

LABORATORY ANALYTICAL PROCEDURES Sediment and/or tissue samples will be analyzed by AScI-DETD for the chemical parameters listedin Table 8-1. AScI-DETD will implement the project required SOPs (Appendices D and E). TheseSOPs provide sufficient details for sample preparation, cleanup, and analysis applicable to thisinvestigation. Table 8-1 summarizes the methods used to measure mercury, PAHs, PCB congeners, TOC, percentmoisture, and percent lipids. The list of PAH compounds and PCB congeners to be included in thisstudy, and their associated method detection limits (MDLs) in Lumbriculus tissue, are given inTables 8-2 and 8-3, respectively. The mercury MDL for Lumbriculus tissue is 53 µg/kg wetweight. The MDLs for PAH compounds, PCB congeners, and mercury in sediment samples arebased on information provided by AScI Corp. Where methodological variances from the methodslisted in Table 8-1 occur, they will be described in an attachment to the data report.


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Table 8-1. Summary of Analytical Methods for Sediments and L. variegatus Tissues Analyte

Method # (description)

Sample cleanup

Blanks

Sediment MDL (dry wt.)

Tissue MDL (wet wt.)

Mercury1 Based on U.S. EPA SW-846,

Method 7471A (cold vapor AA) N/A Every 20

samples 46 µg/kg 53 µg/kg

PAHs1 U.S. EPA SW-846, Method 8270C

(capillary column GC/MS) chromatographic column Every 20

samples 3-6 µg/kg 20-50 µg/kg

PCBs1 U.S. EPA SW-846, Method

3540C: Soxhlet extraction andMethod 8082 (congener analysis)(capillary column GC/ECD)

Florisil (U.S. EPA SW-846,Method 3620B) and SulfurClean-up for sediments only(SW-846, Method 3660B)

Every 20samples

1 µg/kg 20-30 µg/kg

TOC2 U.S. EPA SW-846, Method 9060

(Leco WR-12 induction furnace) N/A Every 20

samples 0.1 % N/A

Percent Moisture2 Standard Method 208G

(gravimetric technique) N/A N/A N/A N/A

Percent Lipids3 Bligh-Dyer Method (U.S. EPA,

1994)

N/A N/A N/A 0.1%

1 Sediment and tissue samples 2 Sediment samples 3 Tissue samples MDL = Method detection limit N/A = Not applicable


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Table 8-2. PAH Compound MDLs for L. variegatus Matrix

PAH Compound

MDL

Wet Weight (mg/kg)

MDL

Dry Weight* (mg/kg)

acenapthene 0.03 0.3

acenapthylene 0.03 0.3

anthracene 0.03 0.3

benzo[a]anthracene 0.03 0.3

benzo[a]pyrene 0.05 0.5

benzo[b&j]fluoranthene 0.04 0.4

benzo[e]pyrene 0.04 0.4

benzo[g,h,i]perylene 0.03 0.3

benzo[k]fluoranthene 0.04 0.4

chrysene 0.03 0.3

dibenzo[a,h]anthracene 0.02 0.2

fluoranthene 0.02 0.2

fluorene 0.02 0.2

indeno[1,2,3-cd]pyrene 0.03 0.3

2-methylnapthalene 0.04 0.4

napthalene 0.04 0.4

phenanthrene 0.03 0.3

pyrene 0.03 0.3

* Calculated based on an average dry weight of 10% for L. variegatus.


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Table 8-3. PCB Congener MDLs for L. variegatus Matrix

PCB

Congener

MDL

Wet Weight (mg/kg)

MDL

Dry Weight* (mg/kg)

8 0.02 0.2 18 0.02 0.2 28 0.02 0.2 52 0.02 0.2 49 0.02 0.2 44 0.02 0.2 66 0.02 0.2 101 0.02 0.2 87 0.02 0.2 77 0.02 0.2 118 0.02 0.2 153 0.02 0.2 184 0.02 0.2 105 0.02 0.2 138 0.02 0.2 126 0.02 0.2 187 0.02 0.2 183 0.02 0.2 128 0.02 0.2 156 0.02 0.2 180 0.02 0.2 169 0.02 0.2 170 0.02 0.2 195 0.02 0.2 206 0.02 0.2 209 0.03 0.3

* Calculated based on an average dry weight of 10% for L. variegatus.


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SECTION 9

INTERNAL QUALITY CONTROL CHECKS 9.1 FIELD QUALITY CONTROL CHECKS The only field measurements planned for this project are those related to positioning the boat (i.e.,GPS unit). Attainable precision is approximately 2-5 m. To verify this precision, the "marking"method can be used to find known geographical locations (e.g., benchmarks) using only thetracking capabilities of the GPS unit. 9.2 LABORATORY QUALITY CONTROL CHECKS AScI-DETD has a QC program they use to ensure the reliability and validity of the analyses theyperform (Appendix C). All analytical procedures are documented in writing as SOPs and each SOPincludes QC information that addresses the minimum QC requirements for the procedure. Theinternal quality control checks might differ slightly for each individual procedure but in general, theQC requirements include the following: • Method blanks• Reagent/preparation blanks (applicable to inorganic analysis)• Instrument blanks• Matrix spikes/matrix spike duplicates (for organic analysis)• Surrogate spikes• Analytical spikes (graphite furnace)• Field replicates• Laboratory duplicates• Laboratory control standards• Internal standard areas for GC/MS or GC/ECD analysis; control limits. Table 9-1 summarizes the internal quality control checks used for each of the critical analyses. Details on the use of each QC check are provided in the analytical SOPs provided for eachmeasurement (see Appendix D). Method detection limits will be calculated for each analyte. The analyses for PAHs and PCBs use a method blank (consisting of an extracted matrix or solventphase sample with "zero" known concentration of the analytes), and a matrix spike (a controluncontaminated sediment spiked with known analyte concentration), which are subjected toanalyses identical to the samples. Analytical duplicate samples will be run after every 7-15samples. These analyses will also include measurement of a surrogate internal standard. Acceptance criteria for these internal QC checks are: a "clean" procedural blank (i.e., significantlyless than the reporting level for analytes of concern), recoveries within the control limits of


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50-120% (PCBs) and 50-130% (PAHs) for both the blank spike recovery (i.e., laboratory fortifiedblank) and matrix spike recovery and 40-120% for the surrogate standard recoveries. Relative errorfor duplicate samples must be less than 50% relative percent difference (RPD). Internal QC checks for mercury include the use of blanks and a NIST standard for mercury. Analytical duplicate measurements will be made after at least every 10 samples to measureprecision. Acceptable precision is 20% RPD. Acceptance criteria for accuracy are 80-120% of theSRM for mercury, and 80-120% of the SRM for TOC. For PCBs, the absolute retention time windows (i.e., 3 x SD of replicate calibration standards) forindividual congeners should not be exceeded. In addition, the operating conditions of the GC usedfor the initial PCB calibration must be verified first by an initial calibration verification and by asolvent blank or method blank which demonstrates the cleanliness of the system and/or extractclean-up steps used to prepare the sample extracts (AScI SOP number OGN-10-P, Appendix D). The calibration factors (CF) or percent recovery, depending on the calibration method, should notexceed +/- 15% difference from the mean CF if CF’s are used for the calibration, or from 100%recovery if a curve is used for calibration. For PAHs, the method accuracy for each matrix studied we be assessed as follows. After analyzingfive spiked samples, calculate the average percent recovery (p) and the standard deviation of thepercent recovery (sp). The accuracy is expressed as a percent recovery interval from p - 2sp to p + 2sp. The acceptable precision limits for surrogate standards are calculated as follows. Once aminimum of thirty surrogate standard samples of the same matrix have been analyzed, calculate theaverage percent recovery (P) and standard deviation of the percent recovery (s) for each of thesurrogates. For a given matrix, calculate the upper and lower control limit for method performancefor each surrogate standard as follows: Upper Control Limit = p + 3s Lower Control Limit = p – 3s All data obtained will be properly recorded. The data package will include a full deliverablepackage capable of allowing the recipient to reconstruct QC information and compare it to QCcriteria. Any samples analyzed in nonconformance with the QC criteria will be reanalyzed by thelaboratory if sufficient volume is available. It is expected that sufficient volumes/weights ofsamples will be collected to allow for re-analysis when necessary.


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Table 9-1. Summary of Analytical Quality Control Checks for Critical Measurements Field Analytical Analyte (matrix) Splits, replicates Spikes Blanks Duplicates Standards PCBs None Matrix Solvent, Method Every 10 samples see SOP (Appendix D) PAHs None Matrix Solvent, Method Every 10 samples see SOP (Appendix D) Mercury None N/A Method Every 10 samples NIST 1646 TOC None N/A Method Every 10 samples EDTA 41.1% ACETENILDE 72% N/A = Not applicable


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SECTION 10

DATA REDUCTION, VALIDATION, AND REPORTING All data generated through field activities, or by the laboratory operations, will be reduced andvalidated prior to reporting. No data will be disseminated by the laboratory until it has beensubjected to these procedures which are summarized in the following subsections. 10.1 DATA REDUCTION 10.1.1 Field Data Reduction Procedures Field data reduction procedures will be minimal in scope compared to those implemented in thelaboratory setting. GPS measurements will be made in the field. These data will be written into thefield notebook immediately after taking the measurement. If errors are made, results will be legiblycrossed out, initialed and dated by the field member, and corrected in a space adjacent to theoriginal (erroneous) entry. Later, when the results forms required for this study are filled out, theField Team Leader will proof the forms to determine whether any transcription errors have beenmade. 10.1.2 Laboratory Data Reduction Procedures Laboratory data reduction procedures will be followed according to the following general protocol.All raw analytical, toxicity, and bioaccumulation data will be recorded in numerically identifiedlaboratory notebooks. If a laboratory has the capability to directly enter or download the data into acomputerized data logger, then this is preferable. Sample data are recorded along with otherpertinent information, such as the sample identification number. Other details which will also berecorded include: the analytical method used (SOP #), name of analyst, the date of analysis ortoxicity/bioaccumulation test, matrix sampled, reagent concentrations, instrument settings, and theraw data. Each page of the notebook will be signed and dated by the analyst. Copies of any stripchart printouts (such as gas chromatograms) will be maintained on file. Periodic review of thesenotebooks by the Laboratory QA Manager will take place prior to final data reporting. Records ofnotebook entry inspections are maintained by the Laboratory QA Manager. For this project, all calculations will be checked by the Laboratory Section Supervisor. Errors willbe noted and corrected by crossing out the original notations. Analytical results for sedimentsamples will be calculated and reported on a dry weight basis. Quality control data (e.g., laboratory duplicates, matrix spikes, matrix spike duplicates, andperformance of negative controls) will be compared to the method acceptance criteria. Data


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considered to be acceptable will be entered into the laboratory computer system. Data summarieswill be sent to the Laboratory QA Manager for review. If approved, data are logged into the projectdatabase format. Unacceptable data will be appropriately qualified in the project report. Casenarratives will be prepared which will include information concerning data that fell outsideacceptance limits, and any other anomalous conditions encountered during sample analysis. Afterthe Laboratory QA Manager approves these data, they will be considered ready for third party datavalidation. 10.2 DATA VALIDATION Data validation procedures will be performed for both field and laboratory operations as describedbelow. 10.2.1 Procedures Used to Validate Field Data Procedures to evaluate field data for this project primarily include checking for transcription errorsand reviewing field notebooks. This task will be the responsibility of the Field Team Leader. 10.2.2 Procedures to Validate Laboratory Data The Laboratory QA Officer will conduct a systematic review of the analytical data for compliancewith the established QC criteria based on the spike, duplicate, and blank results provided by thelaboratory. All technical holding times will be reviewed, the GC/MS-SIM and GC/ECD instrumentperformance check sample results will be evaluated, and results of initial and continuing calibrationwill be reviewed and evaluated. The Laboratory QA officer will conduct a similar systematicreview of the toxicity and bioaccumulation data to ensure the test acceptability requirements listedin Table 7.4 have been met. One hundred percent of the analytical, toxicity, and bioaccumulationdata will be validated. The data review will identify any out-of-control data points and data omissions, and the LaboratoryQA Officer will interact with the laboratory to correct data deficiencies. Decisions to repeat samplecollection and analyses may be made by the MPCA Principal Investigator based on the extent of thedeficiencies and their importance in the overall context of the project. All data generated for this project will be computerized into a spreadsheet format (e.g., Excel)organized to facilitate data review and evaluation. The computerized data set will include the dataflags provided by the laboratory, as well as additional comments of the data reviewer. Theanalytical laboratory-provided data flags will include such items as: 1) concentration belowrequired detection limit, 2) estimated concentration due to poor spike recovery, and 3)concentration of chemical also found in laboratory blanks. The toxicity and bioaccumulationlaboratory-provided data flags will include such items as: 1) unacceptable negative-control


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survival, 2) unacceptable deviations in overlying water quality physico-chemical measurements,and 3) unacceptable reference toxicant test results. The Data Reviewer comments will indicate thatthe data are: 1) usable as a quantitative concentration or biological effect, 2) usable with caution asan estimated concentration or biological effect, or 3) unusable due to out-of-control QC results. The overall completeness of the data package will also be evaluated by the Laboratory DataValidator (QA Officer). Completeness checks will be administered on all data to determinewhether deliverables specified in the laboratory contract and QAPP are present. The reviewer willdetermine whether all required items are present and request copies of missing deliverables. 10.3 DATA REPORTING Data reporting procedures will be carried out for field and laboratory operations as indicated below. 10.3.1 Field Data Reporting Field data reporting will be conducted principally through the transmission of report sheetscontaining tabulated results of all measurements made in the field, and documentation of all GPSfield calibration activities. 10.3.2 Laboratory Data Reporting The task of reporting laboratory data begins after the validation activity has been concluded. Asspecified in AScI Corporation’s contract with the MPCA, a report will be submitted to the MPCAthat contains the following components: • Introduction (brief)• Sample collection and handling• Methods, including:

• exposure system• test organisms• test performance• sediment and tissue chemistry• data analysis procedures• reference toxicity testing

• Results, including:• screening toxicity tests• bioaccumulation tests• reference toxicant tests• associated sediment and tissue chemistry values, as well as water quality parameters


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• References• Appendices, including:

• laboratory data sheets and any associated QA/QC review• statistical printouts• reference toxicant control chart(s).

An electronic copy of the toxicity test report and associated data files will be submitted in a formatcompatible with the MPCA’s software (e.g., Word 6.0 or WordPerfect 6.1, Excel 5.0 or compatiblespreadsheet). The Laboratory QA Manager must perform a final review of the report to determine whether itmeets project requirements. In addition to the general report outline given above, specific detailmust be provided for the following elements: • Date of issuance of report• Table of contents• Project name and number• Condition of samples ‘as-received’• Discussion of whether or not sample holding times were met• Laboratory analyses performed for chemical and biological endpoints• Any deviations from intended analytical, toxicology, and bioaccumulation methods• Laboratory batch number• Numbers of samples and respective matrices• Cross referencing of laboratory sample to project sample identification numbers• Quality control procedures utilized and also references to the acceptance criteria• Description of data qualifiers• Discussion of technical problems or other observations which may have created analytical or experimental difficulties• Sample and laboratory quality control results• Results of (dated) initial and continuing calibration checks• Matrix spike and matrix spike duplicate recoveries, laboratory control samples, method blank results, calibration check compounds, and system performance check compound results• Results of tentatively identified compounds• Discussion of any laboratory QC checks which failed to meet project criteria• Signature of the Laboratory QA Manager.


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SECTION 11

PERFORMANCE AND SYSTEMS AUDITS Performance and system audits of both field and laboratory activities may be conducted to verifythat sampling and analysis are performed in accordance with the procedures established in theQAPP. Potential audits of field and laboratory activities include two independent parts: internaland external audits. 11.1 FIELD PERFORMANCE AND SYSTEM AUDITS 11.1.1 Internal Field Audits Internal audits of field activities, including sampling and field measurements, may be conducted bythe MPCA QA Officer. The purpose of these audits will be to verify that all established proceduresare being followed. If performed, the audits will include examination of field sampling records,field instrument (i.e., GPS) operating records, sample collection, handling, and packaging incompliance with the established procedures, maintenance of QA procedures, sample tracking, etc. The audits will involve review of field measurement records, instrumentation calibration records,and sample documentation. 11.1.2 External Field Audits External field audits may be conducted by GLNPO. External field audits may be conducted anytime during the field operations. These audits may or may not be announced and are at thediscretion of GLNPO. External field audits will be conducted according to the field activityinformation presented in the QAPP. 11.2 LABORATORY PERFORMANCE AND SYSTEMS AUDITS 11.2.1 Internal Laboratory Audit The internal laboratory audit may be conducted by the MPCA QA Officer. The internal lab systemaudit will be conducted during the bioaccumulation tests. The internal lab system audit will includean examination of laboratory documentation on sample receiving, sample log-in, sample storage,sample tracking procedures, sample preparation and analysis, instrument operating records, etc. Internal lab performance audits will not be done due to the short time-frame of this project.


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11.2.2 External Laboratory Audit An external audit may be conducted by the GLNPO QA Officer. An external laboratory audit maybe conducted at least once prior to the initiation of the sampling and analysis activities. This auditmay or may not be announced and is at the discretion of GLNPO. An external laboratory audit willinclude (but not be limited to): review of laboratory analytical procedures, laboratory on-site audits,and/or submission of performance evaluation samples to the laboratory for analysis.


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SECTION 12

PREVENTATIVE MAINTENANCE 12.1 FIELD EQUIPMENT PREVENTATIVE MAINTENANCE The field equipment for this project includes the GPS unit, Shipek grab sampler, and soundingpoles. Preventative maintenance procedures will follow the professional judgment of the FieldTeam Leader for this project. 12.2 LABORATORY INSTRUMENT PREVENTATIVE MAINTENANCE As part of AScI-DETD’s QA/QC program (Appendix C), a routine preventative maintenanceprogram is conducted by them to minimize the occurrence of instrument failure and other systemmalfunctions. All laboratory instruments are maintained in accordance with manufacturer’sspecifications and the requirements of the specific method employed. This maintenance is carriedout on a regular, scheduled basis and is documented in the laboratory instrument service logbookfor each instrument.


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SECTION 13

SPECIFIC ROUTINE PROCEDURES USED TO ASSESS DATA PRECISION,ACCURACY AND COMPLETENESS

13.1 ACCURACY ASSESSMENT In order to assure the accuracy of the analytical procedures, an environmental sample will berandomly selected from each sample shipment received at the laboratory, and spiked with a knownamount of the analyte or analytes to be evaluated. In general, a sample spike will be included inevery set of 20 samples tested on each instrument. The spike sample will be then analyzed. Theincrease in concentration of the analyte observed in the spiked sample, due to the addition of aknown quantity of the analyte, compared to the reported value of the same analyte in the unspikedsample determines the percent recovery. The percent recovery for a spiked sample is calculatedaccording to the following formula: %R = 100% x (S - U)/Csa %R = percent recovery S = measured concentration in spiked sample U = measured concentration in unspiked sample Csa = actual concentration of spike added For situations where a standard reference material is used in addition to a matrix spike: %R = 100% x Cm/Csrm %R = percent recovery Cm = measured concentration of SRM Csrm = actual concentration of SRM 13.2 PRECISION ASSESSMENT For duplicate measurements, relative percent difference (RPD) is calculated as follows:


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RPD = |D1 - D2 |x 100% (D1 + D2)/2 RPD = relative percent difference D1 = sample value D2 = duplicate sample value For three or more replicates: RSD = (s/x) x 100 RSD = relative standard deviation s = standard deviation of three or more results x = mean of three or more results Standard deviation is defined as follows:

s = (( (yi -mean y)2 x 1/(n-1)))0.5

s = standard deviation yi = measured value of the ith replicate mean y = mean of replicate measurements n = number of replicates 13.3 COMPLETENESS ASSESSMENT Completeness is the ratio of the number of valid sample results to the total number of samplesanalyzed with a specific matrix and/or analysis. Following completion of the analytical testing, thepercent completeness will be calculated by the following equation: %C = 100% x (V/n) %C = percent completeness V = number of valid measurements n = number of measurements planned


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SECTION 14

CORRECTIVE ACTION Corrective action is the process of identifying, recommending, approving, and implementingmeasures to counter unacceptable procedures or out of quality control performance which can affectdata quality. Corrective action can occur during field activities, laboratory analyses, data validation,and data assessment. All corrective actions proposed and implemented will be documented in theregular quality assurance reports to management. Corrective actions should only be implementedafter approval by the MPCA Principal Investigator, or her designee, the Field Team Leader. Ifimmediate corrective action is required, approvals secured by telephone from the MPCA PrincipalInvestigator should be documented in an additional memorandum. For noncompliance problems, a formal corrective action program will be determined andimplemented at the time the problem is identified. The person who identifies the problem will beresponsible for notifying the MPCA Principal Investigator, who in turn will notify the GLNPOProject Officer. Implementation of corrective actions will be confirmed in writing through thesame channels. Any nonconformance with the established quality control procedures in the QAPP will be identifiedand corrected in accordance with the QAPP. The GLNPO Project Officer, or her designee, willissue a nonconformance report for each nonconformance condition. Corrective actions will be implemented and documented in the field notebook. No project memberwill initiate corrective actions without prior communication of findings through the properchannels. If corrective actions are insufficient, work may be stopped. 14.1 FIELD CORRECTIVE ACTION Corrective action in the field may be needed when the sample network is changed (i.e., more/lesssamples, sampling locations other than those specified in the QAPP, etc.), or when samplingprocedures and/or field analytical procedures require modification due to unexpected conditions. Technical staff and project personnel will be responsible for reporting all suspected technical or QAnonconformances, or suspected deficiencies of any activity or issued document, by reporting thesituation to the Field Team Leader or designee. This person will be responsible for assessing thesuspected problems, in consultation with the MPCA Principal Investigator, and making a decisionbased on the potential for the situation to impact the quality of the data. If it is determined that thesituation warrants a reportable nonconformance requiring corrective action, then a nonconformancereport will be initiated by the MPCA Principal Investigator.


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The MPCA Principal Investigator will be responsible for ensuring that corrective actions fornonconformances are initiated by: • Evaluating all reported nonconformances• Controlling additional work on nonconforming items• Determining disposition or action to be taken• Maintaining a log of nonconformances• Reviewing nonconformance reports and corrective actions taken• Ensuring nonconformance reports are included in the final report files. If appropriate, the Field Team Leader will ensure that no additional work, that is dependent on thenonconforming activity, is performed until the corrective actions are completed. Corrective actionsfor field measurements may include: • Repeat the measurement to check the error• Re-calibration• Replace the instrument or measurement device• Stop work (if necessary). The Field Team Leader, or his designee, is responsible for all field work activities. In case thesampling program changes, the Field Team Leader will implement the changes after obtainingapproval from the MPCA Principal Investigator. Corrective actions resulting from internal field audits will be implemented immediately if data maybe adversely affected due to unapproved or improper use of approved methods. The MPCA QAOfficer will identify deficiencies and recommend corrective actions to the MPCA PrincipalInvestigator. Implementation of corrective actions will be performed by the Field Team Leader. Corrective actions will be documented in quality assurance reports to the entire projectmanagement. Corrective actions will be implemented and documented in the field notebook. No staff memberwill initiate corrective actions without prior communication of findings through the properchannels. If corrective actions are insufficient, work may be stopped by the GLNPO ProjectOfficer. 14.2 LABORATORY CORRECTIVE ACTION Corrective actions in the laboratory may occur prior to, during, and after initial analysis. A numberof conditions such as broken sample containers, multiple phases, and potentially high concentrationsamples may be identified during sample log-in or just prior to analysis. Following consultationwith laboratory analysts and section leaders, it may be necessary for the Laboratory QA Manager to


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approve the implementation of corrective actions. The submitted SOPs specify some conditionsduring or after analysis that may automatically trigger corrective actions of samples, includingadditional sample extract cleanup and automatic reinjection/reanalysis when certain quality controlcriteria are not met (Appendix D). Corrective actions are required whenever an out-of-control event or potential out-of-control event isnoted. The investigative action taken is somewhat dependent on the analysis and the event. Laboratory personnel are alerted that corrective actions may be necessary if: • QC data are outside the warning or acceptable windows for precision and accuracy• Blanks contain target analytes above acceptable levels• Undesirable trends are detected in spike recoveries or RPD between duplicates• There are unusual changes in detection limits• QC limits for sediment toxicity tests and bioaccumulation tests are not met• Deficiencies are detected by the Laboratory, MPCA, and/or GLNPO QA Officer(s) during

internal or external audits or from the results of performance evaluation samples• Inquires concerning data quality are received. Corrective action procedures are often handled at the bench level by the analyst, who reviews thepreparation or extraction procedure for possible errors, checks the instrument calibration, spike andcalibration mixes, instrument sensitivity, experimental set-up for toxicity and bioaccumulationtests, and so on. If the problem persists or cannot be identified, the matter is referred to theLaboratory Deputy Director and/or Laboratory QA Officer for further investigation. Once resolved,full documentation of the corrective action procedure is filed with the Laboratory QA Officer. These corrective actions are performed prior to release of the data from the laboratory. Thecorrective actions will be documented in both the laboratories corrective action log and thenarrative data report sent from the laboratory to the MPCA Principal Investigator. If correctiveaction does not rectify the situation, the laboratory will contact the MPCA Principal Investigator. 14.3 CORRECTIVE ACTION DURING DATA VALIDATION AND DATA ASSESSMENT The MPCA Principal Investigator may identify the need for corrective action during either the datavalidation or data assessment. Potential types of corrective action may include resampling by thefield team or reinjection/reanalysis of samples by the laboratory. These actions are dependent upon the ability to mobilize the field team, and whether the data to becollected is necessary to meet required quality assurance objectives (e.g., the holding time forsamples is not exceeded). When a corrective action situation is identified, it is the MPCA PrincipalInvestigator who will be responsible for approving the implementation of corrective actions,


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including resampling, during data assessment. All corrective actions of this type will bedocumented by the MPCA QA Manager and Laboratory QA Manager.


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SECTION 15

QUALITY ASSURANCE REPORTS TO MANAGEMENT Written QC reports will be provided to the MPCA Principal Investigator, by the persons identifiedin Section 2, whenever sample measurements are reported. These reports will summarize QA/QCprograms, give detailed results of analysis of QC samples, and provide information on theprecision, accuracy, and completeness for each sample run. These written reports will note anysignificant QA/QC problems encountered during sample analyses, as well as state the correctiveactions taken. Any serious QA problems needing immediate decisions will be discussed orallybetween MPCA personnel and contract staff, with such discussions denoted in writing; theseproblems will be noted in the quarterly reports to the GLNPO Project Officer. MPCA will provide summary QA/QC information in the final written report to GLNPO. Thisreport will include information on adherence of measurements to the QA objectives. The finalreport will contain detailed discussions of QA/QC issues, including any changes in the QAPP, asummary of AScI-DETD’s QA/QC reports, results of any AScI-DETD or MPCA performanceaudits, any significant QA/QC problems, detailed information on how well the QA objectives weremet, and their ultimate impact on decision making. The following is a list of items to be includedin the final project report: • Changes in the QAPP• Results of the internal and external system audits• Significant QA/QC problems, recommended solutions, and results of corrective actions• Data quality assessment in terms of precision, accuracy, representativeness, completeness, and

sensitivity• Indication of fulfillment of QA objectives• Limitations on the use of the measurement data.


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Section 16Page 16-1

SECTION 16

REFERENCES

Breneman, D., C. Richards, and S. Lozano. 1999. Environmental influences on benthiccommunity structure in a Great Lakes embayment. Submitted to Journal of Great LakesResearch for review.

Bridges, T.S., D.W. Moore, P. Landrum, J. Neff, and J. Cura. 1996. Summary of a workshop oninterpreting bioaccumulation data collected during regulatory evaluations of dredgedmaterial. U.S. Army Corps of Engineers, Waterways Experiment Station, DredgingOperations Technical Support Program, Vicksburg, MS. Miscellaneous Paper D-96-1.

Crane. J.L. 1999. Assessment of contaminated sediments in Slip C, Duluth Harbor, MN. U.S.Environmental Protection Agency, Great Lakes National Program Office, Chicago, IL. EPA-905-R-99-007.

Crane, J.L., M. Schubauer-Berigan, and K. Schmude. 1997. Sediment assessment of hot spotareas in the Duluth/Superior Harbor. U.S. Environmental Protection Agency, GreatLakes National Program Office, Chicago, IL. EPA-905-R97-020.

Ingersoll, C.G. 1996. Methods for assessing sediment bioaccumulation in freshwater organisms.Conference presentation given at the National Sediment Bioaccumulation Conference atBethesda, MD during September 11-13, 1996.

Lubin, A.N., M.H. Williams, and J.C. Lin. 1995. Statistical techniques applied to sedimentsampling (STATSS). U.S. Environmental Protection Agency Region 5, Chicago, IL. Draft#3.

McFarland, V.A. 1995. Evaluation of field-generated accumulation factors for predicting thebioaccumulation potential of sediment-associated PAH compounds. U.S. Army Corps ofEngineers Waterways Experiment Station, Vicksburg, MS. Technical Report D-95-2.

Minnesota Pollution Control Agency (MPCA)/Wisconsin Department of Natural Resources(WDNR). 1992. St. Louis River System Remedial Action Plan, Stage One. MPCA, St.Paul, MN and WDNR, Madison, WI.


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Normandeau Associates. 1996. Results of elutriate, whole sediment, and bioaccumulationdredged material evaluations of USACOE: Duluth-Superior management units.Normandeau Associates, Spring City, PA.

Schubauer-Berigan, M. and J.L. Crane. 1997. Survey of sediment quality in the Duluth/SuperiorHarbor: 1993 sample results. U.S. Environmental Protection Agency, Great LakesNational Program Office, Chicago, IL. EPA 905-R97-005.

Trimble Navigation. 1992. Operating manual: GPS Pathfinder Basic Receivers. TrimbleNavigation Ltd. Sunnyvale, CA.

U.S. Environmental Protection Agency (EPA). 1994. Methods for measuring the toxicity andbioaccumulation of sediment-associated contaminants with freshwater invertebrates. U.S. Environmental Protection Agency, Duluth, MN. EPA 600/R-94/024.

U.S. EPA. 1995. QA/QC guidance for sampling and analysis of sediments, water, and tissuesfor dredged material evaluations. U.S. Environmental Protection Agency, Office ofWater, Washington, DC. EPA 823-B-95-001.

U.S. EPA. 1998. National sediment bioaccumulation conference: Proceedings. U.S.Environmental Protection Agency, Office of Water, Washington, DC. EPA 823-R-98-002.

Wisconsin Department of Natural Resources (WDNR). 1995. Guidance for sedimentassessment in the state of Wisconsin. Wisconsin Department of Natural Resources,Bureau of Water Resources, Madison, WI.


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Appendix AA-1

APPENDIX A

MPCA HEALTH AND SAFETY POLICY MANUAL


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Appendix BB-1

APPENDIX B

EQUIPMENT DECONTAMINATION SOP


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Appendix CC-1

APPENDIX C

AScI-DETD QUALITY ASSURANCE MANUAL


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Appendix DD-1

APPENDIX D

AScI-DETD SOPS FOR:

PAHs, PCBs, MERCURY, AND TOC


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Appendix EE-1

APPENDIX E

AScI-DETD SOPS FOR:

ORGANISM HANDLING AND CULTURING, L. variegatus 28-DAY

BIOACCUMULATION TOXICITY TESTS, BASIC WATER

CHEMISTRY METHODS, AND TOTAL LIPID MEASUREMENTS

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