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FINAL

QUALITY ASSURANCE PROJECT PLAN FOR SUPPLEMENTAL REMEDIAL

INVESTIGATION/FEASIBILITY STUDY COLD CREEK SWAMP OPERABLE UNIT

COLD CREEK/LEMOYNE SUPERFUND SITES MOBILE COUNTY, ALABAMA

Prepared for:

Akzo Chemicals Inc. Chicago, Illinois

and

ICI Americas Inc. "Wilmington, Delaware

Prepared by:

EA Mid-Atlantic Regional Operations EA Engineering, Science, and Technology, Inc.

15 Loveton Circle Sparks, Maryland 21152

10785288

December 1990

EA Project 11653.02

GO

FINAL

QUALITY ASSURANCE PROJECT PLAN FOR SUPPLEMENTAL REMEDIAL

INVESTIGATION/FEASIBILITY STUDY COLD CREEK SWAMP OPERABLE UNIT

COLD CREEK/LEMOYNE SUPERFUND SITES MOBILE COUNTY, ALABAMA

Prepared for:

Akzo Chemicals Inc. Chicago, Illinois

and

ICI Americas Inc. "Wilmington, Delaware

Prepared by:

EA Mid-Atlantic Regional Operations EA Engineering, Science, and Technology, Inc.

15 Loveton Circle Sparks, Maryland 21152

December 1990

EA Project 11653.02

0

CONTENTS

LIST OF FIGURES

LIST OF TABLES

EXECUTIVE SUMMARY

1. PROJECT DESCRIPTION

1.1 Description of Current Study

1.2 Objectives 1.3 Site Description 1.4 Toxic or Hazardous Substances that may be Encountered

1.4.1 Contaminant Characterization

1.4.2 Potential Exposure Pathways

1.5 Duration of Project

2. PROJECT MANAGEMENT AND RESPONSIBILITIES

2.1 General

2.1.1 Project Director Responsibilities

2.1.2 Project Manager Responsibilities 2.1.3 Quality Assurance Officer Responsibilities 2.1.4 Health and Safety Officer Responsibilities 2.1.5 Field Activities Manager Responsibilities

2.2 Contractor Laboratory Orgamization

2.2.1 Vice President 2.2.2 Quality Assurance Manager 2.2.3 Administrative Manager 2.2.4 Data Manager 2.2.5 Inorganics and Orgemics Managers 2.2.6 Supervisors 2.2.7 Sample Management Officer

2.3 Analytical Laboratory

3. QUALITY ASSURANCE OBJECTIVES

3.1 Data Quality/Quantity Needs

3.1.1 Soil/Sediment Sampling Data Requirements 3.1.2 Surface Vater Sampling Data Requirements 3.1.3 Biological Tissue Sampling Data Requirements

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CONTENTS (Cont.)

3.2 QA Objectives for Measurement Data

3.2.1 Precision 3.2.2 Accuracy 3.2.3 Representativeness 3.2.4 Completeness 3.2.5 Comparability 3.2.6 Tables of QA Objectives

3.3 Analytical Detection Limits.

4. SAMPLING PROCEDURES

5. SAMPLE CUSTODY

5.1 Field Sampling Operations

5.1.1 Sample Bottle Preparation 5.1.2 Sampling

5.1.3 Sample Labeling

5.2 Laboratory Operations

5.2.1 Duties and Responsibilities of Sample Custodian 5.2.2 Sample Receipt and Logging 5.2.3 Sample Storage and Security

6. CALIBRATION PROCEDURES AND FREQUENCY

6.1 Calibration Program 6.2 Calibration Standards 6.3 Calibration Frequency 6.4 Operational Calibration

6.4.1 General Calibration Procedures 6.4.2 Method Blank 6.4.3 Calibration Curve

6.5 Tuning eUid GC/MS Mass Calibration 6.6 Field Equipment

7. ANALYTICAL PROCEDURES

8. DATA REDUCTION, VALIDATION, AND REPORTING

8.1 Data Collection 8.2 Data Reduction 8.3 Reporting 8.4 Data Validation

CONTENTS (Cont.)

9. INTERNAL QUALITY CONTROLS CHECKS

9.1 Internal Quality Control Samples

9.1.1 Method (Reagent) Blank 9.1.2 Fortified Method Blank Spike 9.1.3 Fortified Sample 9.1.4 Surrogates 9.1.5 Laboratory Duplicate Analyses 9.1.6 Replicate Field Samples

9.2 Other Internal Quality Control Checks

9.2.1 Standard Reference Material 9.2.2 Blind Performance Sample 9.2.3 Known Performance Samples

9.3 Field Blank Quality Control Samples

9.3.1 Field Blank 9.3.2 Rinsate Blank 9.3.3 Trip Blank

9.4 QC Monitoring

10. PROJECT QUALITY ASSURANCE AUDITS

10.1 Quality Assurance Management 10.2 Audits

10.2.1 Responsibility, Authority, and Timing 10.2.2 Reports and Distribution 10.2.3 Forms and Checklists 10.2.4 System Audits 10.2.5 Performance Audits

11. PREVENTIVE MAINTENANCE

11.1 Chromatographic Instruments 11.2 Analytical Balances 11.3 Temperature Control Systems 11.4 Atomic Absorption Spectrophotometer

11.4.1 General Considerations

11.5 Technicon Autoanalyzers 11.6 Hydrogen Ion Meters

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CONTENTS (Cont.)

12. DATA ASSESSMENT

12.1 Application of Controls 12.2 Control Charts

12.2.1 Accuracy and Precision Charts 12.2.2 Calculation of Chart Limits 12.2.3 How the Charts are Used 12.2.4 Out-of-Control Situations 12.2.5 References

12.3 Quality Assurance

12.3.1 Reagent and Titrant Preparation 12.3.2 Standards Preparation 12.3.3 Data Workup 12.3.4 Outlier Identification

13. CORRECTIVE ACTIONS

13.1 Objectives 13.2 Rationale 13.3 Corrective Action Methods

13.3.1 Immediate Corrective Actions 13.3.2 Long-Term Corrective Actions 13.3.3 Corrective Action Steps 13.3.4 Audit Based Non-Conformance

13.4 Corrective Action Report Review amd Filing

13.5 Corrective Actions Reports to Management

14. QUALITY ASSURANCE REPORTS

APPENDIX A: PROJECT QUALITY ASSURANCE STAFF RESUMES

APPENDIX B: STANDARD OPERATING PROCEDURES APPENDIX C: ANALYTICAL METHODS FOR NONSTANDARD ANALYSES APPENDIX D: CONTAINERS, PRESERVATION, AND HOLDING TIMES

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LIST OF FIGURES

Number Title

1-1 Cold Creek Swamp site location map.

1-2 Cold Creek Swamp site showing adjacent Stauffer Chemical Plants.

1-3 Cold Creek Swamp site vicinity showing large tracts of wetlands.

1-4 Conceptual model of potential exposure pathways in Cold

Creek Swamp.

2-1 Project organization.

2-2 Laboratory organization.

5-2 Chain-of-custody form.

5-3 Laboratory log.

8-1 Quality assurance summary form.

12-1 Example of an accuracy control chart.

12-2 Example of a precision control chart.

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LIST OF TABLES

Number Title

1-1 Project Schedule.

3-1 Previous contaminant soil/sediment ssunple results for Cold Creek Swamp.

3-2 Chemical compounds to be analyzed in soil/sediment samples.

3-3 Method detection limit inorganic target analyte list

(TAL).

3-4 Data quality objectives.

3-5 Method detection limit.

4-1 Summary of saunples, analytical procedures, holding time, and containers for Stage I contaminant nature characterization.

4-2 Summary of samples, analytical procedures, holding time, and containers for Steige I soil/sediment contaminant characterization.

4-3 Summary of samples, analytical procedures, holding time and containers for Stage I dry weather in situ surface water characterization.

4-4 Summary of samples, analytical procedures, holding time, and containers for Stage II soil/sediment contaminant characterization.

4-5 Summary of samples, analytical procedures, holding time,

and containers for Stage II bioaccessible contaminant.

6-1 DFTPP key ions and abundance criteria.

6-2 BFB key ions and abundsmce criteria.

7-1 Analytical methods.

7-2 Field procedures.

11-1 Field equipment and recommended maintenance requirements.

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EA -QAP-11653.01 Section No.: 1 Revision No.: 1 Date: November 30, 1990 Page: 1 of 3

EXECUTIVE SUMMARY

In 1989 the U.S. Environmental Protection Agency (EPA) Region IV designated the Cold Creek Swamp as Operable Unit Number 3 (0U3) of the Cold Creek/LeMoyne Superfund sites. Cold Creek Swamp is a freshwater river-bottom hardwood swamp encompassing several hundred acres along the Mobile River. The site is located approximately 20 miles north of Mobile, Alabama. The upper portion of the swamp originates on property formerly owned by the Stauffer Chemical Company. The former Stauffer property includes two chemical processing facilities. The LeMoyne Plant produces industrial chemicals and is currently owned by Akzo Chemicals Inc. (Chicago, Illinois). The Cold Creek Plant manufactures agricultural chemicals and is owned by ICI Americas Inc. (Wilmington, Delaware). Akzo and ICI have been designated by EPA as potentially responsible parties (PRPs) with respect to environmental contamination at the Cold Creek/LeMoyne Superfund sites.

In July 1990, Akzo and ICI initiated supplemental Remedial Investigation/ Feasibility Study (RI/FS) activities to investigate specific environmental concerns in the Cold Creek Swamp that had been identified by EPA, the U.S. Fish and Wildlife Service (USFWS), and the National Oceanic and Atmospheric Administration (NOAA) pursuant to review of the original RI/FS for the Cold Creek/LeMoyne Superfund sites. Akzo and ICI retained EA Engineering, Science, and Technology (Sparks, Marylamd) to develop work plans for supplemental RI/FS activities associated with the characterization of Cold Creek Swamp (0U3). On 16-17 August 1990, EA conducted a preliminary site reconnaissance. The main objective of the site visit was to assimilate sufficient background understanding of current site conditions at Cold Creek Swamp to be able to develop amd scope the strategy for data collection for this supplemental RI/FS.

Project Plans

EA has prepared the four site specific RI/FS project plans as required by EPA guidance. These plans will govern all project activities, including data collection amd amalysis, health and safety, quality assurance/ quality control, contamination smd risk assessments, report development, and examination of potential remedial actions. The following plans have been prepared. Note that the Work Plan and Field Sampling Plan have been combined as a Work Plam/Sampling and Analysis Plan.

. Work Plan/Sampling and Analysis Plan (VP/SAP)

. Site Health and Safety Plan (SHSP)

. Quality Assurance Project Plan

The Work Plan/Sampling and Analysis Plan describes objectives of the RI/FS; data quality objectives, data collection rationale; number and location of samples and analyses; field sampling procedures, contamination and risk assessment approach; and RI/FS report development. Potential hazards, levels of protection, and other considerations affecting the health and safety of field personnel are detailed in the

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Site Health and Safety Plan. Field and laboratory Quality Assurance/ Quality Control (QA/QC) requirements for chemical analyses, laboratory operations, required detection limits, field operations, sampling, sample preservation, sample holding times, equipment decontamination, and chain-of-custody are detailed in the Quality Assurance Project Plan (QAPP).

Objectives of the RI/FS

The overall objective of this RI/FS is to supplement existing investigatory work to support quantitation of site-related risks and assessment of remedial alternatives for the Cold Creek Swamp Operable Unit of the Cold Creek/LeMoyne NPL sites. Specific tasks to be performed to meet these response objectives include the following:

Developing an inventory of environmental receptors present in the swamp, including key wetland plamts and animals, and endangered or threatened species.

Delineating wetland boundaries and the extent of upland in the Cold Creek Swamp.

Characterizing the nature and extent of contamination present in swamp soil, sediment, surface water, and biota, including screening representative samples for Target Compound List analytes and thiocarbamates and quantifying mercury speciation both at depth and in biotically active zones.

Characterizing conteunination upstream, downstream, and within Cold Creek Swamp, amd the interaction of the surface water system with the ground-water regime based on existing data available from other previous and ongoing investigations, information to be gathered under this Work Plan, and other available information.

. Estimating and verifying quamtitative risks to human health and the environment due to site-related contaminants by modeling exposure and toxicity and measuring tissue concentration in key receptors.

. Evaluating potential remedial alternatives.

Approach

A three stage field investigation will be used for data collection at this site. Stage I will include soil, sediment, and surface water sampling to characterize the nature and extent of contamination in the swamp and to focus sampling efforts for subsequent stages. In addition, a wetland delineation/ecological assessment survey will be conducted.

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During Stage II, more intensive sampling will be conducted to characterize the nature and extent of contamination specifically within the bioaccessible zone of the swamp. The Stage II sampling will be focused to concentrate on the parameters determined to be representative of bioaccessible chemical contamination within the swamp. Existing data indicate that mercury will be the primary contaminant of concern for this study. This Work Plan is developed based upon that premise. Should additional contaminants be identified as significant as a result of Stage I testing, additional characterization of these contauninants will be added to the Stage II field effort, as appropriate.

Data generated during Stages I and II will be used to develop a preliminary ecological risk assessment and to conduct ecological risk modeling. Results of ecological risk modeling will be used to select representative numbers and types of biological species to be sampled amd analyzed during Stage III. This staged approach will enable the consultant to optimize biological tissue collection. Species that have been found to be most at risk due to exposure to site contaunination, based upon the ecological risk modeling, will be selected for Stage III sampling.

At the conclusion of Stage III data collection, a contamination assessment will be made to examine the nature and extent of site conteunination and to examine contaminant transport pathways and potential impacts beyond the site area. Risk assessments will also be conducted to identify exposure pathways and magnitude of risk from contauninamt exposure from both ecological amd human health perspectives. The contaunination assessment amd risk assessment data will be compiled and combined into a comprehensive Remedial Investigation (RI) report in accordance with EPA protocols.

The Feasibility Study (FS) will be initiated midway through development of the RI. The FS will identify remedial action objectives, based upon the findings of the RI contamination amd risk assessments, and the applicable or relevant and appropriate requirements (ARARs) governing remediation at the site. Potential remedial action alternatives will be developed amd examined with respect to evaluation criteria defined by EPA in the revised National Contingency Plam (NCP). Treatability studies will be conducted as needed during the FS. A particular consideration related to this site will be potential adverse impacts of remedial action alternatives to the Cold Creek wetlamd ecosystem. Alternatives that may result in greater destruction of the wetland than is necessary for the protection of natural resources will not be considered to be feasible.

The ultimate product of this investigation will be a final supplemental RI/FS report submitted to EPA Region IV. It will be a stand-alone document amd will take into account all available 0U3 data.

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1. PROJECT DESCRIPTION

Cold Creek Swamp is a freshwater cypress swamp that drains into the Mobile River near Axis, Alabauna, approximately 20 miles north of Mobile, Alabama (Figure 1-1). Previous environmental investigations have indicated that the swamp has become contaminated as a result of wastewater discharges from chemical plants previously operated by Stauffer Chemical Company and Halby Chemical Company (Figure 1-2). The two Stauffer Chemical plants (Cold Creek Plant and LeMoyne Plant) are listed as sites on EPA's National Priority List (NPL).

A Remedial Investigation/Feasibility Study (RI/FS) was conducted between 1985 and 1989 to characterize the nature and extent of contamination related to Stauffer Chemical plamt activities. A Final Remedial Investigation (RI) Report was submitted to the Environmental Protection Agency (EPA) Region IV in May 1988. Subsequent to EPA and other regulatory review comments, a follow-up Biota Study was conducted to characterize the effect of mercury contaunination on the biological community in Cold Creek Swaunp. This report was submitted to EPA in June 1989.

In May 1990, the EPA concluded that additional environmental studies were needed to further characterize the nature and extent of contamination in Cold Creek Swaunp and to further examine potential impacts of swamp contamination on the biological community within and around the swamp. EPA requested that a supplemental RI/FS be initiated to address specific concerns raised by the EPA, the U.S. Fish and Wildlife Service (USFWS), and the National Oceamic and Atmospheric Administration (NOAA) related to Cold Creek Swaunp.

1.1 DESCRIPTION OF CURRENT STUDY

In 1989 the U.S. Environmental Protection Agency (EPA) Region IV designated the Cold Creek Swamp as Operable Unit Number 3 (0U3) of the Cold Creek/Lemoyne Superfund sites. Cold Creek Swamp is a freshwater riverbottom hardwood swamp encompassing several hundred acres along the Mobile river. The upper portion of the swamp originates on property formerly owned by the Stauffer Chemical Company. The former Stauffer property includes two chemical processing facilities. The Lemoyne Plant produces industrial chemicals amd is currently owned by Akzo Chemicals Inc. (Chicago, Illinois). The Cold Creek Plamt manufactures agricultural chemicals and is owned by ICI Americas Inc. (Wilmington, Delaware). Akzo and ICI have been designated by EPA as potentially responsible parties (PRPs) with respect to environmental contaunination at the Cold Creek/Lemoyne Superfund sites.

In August 1990, Akzo and ICI selected EA Engineering, Science, and Technology to perform the supplement RI/FS for Cold Creek Swamp. On 16-17 August 1990, EA conducted a preliminary reconnaissance to examine site conditions. The site visit included interviews with key plant personnel, review of plant historical records, a site walk-through, and a site overflight.

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Rgure 1-1. Cold Creek Swamp site location map.

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Previous investigations at the site include the May 1988 RI report and the June 1989 Cold Creek Biota Study. These investigations indicated that the primary contaminamt of concern at Cold Creek Swamp is mercury. Potential impacts from mercury exposure are primarily to the biological community in and around the swamp. Previous studies have not characterized potential ecological impacts of swamp contamination to an extent that satisfactorily allays the concerns of various review agencies, including the EPA, USFWS, and NOAA.

For this supplemental RI/FS, a three stage field investigation will be used to optimize data collection and assure that all Data Quality Objectives are satisfied. Field activities will include shallow soil/sediment samplings and analysis; surface water sampling and analysis; soil borings and analysis; biological tissue collection and analysis; wetland delineation and ecological characterization.

To ensure the quality of the field amd laboratory data produced during the implementation of the supplemental RI/FS this quality assurance project plan (QAPP) has been prepared according to the guidelines set forth by the U.S. Environmental Protection Agency (EPA) in "Interim Guidelines and Specifications for Preparing Quality Assuramce Project Plans," (QAMS-005/80), EPA. This QAPP provides guidance to the filed and laboratory personnel concerning methodology of data collection, proper record keeping protocols, data quality objectives and procedures for data review. All field sampling and amalytical chemical activities or this project will be performed in accordamce with current EPA guidance and with provisions of EPA Region IV Engineering Support Branch Standard operating Procedures and Quality Assurance Manual (April 1986).

1.2 OBJECTIVES

The objective of this RI/FS is to develop a database sufficient to:

1. Characterize the nature and extent of pollutant-specific contamination within the swamp, both vertically and horizontally.

2. Characterize the nature and extent of pollutamt-specific contamination within the biologically active zone of Cold Creek Swamp.

3. Characterize potential impacts of pollutant-specific contamination in Cold Creek Swamp on the biological community within and around the swaunp.

4. Further assess the potential relationship between surface water in the swamp and the underlying ground-water system.

5. Identify the areal and ecological limits of Cold Creek Swamp.

6. Evaluate potential human health and environmental risks based upon data collection and ecological modeling.

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7. Develop an RI report.

8. Support an informed risk management alternatives analysis for remedial actions to be evaluated in the Feasibility Study (FS).

Data collected for this study will be used to develop the final RI amd FS reports.

1.3 SITE DESCRIPTION

Cold Creek Swamp is located in the northeast section of Mobile County, Alabauna, approximately 20 miles north of Mobile, 6 miles south of Mt. Vernon amd 5 miles north of Creola (Figure 1-1). The site encompasses several hundred acres (precise area to be determined as a component of this study) situated between U.S. Highway 43 to the west and the Mobile River to the east (Figure 1-2). The surrounding area is sparsely populated and consists primarily of riverbottom swamp land and other wetlands (Figure 1-3).

The Mobile River in Mobile County is an important water source for industrial, agricultural, and recreational uses. Other water supply sources in the site vicinity include wells, springs, and farm ponds.

The main industries that are adjacent to the Cold Creek Swaunp are the chemical production plants to the west and south and a coal fired electrical power generating plant to the north (Alabauna Power Compamy).

1.4 TOXIC OR HAZARDOUS SUBSTANCES THAT MAY BE ENCOUNTERED

1.4.1 Contaminant Characterization

While a substantial effort has been made to characterize contauninants associated with the Cold Creek/LeMoyne site, much of the sampling effort to date has focused on contamination at the plamt sites rather than at the Cold Creek Swamp. Existing information on the nature amd extent of swamp contamination includes a series of tissue amalyses amd depth-composite cores taken in 1986 for the original RI/FS (ERT 1988). While composite saunples do not provide sufficient information to document the vertical extent of contamination, existing sample results can provide a basis for determining the lateral extent of contamination. Furthermore, three of the samples were screened for the range of EPA Priority Pollutant List compounds. These results provide useful information concerning the nature of soil contamination in the Cold Creek Swamp.

Indicator compounds selected according to EPA guidamce on the basis of detection frequency, concentrations, and toxicity for the initial RI/FS were carbon tetrachloride, carbon disulfide, cyanide, mercury, thiocarbamates, organophosphates, chloride, and thiocyanate. Of these, only mercury was detected at significamt levels in Cold Creek Swamp.

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EA QAP-11653.01 Section No.: 1 Revision No.: 1 Date: November 30, 1990

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Figure 1-3. Cold Creek Swamp site vidnlty showing large tracts of wetlands.

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Thiocarbamates were present at low levels. Inorganics (chromium, copper, lead, and zinc) were observed in some soil samples from the swamp; however, most of these concentrations were within expected ranges for normal soils (EPA 1983). A data summary is provided in Table 3-1.

Primary concern for impacts to Cold Creek Swamp environmental receptors has focused on mercury contamination (USDOI 1987, 1989, 1990; NOAA 1989; EPA 1990) since mercury is the most ubiquitous and toxic contaminant that has been found in swamp sediment amd biota. While there is reason to believe that sulfide in swamp sediment reduces mercury bioavailability, saunples collected in 1986 indicate that mercury has been sequestered in finfish tissue. Total mercury was recovered consistently in composite samples of swamp sediment, with a detection frequency >95 percent at quamtified concentration levels ranging from below the method detection level to 690.0 mg/kg.

1.4.2 Potential Exposure Pathways

Primary concerns for the environment amd human health associated with contamination in Cold Creek Swamp are for potential toxicity to ecological receptors and for potential food-web-based exposure to humans. Because of these concerns and based on existing data, the following exposure pathways are of potential ecological or human health concern:

Ecological Pathways

exposure to dissolved and sediment-bound contaminants in the surface water column

exposure to contaminated upland soils

exposure to contaminated aquatic sediments

food-web exposure

Human Health Pathways

food-web exposure

exposure to dissolved and sediment-bound contaminamts in the surface water column

exposure to contaminated aquatic sediments

Figure 1-4 illustrates a conceptual model of potential exposure pathways in Cold Creek Swamp.

Primary Sources

Primary Release Mechanisms

Secondary Sources

Secondary Release Mechanisms

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1.5 DURATION OF PROJECT

Table 1-1 shows the performance schedule and schedule of deliverables for project activities associated with the Cold Creek Swamp Operable Unit Supplemental RI/FS.

A three stage field sampling effort is scheduled. Stages I and II are scheduled to be conducted during dry weather conditions, and will concentrate on soil/sediment and dry season surface water data collection. Stage III field sampling is scheduled to be conducted during the spring wet-weather conditions. Stage III saunpling will collect biological tissue for analysis. Stage III sampling is scheduled to allow adequate time to compile Stage I and II data amd to perform ecological risk modeling activities. This information is necessary to design and optimize Stage III sampling.

The project is phased to begin feasibility study activities at the earliest reasonable time during the RI phase. This streamlined approach results in significant time savings and an anticipated project perfor-mamce period of less tham 24 months.

Two review conferences with all regulatory agencies have been scheduled. The first review conference will be held approximately 6 weeks after submission of the draft RI report. The second review conference will be held approximately 9 weeks after submission of the draft FS report. Both review conferences will be held at EPA Region IV offices in Atlanta.

It is recommended that an additional meeting be scheduled shortly after EPA has had an opportunity to review the Work Plans. This meeting should be held at EPA Region IV headquarters in Atlamta.

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TABLE 1-1 PROJECT SCHEDULE

1 Oct 90 Submit Work Plans to EPA 26 Oct 90 Receive EPA review comments 6 Nov 90 EPA review comment meeting 3 Dec 90 Submit final plans to EPA 14 Jan 91 Stage I field investigation begin 26 Jan 91 Stage I field investigation end 8 Mar 91 Stage I chemistry data available 18 Mar 91 Stage II field investigation begin 27 Apr 91 Stage II field investigation end 7 June 91 Stage II chemistry data available 8 July 91 Revised Stage III field plan submitted to USEPA 9 Aug 91 Receive EPA review comments

26 Aug 91 Stage III field investigation begin 14 Sep 91 Stage III field investigation end 28 Oct 91 Stage III chemistry data available 4 Nov 91 Nature/Extent Characterization complete

(excluding ecological risk) 4 Dec 91 Establish ARARs/Remedial Objectives/General

Response Actions 4 Dec 91 Ecological Risk Assessment complete 4 Dec 91 Human Health Risk Assessment complete 12 Feb 92 Draft RI to EPA 11 Mar 92 RI Review Comments from EPA 25 Mar 92 RI Review Conference (with regfulators) at

Region IV 15 Apr 92 Final RI to EPA 15 July 92 Draft FS to EPA 17 Aug 92 FS Review Comments from EPA 25 Aug 92 FS Review Conference (with regulators) at

Region IV 16 Sep 92 Final FS to EPA

1. This schedule assumes 30 day review period for all project submittals and all projected dates are dependent on timely document review.

2. It is imperative that Stage I and II sampling events occur during the drier season (November-March) amd that Stage III sampling occur during the wettest season (July/August/September) to assure relatively accessible sampling conditions.

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PROJECT MANAGEMENT AND RESPONSIBILITIES

2.1 GENERAL

Management of this project will require flexibility in the organization of a team of scientific and engineering personnel and technical resources in order to conduct am RI/FS which exaunines the chemical contamination at the Cold Creek Swamp. The field investigation will be implemented in three stages and will employ pre-approved field procedures, sampling techniques, and analytical methods to accomplish data collection objectives. Effective prograun organization will accommodate these requirements for both flexibility and consistency while maintaining a manageable degree of control over all activities.

Figfure 2-1 illustrates the proposed orgamization for accomplishing this effort. The core of the technical organization is the Project Manager amd the assigned Project Team. Additional individuals can be made available if warramted.

2.1.1 Project Director Responsibilities

The Project Director is responsible for oversight of all contractual activities and provides direction and guidamce to the Project Mamager in contractual matters. The Project Director is responsible for reviewing and approving any amd all contractual submittals, including negotiation of contractual rates, submission of fee proposals, negotiation of fee proposals and project scopes, selection of specialty subcontractors (with concurrence of ICI amd Akzo) amd preparation of subcontractor agreements, monthly invoicing, and project status reports. The Project Director ensures that all activities under this project are carried out in accordance with contractual requirements and in accordance with the corporate Hazardous Waste Program requirements.

2.1.2 Project Mamager Responsibi l i t ies

The Project Mamager is responsible for effective overall management of all project-related activities. The Project Manager serves as the primary technical point of contact with Akzo and ICI and coordinates management of project subtasks. Specific responsibilities of the Project Manager include (1) mamagement of all technical activities; (2) preparation of work flow diagrauns, schedules, labor allocations, and survey plans; (3) management of all funds for labor amd materials procurement; (4) review and administration of all work-order changes; (5) successful accomplishment of all contractual obligations, including costs, schedules, and technical performamce; (6) management of the Project Team toward a unified, productive project accomplishment; (7) format and quality control of all documents amd data reports; and (8) technical leadership.

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AZKO CHEMICALS INC. ICI AMERICAS INC.

HEALTH & SAFETY

PROJECT DIRECTOR

PROJECT MANAGER

QUALITY ASSURANCE

FIELD ACTIVITIES MANAGER

SITE MANAGER

I

ECOLOGICAL RISK EVALUATION

1 FEASIBILITY

STUDY

1 CHEMICAL ANALYSIS

Figure 2-1. Project organization.

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2.1.3 Quality Assurance Officer Responsibilities

The Quality Assurance (QA) Officer will be responsible for overall quality assurance of all aspects of the project. The QA Officer reports directly to the Consultant's President and has the authority to audit all phases of all corporate operations. The QA Officer oversees the Corporate Quality Assurance/Quality Control Program and is responsible for development of Standard Operating Procedures (SOPs) related to analytical chemistry laboratory methods; field investigation amd sampling prograuns; engineering design; and construction quality control. The QA Officer is responsible for development amd oversight of the Sampling and Analysis Plan and Quality Assurance Project Plan.

2.1.4 Health and Safety Officer Responsibilities

The Health and Safety Officer is responsible for development of project-related Health amd Safety Plans. The Health and Safety Officer will assign site safety supervisors for various phases of construction activities in accordance with the project-specific Health and Safety Plam. The Health and Safety Officer will have the authority to temporarily halt any and all construction activities based on identified health and safety concerns.

2.1.5 Field Activities Manager Responsibilities

The Field Activities Manager is responsible for direction and management of field sampling teams and assurance of quality data collection. The Field Activities Manager is responsible for implementation of the provisions of the Work Plam/Sampling and Analysis Plan, the Quality Assurance Project Plan, amd the Site Health and Safety Plan during data collection activities, and for coordination with the analytical chemistry laboratory for sample handling amd tramsport.

2.2 CONTRACTOR LABORATORY ORGANIZATION

The organizational positions, management and technical staff, and their responsibilities are shown in Figure 2-2. The contractor laboratory has the overall responsibility for performance of specified analyses for projects at prescribed levels of quality; custody control, and traceability responsibility from sample delivery to results reported to clients; amd responsibility for implementing and maintaining quality control procedures amd documentation for those saunples analyzed according to approved, written instructions and methods. The functional responsibilities for each position shown in Figure 2-2 are described below.

2.2.1 Vice President

1. Ensures laboratory data quality.

2. Maintains laboratory staffing.

r

EA LABORATORIES VICE PRESIOEMT

PUnCHASMO SPECIALIST

QA«X MANAGER

(.MS SVSTEM MANAOER

AOMMVmATIVE UANAOCR

SENIOR CHEMIST

AOMMISTRATIVB ASSISTANT

OnOANICt MANAQER

QC SPECIALIST

REPORTS SUPERVISOR

HOnOANICS HANAaSR

TECHNKML 8UPPOR1 SPECtALIST

CHnOMATOQRAPHY SUPERVISOR

EXTRACTIONB SUPERVISOR

SPECIAL PRCUGCTS SUPPORT MANAQER

TECHNICAL SUPPORT SPECIALIST

A C T I M M « T CHEMI8TRV SUPERVtSOf

METALS SUPERVISOR

MASS SPECTROMETRY SUPERVISOR

•AMPUE MANAQER OFFICER

SAFETY ft HEALTH (XIORDMATOR

QLASSWARE LAB SUPPORT

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3. Develops laboratory budget.

4. Ensures laboratory safety.

5. Approves laboratory equipment acquisition.

6. Promotes laboratory marketing amd client interface.

7. Sets amalytical priorities.

2.2.2 Quality Assuramce Manager

1. Selects, reviews, amd troubleshoots analytical methods.

2. Develops, refines, and monitors the laboratory QA/QC program.

3. Responsible for the review and approval of data and reports generated in the laboratory.

4. Responsible for maintaining, updating and distributing the mamual, SOPs and methods.

5. Maintains state, federal, and client laboratory certifications.

6. Reviews and approves data quality and quality checks performed by staff.

7. Reviews quality control procedures and criteria for compliance with method and project requirements.

8. Represents the laboratory during all regulatory and client inspections. Conducts routinely scheduled audits of each laboratory section.

9. Conducts periodic training programs for all laboratory personnel on QA/QC issues, updates to regulatory or other quality matters.

2.2.3 Administrative Manager

1. Manages the analytical flow from container supply and sample receipt through data acquisition and client report generation.

2. Directs the activities of the first-line supervisors in the completion of client-generated amalytical task orders, i.e., scheduling, problem-solving, and general administrative duties.

m 3 4 0 0 6 i


3. Maintains active contact with outside clients and internal project managers with regard to: supplying technical information, regulatory assistance in regard to analytical needs, and saunple status updates; amswering billing and costing inquiries; providing price quotations.

4. Monitors expenditures debited and income credited to specific laboratory accounts to assess profitability of the various lab areas.

5. Coordinates lab and field personnel activities through the consulting, conferring amd scheduling of client needs.

2.2.4 Data Manager

1. Responsible for the site preparation, and onsite configuration of hardware and software for the Laboratory Management Information System (LIMS).

2. Identifies custom programming needs, and prepares protocols for system operation.

3. Responsible for user training, and routine system maintenance.

4. Assists the Vice President, by providing specialized technical knowledge in overall computerization of laboratory functions, including data mamagement, scheduling, mamagement reports, and financial reports.

2.2.5 Inorganics amd Orgamics Managers

1. Responsible for the implementation of their respective analytical programs operating in the inorganics and organics laboratories.

2. Provides technical knowledge of methodologies and instrumentation for group, company, and clients.

3. Responsible for data review against project requirements and internal quality control criteria.

4. Plans for expansions or purchases in order to increase the efficiency of the operation.

5. Provides information on capacity, pricing, and scheduling of work.

6. Performs personnel functions such as hiring, reviews, timesheet approval, time-off approval, recommending salary adjustments.

7. Troubleshoots instruments and keeps up-to-date with the software developed in the area of organic analysis.

m 5 4


ll u b , - '

1990

2.2.6 Supervisors

1. Participate in planning laboratory programs on the basis of specialized knowledge of problems and methods amd probable value of results.

2. Assist the Laboratory Managers in one or more areas of overall mamagement of the amalytical laboratory, including personnel, physical plant, amd financial budgeting and planning.

3. Troubleshoot problems regarding analytical procedures and equipment performance.

4. Perform quamtitative and qualitative analyses using manual or specialized and complex instrumental methods.

5. Fully competent and proficient in the operation of sophisticated scientific equipment.

6. Interpret results, prepare reports, and provide technical advice in specialized area.

7. Supervise and train staff in methods of analyses, standard operating procedures, amd QA/QC requirements.

8. Provide advice to Laboratory Managers in budgetary amd personnel matters.

2.2.7 Sample Management Officer

1. Receives, logs, amd assigns control numbers to incoming samples.

2. Follows standard operating procedures and QA/QC requirements for all analyses performed and assignment of samples for analysis and storage by other amalysts.

3. Responsible for saunple storage facilities. Maintains a log record on these facilities, including temperature of storage rooms, and procedures for sample storage area.

4. Assists in ordering laboratory supplies, chemicals, and glassware.

5. May assist in training and supervising technicians in amalyses and quality control procedures for sample tracking.

6. Follows all laboratory safety rules.

^ 4 u u 6 :


2.3 ANALYTICAL LABORATORY

An amalytical laboratory will be selected for this project after EPA review of the Work Plan. The laboratory selected for this project must meet EPA CLP requirements amd will be submitted for acceptance by EPA.

A laboratory Project Manager amd Quality Assurance Officer will be appointed to this project. The Project mamger for the laboratory will be responsible for liaison between the laboratory and the Contractor QAO and Project Manager. The laboratory Project Manager also will be responsible for reviewing all analytical reports to ensure: (1) data quality objectives have been met; (2) all requested work has been completed; (3) all reports have identical format; (4) quality assurance reporting requirements are complete; amd, (5) timely delivery of the proper number of report copies to designated recipients. The laboratory Project Manager will also be indirectly involved with sample receipt, log-in and tracking, amalysis, quality assurance, report preparation, and initial review.

The laboratory Quality Assurance Officer will be responsible for establishment of quality assurance program within the laboratory to provide consistency, accuracy and precision in the amalysis of samples. The laboratory Quality Assurance Officer will also be responsible for internal laboratory data validation prograuns and quality assurance audits.

Qualifications of the laboratory's personnel will be presented along with a copy of their generic QAP (Attachment 1).

3 4 0 0 6-:

•

u o EA QAP-11653.01 Section No.: 3 Revision No.: 1 Date: November 30, 1990 Page: 1 of 19

3. QUALITY ASSURANCE OBJECTIVES

3.1 DATA QUALITY/QUANTITY NEEDS

The following sections discuss determination of the specific data quality/quantity needs for each environmental medium to be sampled during field activities for the supplemental RI/FS at the Cold Creek Swamp Operable Unit. It should be noted that the number amd type of analyses to be performed in Stages I and III may be modified pursuant to assessment of data from previous stages.

3.1.1 Soil/Sediment Sampling Data Requirements

Existing data collected during the original RI/FS revealed concentrations of mercury ramging from below quantitation limits to 690 mg/kg in samples collected from shallow soil cores throughout Cold Creek Swamp. Other observed compounds included arsenic (5 mg/kg), chromium (130-180 mg/kg), lead (below detection level to 31 mg/kg), nickel (32-56 mg/kg), zinc (171-561 mg/kg), and several thiocarbamate pesticides (not detected to 1.8 mg/kg). Concentrations of all observed compounds were within order of magnitude levels typical of natural soils (Table 3-1) with the exception of mercury and the thiocarbamates. Previous data collection did not characterize contaminamt concentrations at discrete vertical depths and did not differentiate between total and organic (methyl) mercury. The vertical distribution of contaminants is needed to identify whether contamination is concentrated in the biologically active zone of swamp sediments or is distributed throughout the soil matrix. Differentiation of total and organic (methyl) mercury is needed to indicate how much mercury is inorganic and how much is organic. Table 3-2 identifies sampling requirements for investigation activities for this supplemental RI/FS. Available data indicate that mercury will be the primary contaun-inant of concern in swamp soil/sediment. As such, Stage II saunpling is designed to focus on refining mercury characterization. If additional contaminants of concern are identified during Stage I, Stage II will be modified, as appropriate.

Data collected from soil/sediment saunpling will be used for several purposes. All of the Stage I soil/sediment saunpling data and approximately half of the Stage II soil/sediment saunpling data will be used for determination of the nature amd vertical amd horizontal extent of contamination; potential migration pathways (erosional amd depositional) amd rate of migration; and preliminary indication of source areas and "hot spots." Background concentrations of metals will be determined by calculating the geometric mean of soil/sediment samples taken at selected background locations. Cold Creek Swamp soil/sediment samples will be compared to background data to determine whether or not to analyze Stage II samples for specific metals contamination. The remainder of Stage II sampling data will be used to assess the nature and extent of contamination located specifically within the biologically active zone (upper 4 in.) of Cold Creek Swamp sediments. In addition to site characterization,

TABLE 3-1 PREVIOUS CONTAMINANT SOIL/SEDIMENT SAMPLE RESULTS FOR COLD CREEK SWAMP

Compound

VOCs Semlvolatiles PCB's/Pestlcides-

No. of Locations sampled

3 3 3

Concentration Range (mg/kg)

ND ND ND

(b)

Average Concentration

(mg/kg)

ND ND ND

Average Concentration on Natural Soils^

(mg/kg)

NA NA NA

(c)

Metals Mercury Arsenic Beryllium Chromium Copper Lead Nickel Zinc

34 3 3 3 3 3 3 3

ND-690 5-5 .31-.81 120-180 14-35 ND-31 32-56 171-561

54.7 5 0.53 150 27.7 19 46.9 348

.03 5 6 100 30 10 40 50

Thiocarbamates EPTC (Eptam) Butylate (Sutan) Vernolate (Vernam) Pebulate (Tillam) Holinate (Ordram) Cycloate (Ro neet)

Chloride

.1-1.0 ND-1.8 ND-1.1 ND-.3 .1-.9 ND-l.B

ND-50

.4

.7

.4

.1

.5

.8

33.3

NA NA NA NA NA NA

NA

(a) = Reference: USEPA Office of Solid Waste and Emergency Response, Hazardous Waste Land Treatment, SW-874 (April 1983) p.275, Table 6.46.

(b) = ND - Not Detected (c) = NA - Not Available

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3 4 EA QAP-11653.01 Section No.: 3 Revision No.: 1 Date: November 30, Page: 3 of 19

u u 6 0

1990

TABLE 3-2 CHEMICAL COMPOUNDS TO BE ANALYZED IN SOIL/SEDIMENT SAMPLES

Number of Compound Sample Locations

Stage I

TCL Volatile Organics 12 TCL Semivolatile Organics 12 TCL Pesticides/PCBs 12 Cyanide 12 Thiocarbamates 12 Mercury (Total) 19 Other TAL Metals 16 Methyl Mercury 19 Sulfide 15

Stage 11^^^

Mercury (Total) 105 Methyl Mercury 72 Sulfide 105 Total Organic Carbon 60

Stage III^^^

Not addressed at this time

(a) The final number of samples and parauneters to be analyzed for during Stages II and III may be modified pursuant to assessment of data results from previous stages.

'-' ' -u U i j •


soil/sediment data will be used for ecological modeling and risk assessment purposes. Soil/sediment sampling locations have been selected based upon examination of previous Cold Creek Swamp characterization and preliminary site reconnaissance by EA in August 1990.

Since this site is an Operable Unit for two NPL sites, analytical detection levels for chemical analysis will meet EPA Level III requirements. This level employs approved EPA procedures with specified detection limits. The appropriate analytical methods and detection limits are provided in the Quality Assuramce Project Plan.

3.1.1.1 Applicable or Relevamt and Appropriate Requirements (ARARs) for Soil/Sediment Sampling

Section 121 (d) of CERCLA, as amended by the Superfund Amendments amd Reauthorization Act (SARA), requires that remedial actions at Superfund sites comply with requirements or standards under Federal or State environmental laws that are "applicable" or "relevant and appropriate" to the hazardous substances, pollutants, or contaminants at a site or the circumstances of the release. A requirement may be either applicable or relevant and appropriate to a remedial action, but not both. An applicable requirement is one that specifically addresses a hazardous substance, pollutamt, contaminant, remedial action, location, or other circumstances at a hazardous waste site. Relevamt and appropriate requirements, while not applicable, address problems or situations sufficiently similar to those encountered at a hazardous waste site so that their use is well suited to the particular site (55 FR 8666, 8 March 1990).

No federal or Alabama state standards, criteria, or guidelines are relevant to chemical contamination in soil or sediment; however, certain technical documents may be reviewed to assess potential exposure (including a March 1990 publication by NOAA entitled "The Potential for Biological Effects of Sediment-Sorbed Contaminants Tests in the National Status amd Trends Program," and documents related to AET, EP, amd sediment toxicity testing).

3.1.1.2 Critical Samples for Soil/Sediment Analysis

Critical samples are those samples for which scaled data must be obtained to satisfy the objectives of the saunpling amd amalysis task. They are as follows:

. Field Duplicate—to be collected one per 20 samples per matrix, for purposes of comparing repeatability of laboratory chemical analysis results and sampling procedures.

. Rinsate Blank—to be collected one per site per saunpling event to demonstrate field sampling decontaunination procedure effectiveness. Rinsate blanks will not be collected on dedicated sampling devices.

• 4 U0 63 EA QAP-11653.01 Section No.: 3 Revision No.: 1 Date: November 30, 1990 Page: 5 of 19

. Field Blank—to be collected one per site per sampling event to demonstrate preservation reagent quality and aliquot container cleanliness.

. Trip Blank—[volatile organics analysis (VOA) only] to accompany eacn shipment of samples (if VOA analysis is part of shipment) for purposes of demonstrating the effect of transport on the sample matrix.

In addition, soil samples will be collected from uplamd locations beyond the limits of the swamp and will be used as background soil samples. Those samples, along with background soil samples collected during the original RI/FS, will be used as a background baseline for soil.

3.1.2 Surface Water Sampling Data Requirements

No sampling has been conducted in the Cold Creek Swamp, although limited surface water saunpling was conducted in the vicinity of Cold Creek Swaunp as a component of the original RI/FS. Two surface water samples were collected from unnamed tributaries to Cold Creek. One tributary is located north of the Hoechst-Celanese Plant (north of Cold Creek), and the other is located approximately 100 ft north of the LeMoyne-Courtaulds Fibers property line near the railroad tracks. Previous surface water saunples did not exhibit concentrations of priority pollutamts above detection levels, with the exception of mercury (0.0002 mg/L) amd zinc (0.31 mg/L) in one of the two samples.

Surface water data collection for this project is proposed to characterize surface water quality within the Cold Creek Swamp, within waters discharging to Cold Creek Swamp, at the mouth of Cold Creek and within the Mobile River, upstream and downstream of the swaunp discharge location. The objectives of surface water data collection are to characterize contamination upstream, downstream, and within the Cold Creek Swamp; and to characterize contauninant transport via surface water and the potential for ground-water contaunination through surface water aquifer recharge. Table 3-3 shows the proposed sampling prograun for investigation activities for this supplemental RI/FS.

Since surface water quality data will be used in ecological modeling and risk assessment, amd since the site is am operable unit for two NPL sites, EPA Level III analytical data levels will be utilized.

3.1.2.1 ARARs for Surface Water Sampling

The Cold Creek/LeMoyne Superfund sites RI/FS concluded that surface water exposure at the Cold Creek and LeMoyne plants does not constitute a human health exposure pathway, based upon site use and limited site access. Cold Creek Swamp, however, represents am excellent habitat for wildlife, and potential receptors are the native plant and animal species. Water

- ^ u u o.


TABLE 3-3 CHEMICALS TO BE ANALYZED IN STAGE I SURFACE WATER SAMPLING

Compound Number of Samples

TCL Volatile Organics 6 TCL Semivolatile Organics 6 TCL PCBs/Pesticides 6 Thiocarbamates 6 Cyanide 6 Methyl Mercury 6 Other TAL Metals 6


Quality Criteria (WQC) values established under the Federal Water Pollution Control Act, as aunended by the Clean Water Act of 1977, and the Water Quality Act of 1987, will be probable ARARs governing surface water quality.

3.1.2.2 Critical Samples for Surface Water Analyses

The samples that will be classified as critical for purposes of this investigation are the same type of saunples as described for soil/sediment sampling. Three of the ten proposed surface water saunpling locations are intended for use as background water quality assessment. Background samples will be taken upstreaun of the project site along Cold Creek south and west of the site, and along the Mobile River north of the site.

3.1.3 Biological Tissue Sampling Data Requirements

Biological tissue sampling was conducted in Cold Creek Swaunp in 1986 (1988 RI Report by CDM) and in 1988 (1989 Biota Study by BCM). Five species-composite samples of finfish were amalyzed for whole-body mercury concentrations in 1986, and species-specific analyses including invertebrates were conducted in 1988. Some samples, including one taken above Cold Creek Sweunp at a reservoir outfall in the headwaters of Cold Creek, carried mercury body burdens above those that would be expected in uncontaminated areas.

Samples to support quamtitative risk estimates will be based on mercury food web and bioaccumulation model calculations. These models will incorporate information on resources present in the swamp, trophodynamics of the swamp ecosystem, amd key receptor species chosen on the basis of scientific and regulatory requirements. Criteria to support selection of key receptors will include (1) potential risk of contaminant uptake and associated population effects, (2) unique value or regulatory status, and (3) potential for community or ecosystem-level effects. Samples will be taiken of appropriate species to determine potential bioaccumulation, toxicity, and impacts as indicated by models. This approach minimizes the number of destructive samples that must be taken from swamp populations, and maximizes the value of each saunple by providing a mechanistic basis for understamding mercury dynamics in the ecosystem.

Tissue data are required for specific comparative and risk assessment purposes, amd detection limits, quantitation limits, precision, and accuracy will be defined by the analysis and study purpose. DQOs will provide accuracy amd precision sufficient to meet the modeling objectives amd characterize site-related risks. Within the limits of available methods, analytical methods will provide quantitation limits compatible with those employed for samples from other environmental media.

The existing database provides an opportunity to assess temporal trends in tissue contamination, allowing projection of future conditions given ongoing ecological processes. Biological tissue saunpling for mercury will be conducted to characterize possible changes since 1986 amd to

3 4 U O / ' i


support quamtitative estimation of risks to human health and ecological resources. Samples to characterize temporal trends will reproduce as closely as possible the saunpling that was conducted in 1986. Reports, notes, and interviews with and direction by personnel present at the past sampling will be employed to locate new samples in the vicinity of the old. Collection, analysis, and reporting methods will be similar, maximizing the comparative value of these samples.

3.1.3.1 ARARs for Tissue Samples

Consistent with EPA guidance (EPA 1989b), criteria will be identified which serve as potential ARARs. In general, tissue ARARs are limited and vary among states and regions. For Cold Creek Swamp, it is anticipated that federal or state tissue consumption limits, criteria possibly derived from CERCLA/NEPA equivalence, and/or additional state criteria may apply as ARARs or criteria to be considered (TBCs). Applicability will be assessed for each potential ARAR, based on study findings relating to human and environmental exposure, nature and extent of contaunination, and contaminants potentially present.

3.1.3.2 Critical Saunples for Tissue

Critical samples for quality assurance will be determined by analytical methods amd will include blanks amd duplicates as appropriate. The study as designed on the basis of environmental risk modeling does not rely on comparison with a "reference" area for tissue, because contaminant-associated risks in Cold Creek Swamp may be quantified amd are of primary interest. However, at least one reference station with multiple samples will be included for samples taken in the Mobile River to determine upstream background concentrations of mercury.

3.2 QA OBJECTIVES FOR MEASUREMENT DATA

This section presents the QA objectives for the chemical data in terms of precision, accuracy, completeness, representativeness, and comparability. See Table 3-4.

3.2.1 Precision

Precision is the mutual agreement aunong individual measurements of the same property and is a measure of the random error component of the data collection process. The overall precision of the data is the sum of that due to the sampling amd analysis. The sampling precision is assessed by collecting field duplicates. The analytical precision is determined by preparing and analyzing duplicate subsaunples. Precision can be expressed in several different ways, each of which has its uses; for multiple measurements these include the standard deviation, the relative standard deviation, and the ramge, and for duplicates the relative percent difference.


TABLE 3-4 DATA QUALITY OBJECTIVES

Parameter Matrix'

Volatile Organics

Semivolatile Organics

Halogenated hydrocarbon pesticides

Thiocarbamate pesticides

Methylmercury

Metals

Mercury

Inorganics

Chloride

Sulfide

Physical Total dissolved solids (TDS) pH eH

W s

w s

s

w s

s

w w s s w s T

w s w s

w w s

Method'

M M

M M

G

G G

G

F I F I V V V

IC IC T T

G E E

Precision (X)

80 0.1 0.1

80-120 70-130

40-140 30-150

50-150

40-140 30-150

(3)

80-120 80-120 80-120 80-120 80-120 80-120 60-120

85-110 60-120 85-110 60-120

-120 units units

Accuracy

10 15

15 20

25

15 20

(3)

10 10 10 10 10 10 25

5 10 5 10

15 0.2 units 0.2 units

Completeness

90 90

90 90

90

90 90

90

95 95 95 95 95 95 95

95 95 95 95

95 95 95

(1) (2)

(3)

Matrix codes: W = water; S = soil; T = tissue. Method codes: I = ICP; F = furnace; V = cold vapor; G = GC; M = GC/MS; R = infrared; G = gravimetric; E = electrometric; IC = ion chromatography; T = titrimetric Limits are to be determined during the method performance study.

6 'T U 0 '


3.2.2 Accuracy

Accuracy is the degree of agreement of a measured value with the true or expected value of the measured quantity. It is a measure of the bias or systematic error of the entire data collection process. Sources of these errors include the sampling process, field amd laboratory contamination, sample preservation and handling, sample matrix, sample preparation methods, and calibration and amalysis procedures. Sampling accuracy is assessed by evaluating the results of field/trip blanks, analytical accuracy through the use of calibration and method blanks, calibration verification saunples, laboratory control samples, amd matrix spikes.

3.2.3 Representativeness

Data representativeness is the degree to which data accurately and precisely represent a characteristic of a population, parameter variations at a sampling point, or an environmental condition. Representativeness is a quantitative parameter that is most concerned with the proper design of the sampling program. The sampling program has been designed so that the saunples collected are as representative as possible of the medium being sampled and that a sufficient number of saunples will be collected. Representativeness is addressed by the description of the sampling techniques and the rationale used to select the sampling locations.

3.2.4 Completeness

Completeness is defined as the percentage of measurements made that are judged to be valid data. To achieve this objective, every effort is made to avoid sample loss through accidents or inadvertence. Accidents during sample transport or lab activities which cause the loss of the original sample will result in irreparable loss of data. Collection of sufficient sample allows reanalysis in the event of an accident involving a sample aliquot. The assignment of a set of continuous laboratory numbers to a batch of samples which have undergone chain-of-custody inspection makes it more difficult for the analyst to overlook saunples when setting up a batch of samples for amalysis. The continuous laboratory numbers also make it easy during the data compilation stage to pick out the saunples which have not been analyzed and to order their analysis before the data are reported and before holding times have been exceeded. The completeness of each batch of samples can be calculated by dividing the total number of amalyses completed by the number that should have been performed on that batch times 100.

3.2.5 Comparability

Data comparability is a measure of the confidence with which one data set can be compared to another. It cannot be described in quantitative terms, but must be considered in designing the sampling plans, analytical methodology, quality control, and data reporting. The use of standard sampling techniques and validated, EPA-approved analytical methods


assures that the parameters being measured are comparable with data generated from other sources. Reporting of data in units used by other organizations also assures comparability.

3.2.6 Tables of QA Objectives

Table 3-4 presents the accuracy, precision, and completeness goals for the various parameter groups. The accuracy figures represent the mean percent recovery plus and minus the three standard deviation (99X) limits for the analysis of laboratory control samples (see Section 12). The precision is the mean moving range between successive measurements of the laboratory control samples.

3.3 ANALYTICAL DETECTION LIMITS

Table 3-5 summarizes the method detection limits that will be used for chemical analysis of samples for the Cold Creek Operable Unit RI/FS.

•ii) 4 Li U


TABLE 3-5 METHOD DETECTION LIMIT

INORGANIC TARGET ANALYTE LIST (TAL)

Contract Required ... »•» Detection Limit Water^ ' ^

Analyte (ug/L)

Aluminum 200 Antimony 60 Arsenic 10 Barium 200 Beryllium 5 Cadmium 5 Calcium 5000 Chromium 10 Cobalt 50 Copper 25 Iron 100 Lead 3 Magnesium 5000 Manganese 15 Mercury 0. Nickel 40 Potassium 5000 Selenium 5 Silver 10 Sodium 5000 Thallium 10 Vanadium 50 Zinc 20 Cyamide 10

(1) Subject to the restrictions specified in the first page of Part G, Section IV of Exhibit D (Alternate Methods - Catastrophic Failure) any analytical method specified in SOW Exhibit D may be utilized as long as the documented instrument or method detection limits meet the Contract Required Detection Limit (CRDL) requirements. Higher detection limits may only be used in the following circumstance:

If the sample concentration exceeds five times the detection limit of the instrument or method in use, the value may be reported even though the instrument or method detection limit may not equal the Contract Required Detection Limit. This is illustrated in the example below:

•J - Li U .' [•)

EA QAP-11653.01 Section No.: 3 Revision No.: 1 ~ te: November 30, 1990 Page: 13 of 19

TABLE 3-5 (Cont.)

For lead:

Method in use = ICP Instrument Detection Limit (IDL) = 40 Sample concentration = 220 Contract Required Detection Limit (CRDL) = 3

* CRDLs are not available for tissue. Detection limits appropriate to the level of resolution necessary for the study will be applied to tissue samples. For methyl mercury, detection limits between 10 and 100 ppb will provide appropriate resolution.

#

•J "1-

TABLE 3-5 (Cont.)


Target Compound List (TCL) and Contract Required Quantitation Limits (CRQL)*

Volatiles

Quantitation Limits** Water Low Soil/Sediment'

CAS Number ug/L yg/Kg

1. Chloromethane 74-87-3 10 2. Bromomethane 74-83-9 10 3. Vinyl Chloride 75-01-4 10 4. Chloroethane 75-00-3 10 5. Methylene Chloride 75-09-2 5

6. Acetone 67-64-1 10 7. Carbon Disulfide 75-15-0 5 8. 1,1-Dichloroethene 75-35-4 5 9. 1,1-Dichloroethane 75-34-3 5 10. 1,2-Dichloroethene (total) 540-59-0 5

11. Chloroform 67-66-3 5 12. 1,2-Dichloroethane 107-06-2 5 13. 2-Butanone 78-93-3 10 14. 1,1,1-Trichloriethane 71-55-6 5 15. Carbon Tetrachloride 56-23-5 5

10 10 10 10 5

10 5 5 5 5

5 5 10 5 5

16. Vinyl Acetate 108-05-4 10 17. Bromodichloromethane 75-27-4 5 18. 1,2-Dichloropropane 78-87-5 5 19. cis-l,3-Dichloropropene 10061-01-5 5 20. Trichloroethene 79-01-6 5

10 5 5 5 5

21. Dibromochloromethane 124-48-1 5 22. 1,1,2-Trichloroethane 79-00-5 5 23. Benzene 71-43-2 5 24. trans-l,3-Dichloropropene 10061-02-6 5 25. Bromoform 75-25-2 5

5 5 5 5 5

%

26. 4-Methyl-2-pentamone 27. 2-Hexanone 28. Tetrachloroethene 29. Toluene

(continued)

108-10-1 591-78-6 127-18-4 108-88-3

10 10 5 5

10 10 5 5

m

TABLE 3-5 (Cont.)

J U .'


Volatiles Water

CAS Number yg/L

Quamtitation Limits** Low Soil/Sediment^

Wg/Kg

30. 1,1,2,2-Tetrachloroethane 79-34-5 31. Chlorobenzene 108-90-7 32. Ethyl Benzene 100-41-4 33. Styrene 100-42-5 34. Xylenes (Total) 1330-20-7

5 5 5 5 5

5 5 5 5 5

a Medium Soil/Sediment Contract Required Quantitation Limits (CRQL) for Volatile TCL Compounds are 125 times the individual Low Soil/Sediment CRQL.

* Specific quantitation limits are highly matrix dependent. The quamtitation limits listed herein are provided for guidance amd may not always be achievable.

** Quantitation limits listed for soil/sediment are based on wet weight. The quantitation limits calculated by the laboratory for soil/sediment, calculated on dry weight basis as required by the contract, will be higher.

Ju


1990

TABLE 3-5 (Cont.)

35. 36. 37. 38. 39.

40. 41. 42. 43.

44.

45.

46. 47. 48. 49.

50. 51. 52.

53. 54.

55. 56. 57. 58.

59.

60. 61. 62. 63. 64.

Target Compound List Contract Required

Semlvolatiles

Phenol bis(2-Chlorethyl) ether 2-Chlorophenol 1,3-Dichlorobenzene 1,4-Dichlorobenzene

Benzyl alcohol 1,2-Dichlorobenzene 2-Methylphenol bis(2-Chloroisopropyl) ether 4-Methylphenol

N-Nitroso-di-n-dipropylamine Hexachloroethane Nitrobenzene Isophorone 2-Nitrophenol

2,4-Dimethylphenol Benzoic acid bis(2-Chloroethoxy) methane 2,4-Dichlorophenol 1,2,4-Trichlorobenzene

Napthalene 4-Chloroamiline Hexachlorobutadiene 4-Chloro-3-methylphenol (para-chloro-meta-cresol) 2-Methylnapthalene

Hexachlorocyclopentadiene 2,4,6-Trichlorophenol 2,4,5-Trichlorophenol 2-Chloronaph thalene 2-Nitroaniline

(TCL) and Quantitation Limits

CAS Number

108-95-2 111-44-4 95-57-8 541-73-1 106-46-7

100-51-6 95-50-1 95-48-7

108-60-1 106-44-5

621-64-7 67-72-1 98-95-3 78-59-1 88-75-5

105-67-9 65-85-0

111-91-1 120-83-2 120-82-1

91-20-3 106-47-8 87-68-3

59-50-7 91-57-6

77-47-4 88-06-2 95-95-4 91-58-7 88-74-4

(CRQL)*

Quantitation Limits** i. Water Ug/L

10 10 10 10 10

10 10 10

10 10

10 10 10 10 10

10 50

10 10 10

10 10 10

10 10

10 10 50 10 50

Low Soil/Sediment yg/Kg

330 330 330 330 330

330 330 330

330 330

330 330 330 330 330

330 1600

330 330 330

330 330 330

330 330

330 330 1600 330 1600


TABLE 3-5 (Cont.)

65. 66. 67. 68. 69. 70. 71. 72. 73. 74.

75. 76. 77. 78. 79.

80. 81. 82. 83. 84.

85. 86. 87. 88. 89.

90. 91. 92. 93. 94.

Semlvolatiles

Dimethylphthalate Acenaphthylene 2,6-Dinitrotoluene 3-Nitroaniline Acenaphthene 2,4-Dinitrophenol 4-Nitrophenol Dibenzofuran 2,4-Dini trotoluene Diethylphthalate

4-Chlorophenyl-phenyl ether Fluorene 4-Nitroaniline 4,6-Dini tro-2-methylphenol N-ni trosodiphenylamine

4-Bromophenyl-phenylether Hexachlorobenzene Pen tachlorophenol Phenanthrene Anthracene

Di-n-butylphthalate Fluoranthene Pyrene Butylbenzylphthalate 3,3'-Dichlorobenzidine

Benzo(a)anthracene Chrysene bis(2-Ethylhexyl)phthalate Di-n-oc tylph thalate Benzo(b)fluoranthene

CAS Number

131-11-3 208-96-8 606-20-2 99-09-2 83-32-9 51-28-5 100-02-7 132-64-9 121-14-2 84-66-2

7005-72-3 86-73-7 100-01-6 534-52-1 86-30-6

101-55-3 118-74-1 87-86-5 85-01-8 120-12-7

84-74-2 206-44-0 129-00-0 85-68-7 91-94-1

56-55-3 218-01-9 117-81-7 117-84-0 205-99-2

Quantitation Limits** Water Ug/L

10 10 10 50 10 50 50 10 10 10

10 10 50 50 10

10 10 50 10 10

10 10 10 10 20

10 10 10 10 10


330 330 330 1600 330 1600 1600 330 330 330

330 330 1600 1600 330

330 330 1600 330 330

330 330 330 330 660

330 330 330 330 330

•-> I ' ; K J ' . J


TABLE 3-5 (Cont.)

95. Benzo(k)fluoramthene 96. Benzo(a)pyrene 97. Indeno(l,2,3-cd)pyrene 98. Dibenz(a,h)anthracene 99. Benzo(g,h,i)perylene

207-08-9 50-32-8 193-39-5 53-70-3 191-24-2

10 10 10 10 10

330 330 330 330 330

b Medium Soil/Sediment Contract Required Quantitation Limits (CRQL) for Semivolatile TCL Compounds are 60 times the individual Low Soil/Sediment CRQL.

* Specific quantitation limits are highly matrix dependent. The quantitation limits listed herein are provided for guidance and may not always be achievable.


I; u u


TABLE 3-5 (Cont.)

100. 101. 102. 103. 104.

105. 106. 107. 108. 109.

110. 111. 112. 113. 114.

115. 116. 117. 118. 119.

120. 121. 122. 123. 124.

125. 126.

Target Compound List (TCL) and Contract Required Quantitation Limits

Pesticides/PCB's

alpha-BHC beta-BHC delta-BHC gamraa-BHC (Lindane) Heptachlor

Aldrin Heptachlor epoxide Endosulfam I Dieldrin 4,4'-DDE

Endrin Endosulfan II 4,4'-DDD Endosulfan sulfate 4,4'-DDT

Methoxychlor Endrin ketone alpha-Chlordane gamma-Chlordane Toxaphene

Aroclor-1016 Aroclor-1221 Aroclor-1232 Aroclor-1242 Aroclor-1248

Aroclor-1254 Aroclor-1260

CAS Number

319-84-6 319-85-7 319-86-8 58-89-9 76-44-8

309-00-2 1024-57-3 959-98-8 60-57-1 72-55-9

72-20-8 33213-65-9

72-54-8 1031-07-8 50-29-3

72-43-5 53494-70-5 5103-71-9 5103-74-2 8001-35-2

12674-11-2 11104-28-2 11141-16-5 53469-21-9 12672-29-6

11097-69-1 11096-82-5

(CRQL)*

Quantitation Limits** Water Ug/L

0.05 0.05 0.05 0.05 0.05

0.05 0.05 0.05 0.10 0.10

0.10 0.10 0.10 0.10 0.10

0.5 0.10 0.5 0.5 1.0

0.5 0.5 0.5 0.5 0.5

1.0 1.0


8.0 8.0 8.0 8.0 8.0

8.0 8.0 8.0 16.0 16.0

16.0 16.0 16.0 16.0 16.0

80.0 16.0 80.0 80.0 160.0

80,0 80.0 80.0 80.0 80.0

160.0 160.0

~"c Medium Soil/Sediment Contract Required Quantitation Limits (CRQL) for Pesticide/PCB TCL Compounds are 15 times the individual Low Soil/Sediment CRQL.

* Specific quantitation limits are highly matrix dependent. The quamtitation limits listed herein are provided for guidance amd may not always be achievable.



4. SAMPLING PROCEDURES

Effective sample collection procedures are a primary quality assurance/ quality control (QA/QC) consideration in assuring the technical and legal defensibility of data collection for an NPL-listed RI/FS. A detailed discussion of the number and location of samples; sampling equipment and procedures; sample containers, preservation, and holding time; and decontamination and waste handling procedures for soil borings, shallow soil samples, surficial soil/sediment samples, suijface water samples, and biological tissue samples during the three stage field sampling effort for this project is presented in Chapter 5 of the Work Plan/Sampling and Analysis Plam (submitted under separate cover). Tables 4-1 through 4-5 summarize sample collection activities for this project. Sample handling and field data collection procedures and protocols are described in detail in Chapter 6 of the Work Plan/Saunpling and Analysis Plan.

Analytical laboratory QA/QC provisions are described in other sections of this Quality Assurance Project Plan.

1165301 Doc. 86

CLP (2/88)

CLP (2/88)

CLP (2/88)

CLP (7/88)

Total Number of Conta ine rs

4 OZ wide Bouth glass jar with Teflon liner

Conta ine rs

42<^'

TABLE 4-1 SUMMARY OF SAHPLES, ANALYTICAL PROCEDURES, HOLDING TIME, AND COWTAINERS FOR STAGE I CONTAMINANT NATURE CHARACTERIZATION

NuBber of Nuaber Field . . Sa>ple of Dupli- Field Trip Total Analytical , , , .,

(c) (d) Paraaeter Locations Saaples cates Blanks Blanlts Saaples Procedures Preservation Holding Tiae

Volatile 13 18 1 1 1 21 CLP Hold ? 4 C 14 days Organics

Seaivolatile' 13 18 1 1 0 20 CLP Hold ? 4 C 7 days extraction 8 oz wide-aouth 20 Organics (2/88) 40 days extract glass jar uith

Teflon 1ine r

Pesticides/ 13 18 1 1 0 20 CLP Hold g 4 C 5 days extraction 8 oz wide-mouth 20 PCBs (2/88) 40 days extract glass jar with

Teflon 1ine r

Metals 16 21 1 1 0 24 CLP Hold @ 4 C (f) 8 oz wida-mouth 24 (TAL) (7/88) glass jar with

Teflon 1ino r

Methyl 13 18 1 1 0 20 (e) Hold g 4 C 7 days extraction 8 oz wide-mouth 20 Mercury 40 days extract glass jar with

Teflon 1ine r

Thio- 13 18 1 1 0 20 EPA Hold g 4 C 7 days extraction 8 oz wida-mouth 20 Carbaaato 634 40 days extract glass jar with Pesticides Teflon liner

Sulfide 13 18 1 1 0 20 9030 Hold 9 4 C 7 days 8 oz wida-aouth 20 glass jar with Teflon liner

(a) Trip blanks taken for volatile organics analysis only. (b) All aethoda are EPA SW-846 unless otherwise notad. (c) No chaaical preservatives added to soils. (d) Froa tiae of saaple collection. (e) Method for aethyl mercury analysis is described in the QAPP. (f) Holding tiae for all aetals is 6 aonths , with the exception of aercury whose holding tiaa is 28 days. '-.''-(g) Two containers per saaple. (h) See Table 7-1. f .

c

TABLE 4-2 SUMMARY OF SAMPLES, ANALYTICAL PROCEDURES, HOLDINO TIME, AMD CONTAINERS FOR STAGE I SOIL/SEDIMENT CONTAMINAMT CHARACTERIZATION

Nuaber of Nuabar Filed . . . ^ . Total Saaple of Dupli- Field Trip Total Analytical Nuaber of

Paraaeter Locationa Saaplea catea Blanks Blanks Saaplea Procedurea Preservation Holding Tiae Containers Containe rs

Methyl aercury 3 30 2 1 0 33 (a) Hold 9 4 C 7 days extraction 8 oi wide-aouth 33 40 days extract glass jar with

Teflon liner

Total aercury 3 30 2 1 0 33 24S.2-CLP Hold » 4 C 28 days 8 oz wida-aouth 33 glass jar with Teflon liner

Sulfide 3 30 2 1 0 33 9030 Hold « 4 C 7 days 8 os wide-aouth 33 glassjarwith Teflon liner

pH 3 30 2 1 0 33 9045 Hone Analyse 8 os wida-aouth 33 iaaadiataly glass jar with

Teflon liner

(a) Trip blanks taken for volatile organics analysis only. lb) Unless otherwise noted, aathods will ba froa USEPA SW-S46. (c) Mo chaaical preservatives added to soils. Id) Froa tiae of saaple collection. (e) Method for aethyl aercury analysis Is described in tha QAPP.

•TJ O pd c/ l M PI p> ro n> >

Oq rt < n (D (0 !-•• r t t o ' . . . (/} M. > .

>-•• O T } O 3 I

LO 2 3 h-. O 2 1-*

O < 2 O ov »-«i (0 O • Ln

3 • •• U ) Ov cr ••

n> o

L J o

VO vo o

1165301 Doc. 67

TABLE 4-3 SUMMARY OF SAMPLES, ANALYTICAL PROCEDURES, HOLDING TIME AND CONTAINERS FOR STAGE I IN SITU SURFACE WATER CHARACTERIZATION

Pa raaater

Total dissolved solids

Ha rdness

pH

Chio rides

Sulfides

Total dissolved mercury

Tota 1 mercury

Methyl mercury

Volatile Organics

Seaivolatile Organics

Pesticidas/PCBs

Metals (TAL)

Nuaber of Saaples and Fie Locations Dupli

d Field Total Analytical ates Blanks Saaples Procedure

(a)

8 EPA 160.1

8 APHA 314A

8 9040

1 8 9250

1 8 9030

Preserva tion Holding Time (b)

Hold e 4 C

Hold e 4 C HNO, to pH<2

None

None

Hold e 4 C Zinc acetate NaOH to pH>9

8

8

8

8

8

8

8

245.1

245.1

(c)

CLP (2/88)

CLP (2/88)

CLP (2/88)

CLP (7/88)

CLP-

CLP-

-M

-M

HNO,

HNO,

Hold

Hold

Hold

Hold

Hold

to pH<2

to pH<2

e 4 C

e 4 c

e 4 c

e 4 C

e 4 c

7 days

6 months

Analyza immediataly

28 days

7 days

28 days

28 days

Conta iner3

P, a

p, a

P, G

P, G

P, G

P, G

P, G

7 days extraction G, Teflon cap 40 days extract

14 days G

7 days extraction G 40 days ext ract

5 days extract G 40 days extract

(d) P,

(a) All anlaytical procedures are froa EPA SW-846 unless otherwise noted (see Table 7 - 1 ) . (b) Froa tiae of saaple collection. (c) Described in QAPP. (d) Holding tiaa for all aetals is 6 aonths, with the exception of aercury whose holding tiae is 28 days P " plastic G > glass

c

TABLE 4-4 SUMMARY OF SAMPLES, ANALYTICAL PROCEDURES, HOLDING TIME, AMD CONTAINERS FOR STAGE II SOIL/SEDIMENT COMTJVMINANT CHARACTERIZATION

(b) Nuaber o t Nuabar Filed . Ana- Total Staple of Dupli- Field Rinsate Trip Total lyfcical . . Number of

Paraaeter Locations Saaples catea Blanks Blanks Blanks Saaples Procedures Preservation Holding Tiae Containers Conta inars

Total aercury 45 91 5 I 2 0 lOl 24S.2-CLP Hold 0 4 C 28 days 8 os wide-aouth 99 99 glass jar with

Teflon liner

Methyl aercury 12 36 2 I 2 0 41 (e) Hold 9 4 C 7 days extraction 8 os wide-aouth 41 40 days extract glass jar with

Teflon liner

Sulfide 45 91 5 I 2 0 99 9030 Hold 9 * C 7 days 8 os wide-aouth 99 glass jar with Teflon liner

pH 45 91 S 1 2 0 99 9045 Hone Analyse 8 oz wide-aouth 99 iaaediately glass jar with

Teflon liner

(a) Trip blanks taken for volatile organics analysis only. (b) Analytical procedures Iwll be in accordance with EPA SW-846 unless otherwise noted. (c) Mo chaaical preservatives added to soils. Id) Froa tiae of saaple collection. (e) Method for aethyl aercury analysis is described in the QAPP.

•TJ O PI PI

oq r t I t n> «• ea

Ln 2 O

O < t-h (0

a CTi c r ID l-l

L J o

t-» vo vo o

!M n> < M. C/I

( -" . o 3

2 O

.. t -*

C/J ID n r t

* -» . O 3

2 O

. ..

*-

w >

' • - . (

o -"^ > ^ . 1 . ^ : . •

>-' !-• c^ L/1 Lo

O <•••-:

!_, . - - - - •

—

TABLE 4-5 SUMMARY OF SAMPLES, ANALYTICAL PHOCEDURES, HOLDING TIME, AMD COMTAINERS FOR STAGE II BIOACCESSIBLE COWTAMIWAWT CHABACTERIZATIOH

(bt Nuaber ot Nuaber Filed . . Ana- Total Saaple of Dupli- Field Rinsate Trip Total lytical Number of

Parameter Locations Saaples catas Blanks Blanks Blanks Saaples Procedures Preservation Holding Tiae Containers Conta inars

Methyl aercury 60 60 3 1 2 0 66 (e) Hold % 4 C 7 daya extraction 8 os wide-aouth 66 40 days extract glass jar with

Teflon liner

Total aercury 60 60 3 1 2 0 66 245.2-CLP Hold 9 t C 28 days 8 oz wide-aouth 66 glass jar with Teflon liner

Sulfide 60 60 3 1 2 0 66 9030 Hold 9 4 C 7 days 8 oz wide-aouth 66 glass jar with Teflon liner

Total Organic Carbon 60 60 3 1 2 0 66 9060 Hold # 4 C 28 days 8 oz wide-aouth 66

glass jar with Teflon liner

pH 60 60 3 1 2 0 66 9045 None Analyze 8 oz wide-aouth 66 required iaaediately glass jar with

Teflon liner

Eh 20 20 I I 2 0 24 None Analyze 8 oz wide-aouth 24 iaaediately glass jar with

Teflon liner

(a) Trip blanks takan for volatile organics analysis only. (b) Analytical procedures ara In accordance with EPA SW-846, unless otherwise noted. |c) No cheaical preservatives added to soils. Id) Froa tiae of saaple collection. le) Method for aethyl aercury analysis Is described in the QAPP.

TJ a (U p

oq r t ID ID

.. ..

CJN 2 O

O < h«i (0

3 ON c r

ID >i

L J O

I-* vo vO O

PO ID

< M. (/I t-i-o 3

2 O

. ..

I - "

l . . . ^ CO m ID >

n rt O - i • • H- > O >X) 3 1

I-* 2 I - " o cr. • ^ C j . . CO

. 1 — •

o ^ . * - k-^C...

^ • -

.5 4 EA QAP-11653.01 Section No.: 5 Revision No.: 1 Date: November Page: 1 of 10

Li 0 0:

30, 1990

5. SAMPLE CUSTODY

5.1 FIELD SAMPLING OPERATIONS

5.1.1 Sample Bottle Preparation

The chain-of-custody procedure begins with the cleaning of the sample containers to be used. The sample containers are cleaned according to the procedures given in Table 5-1, which are specific for the parameters to be determined. These procedures are documented in Laboratory specific standard operating procedures to be provided by the Contract Laboratory.

5.1.2 Sampling

The samples are collected by trained, experienced teams who will be alerted to any special considerations necessary to ensure collection of representative saunples. After the samples are collected, they are split as necessary among containers amd preservatives appropriate to the parameters to be determined. Each container is provided with a sample label (Figure 5-1) that is filled out at the time of collection. At this time, a chain-of-custody form (Figure 5-2) is initiated. The collected samples are cooled, if necessary, amd returned to the laboratory by the most expedient means to ensure that holding times will be met. The chain-of-custody form is signed and dated as necessary as the samples pass from the collectors to those persons responsible for their transportation.

5 . 1 . 3 Saunple Label ing

The importance of sample labeling cannot be overstated. Improperly or inadequately labeled samples are of little value in a monitoring program. Improperly labeled saunples lead to questions with regard to location, project, sampling station, date sampled, and sampler. All of this information is essential for proper sample handling. The use of water-proof ink when filling out the label is essential to prevent the loss of information during sample shipment.

The following information, at a minimum, is required on each sample label:

Client Date collected Project number Time collected Location Collected by Station Preservative(s) Sample Number Designation

After the label has been completed in the field and has been affixed to the sample container, the label is covered with clear tape. Pre-printed pressure-sensitive labels are available from the laboratory.

7 ,• r . . • .

^ ' i ' u i r . i EA QAP-11653.01 Section No.: 5 Revision No.: 1 Date: November 30, 1990 Page: 2 of 10

TABLE 5-1 CLEANING PROCEDURES FOR SAMPLE CONTAINERS

Parameter Group Material Cleaning

Unpreserved inorganics Plastic Detergent & hot water wash Deionized water rinse

Nutrients Plastic Detergent & hot water wash HCl soak Deionized water rinse

Pesticides Glass Detergent & hot water wash Acetone and deionized

water rinse Dry at 400 C

Metals Plastic Detergent & hot water wash HNO 3 soaik Deionized water rinse

Cyanide Plastic Detergent & hot water wash HCl soak Deionized water rinse

Sulfide Plastic Detergent & hot water wash Deionized water rinse

Volatile organics 40-mL glass Detergent & hot water wash Deionized water rinse Methanol rinse Bake at 400 C

Semivolatile organics Amber glass Detergent & hot water wash Acetone and deionized

water rinse Dry at 400 C Methanol rinse

1 ; ;

EA QAP-11653.01 Sect ion No.: 5 Revision No.: 1 Date: November 30, 1990 Page: 3 of 10

Sample No.

Client

Project

Location

Station

Collected by

Date Time

Preservative(s)

EACC52 12/9/82

Rgure 5-1. Sample bottle label.

®

IO c 3 V TO

O e. 6 01

^^

I

C t M l :

P l o l K l N a . :

E A C l M i r W . N o , :

Plo|«cl ManiH)« « Con iMl :

Piofttcl Nam«:

SMipJ* LfiCAttont:

P ^ « •« B > k h I D :

0>u Tlmt

—

-

2

-

-

—

f . 0 . ftnd M«hi i )

1 1 1 1 f 1 1 1 1 1 1 1 1 1 1 1

J . 1 ( 1 1 1 1 t

i i l J I I I I

1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

_ L J .

J . I . .

- L - l -

1 1

1 1 1 1 1 1 1 1 1 1 1 1 ' 1 1 1 1 1 f

1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 f

1 1 1 1 1 1 1 t 1 1 t 1 1 1 1 1 • '

J _ l -

1 I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 f

1 1 t 1 1 1 1 1 1 1 1 1 1 1 1 * 1 1

ScnpM by: (Slgrwtjra)

F W « h w l b r : | S l g n . l u r i |

C O O I M T M P . : C

Oala/TIm*

1 Dato/TVlK

1

pH; D Y . » D N O ComifiMOi:

I401E: n . « » « lnd.c.10 m.Dtod numtwr fof anftlytoa ivquot lMl . D u i .

e

i

• —

—

r . i . m . l M t / M . H M i d U i m U H l kx A n i i l , .

—

—

—

—

—

—

—

—

— —

—

fV i l lnqdihod by: (Slgmlura)

Racalv«dby:|Si«n>luia)

—

—

. »•

—

Chain Ol Ctislody Rocord

M B B ^ ^ ^ k EA LaborslofUfl ^ y ^ . W ^ k ISLovdonClrcU ^ ^ ^ ^ ^ Spirka. M0 2IIS2 W U K m ^ K t f (301)771-4950

R o p w u A M i v o i ' b l a i Only

E A L > b l Ac«>ik in l i m U r

--

Dala/Tma

1 Oam/Tinia

1

FWnort i i

1

'. H K a i v w l by: (Sionalurt)

l i dd i ng 71<n>i lo> VOA<

nHlitilf Clwily . . . , q H i i h > . , . • ^Ih lu bofui (wy te chfw llUtt

DaWTVnt

1

Scntiiti i SMppod by: (Cbclo)

F»d. B l . Puro. UPS

O D M :

AJ( IUI Nunilxr

, r

•tj a po cn M P) P> ID ID >

« rt < O 10 (D M- rt O . . . . u l->- >

M. O • T J * - O 3 I

2 3 k- O O 2 I-* l-h < 2 O Ov

ID O • Ln i-» 3 . . . LO O C • • •

I t Ln O l-l i -» l - l

L O O

v o v o O

' . . • • v l

'-' ' 0 0 y EA QAP-11653.01 Section No.: 5 Revision No.: 1 Date: November 30, 1990 Page: 5 of 10

Failure to provide the requested information may result in wasted time and resources if it is necessary to discard samples because of inadequate information.

5.2 LABORATORY OPERATIONS

The laboratory shall have a designated Sample Management Officer. This individual is responsible for receiving samples in the laboratory, opening the coolers amd checking the sample integrity and the custody seal, logging samples into the laboratory system, and controlling the hamdling and storage of samples while in the laboratory.

5.2.1 Duties and Responsibilities of Sample Custodian

The duties and responsibilities of the sample custodian include but are not limited to the following:

Receiving samples

Inspecting sample shipping containers for presence/absence and condition of:

- Custody seals, locks, "evidence tape," etc. - Container breakage amd/or container integrity

Recording condition of both shipping containers and sample containers (bottles, jars, cans, etc.) in appropriate logbooks or on appropriate forms.

Signing appropriate documents shipped with samples (i.e., air bills, chain-of-custody records, etc.).

Verifying amd recording agreement or nonagreement of information on sample documents (i.e., sample tags, chain-of-custody records, traffic reports, air bills, etc.) in appropriate logbooks or on appropriate forms. If there is nonagreement, recording the problems, and notifying appropriate laboratory personnel for contacting the Project Manager for direction.

Initiating the paperwork for sample amalyses on appropriate laboratory documents (including establishing case and sample files and inventory sheets) as required for amalysis or according to laboratory standard operating procedures.

Marking or labeling saunples with laboratory sample numbers as appropriate and cross-referencing laboratory numbers to client numbers amd sample tag numbers as appropriate.

Placing samples, sample extracts, and spent samples into appropriate storage and/or secure areas.

3 4 0 00--1 EA QAP-11653.01 Section No.: 5 Revision No.: 1 Date: November 30, 1990 Page: 6 of 10

Controlling access to samples in storage and assuring that laboratory standard operating procedures are followed when samples are removed from and returned to storage.

Monitoring chain of custody of samples in the laboratory. Samples are physical evidence and should be handled according to certain procedural safeguards. For the purposes of some types of legal proceedings, a showing to the court that the laboratory is a secure area may be all that is required for the analyzed evidence to be admitted. However, it is amticipated that in some cases, the court may require a showing of the hand-to-hand custody of the samples while they were at the laboratory. In the event that the court requires such a comprehensive chain-of-custody demonstration, the laboratory must be prepared to produce documentation that traces the in-house custody of the samples from the time of receipt to the completion of the amalysis.

The National Enforcement Investigations Center (NEIC) of U.S. EPA defines custody of evidence in the following ways:

- It is in your actual possession; or - It is in your view, after being in your physical possession;

or It was in your possession and then you locked or sealed it up to prevent tampering; or

- It is in a secure area.

Assuring that sample tags are removed from the sample containers and included in the appropriate sample file; accounting for missing tags in a memo to the file or documenting that the sample tags are actually labels attached to sample containers or were disposed due to suspected contamination.

Monitoring storage conditions for proper sample preservation such as refrigeration temperature and prevention of cross-contamination.

• Returning shipping containers to the proper sampling teams.

5.2.2 Sample Receipt and Logging

After samples have been collected and labeled and the chain-of-custody forms initiated, the project manager completes the right side of the chain-of-custody form, which is an analytical task order form. This form provides sample-specific information amd a listing of the parameters required on each sample, along with the required analytical sensitivity. The chain-of-custody/analytical task order form and appropriate field data sheets (if required by client) are sealed in a water-tight plastic envelope and shipped with the samples to the laboratory.

7 •J i ^ U


Upon receipt at the laboratory, the sample custodian inspects the samples for integrity and checks the shipment against the chain-of-custody/analytical task order form. Discrepancies are addressed at this point and documented on the chain-of-custody form. When the shipment and the chain-of-custody are in agreement, the custodian enters the samples into the Laboratory Log (Figure 5-3) and assigns each sample a unique laboratory number. This number is affixed to each sample bottle. The custodian then enters the sample and amalysis information into the laboratory computer system. The original of the chain-of-custody form is given to the data management group, with a copy to the laboratory operations manager.

5.2.3 Sample Storage amd Security

While in the laboratory, the samples amd aliquots that require storage at approximately 4 C are maintained in a locked refrigerator unless they are being used for analysis. Samples for purgeable orgamics determinations are stored in a separate locked refrigerator from other samples, sample extracts, and standards.

All the refrigerators in the laboratory used for storage of samples are locked, numbered, and dedicated to specific types of samples, as shown in the following table:

Refrigerator Type Location Sample Type

Ualk-in

Valk-in

Under-the-counter

Under-the-counter

Sample receiving area

Sample receiving area

GC laboratory

GC/MS laboratory

Organic extractables

Inorganics and orgamics

Organic VOA

BNA extracts amd standards

Similarly, there are refrigerators designated for extracts and standards. Samples that are required to be frozen are stored in a freezer. The saunple storage areas are within the laboratory to which access is limited to laboratory chemists and controlled by doors with combination locks. The samples are routinely retained at the laboratory for 30 days (or longer if required by the project) after the data have been forwarded to the client so that any analytical problems can be addressed. The samples are discarded at the end of 30 days.

NOTE: Do nol obVleiala errort-crot* oul wllh a alngla Ine only.

1991 ANALYTICAL CUSTODY AND PRESERVATION Page No.

Job No.

Client Protect Code or P.O. No. Matrix

Received

Dale Time

EA Sample NqsJ Stan End

Locator Code

Aliquot Preservation | A B C F G H 1 J ' • n I 5 Dlher toi

Yes No Logger's

Initials Billing Oata

-

Figure 5-3. Laboratory log.

CNI

®

TJ O P> P>

oq rt ID fl)

.. .. 00

2 o o l-h <

fl) *-* 3 o o-ID

l-l

LO O

I - " vo vO O

PO (D

< M . U M . O 3

C/J m ID > o r t O M. > o •TJ 3 1

(-> 2 I- -2 o ov O

.

.. i-»

• Ln . . t o

. Ln O i->

C"


Specific tasks for sample storage are the following:

Samples and extracts are stored in a secure area.

The secure area is designed to comply with the storage method(s) defined in the contract.

The samples are removed from the shipping container and stored in their original containers unless damaged.

Damaged samples are disposed in an appropriate mamner and this disposal is documented.

The storage area is kept secure at all times. The sample custodiam controls access to the storage area. (Duplicate keys for locked storage areas are maintained only by the appropriate personnel.)

Whenever samples are removed from storage, the removal is documented. All transfers of samples are documented on internal chain-of-custody records.

Saunples and extracts are stored after completion of analysis in accordance with the contract or until instructed otherwise by the Project Manager.

The location of stored extracts is recorded.

VOA samples are stored separately from other samples.

Standards are not stored with samples or saunple extracts.

The sample storage area is described.

So that the laboratory may satisfy sample chain-of-custody requirements, the following standard operating procedures for laboratory/sample security are implemented:

- Samples are stored in a secure area. - Access to the laboratory is through a monitored area. Other

outside-access doors to the laboratory are kept locked. - Visitors sign a visitor's log and are escorted while in the

laboratory. - Refrigerators, freezers, and other sample storage areas are

securely maintained or locked. - Only the designated sample custodian amd supervisory personnel

have keys to locked sample storage area(s). - Samples remain in secure sample storage until removed for

sample preparation or analysis. - All transfers of samples into and out of storage are

documented on am internal chain-of-custody record.

6 4

EA QAP-11653.01 Section No.: 5 Revision No.: 1 Date: November Page: 10 of 10

30,

uo:

1990

I.)

These internal custody records are maintained in the project files. After a sample has been removed from storage by the analyst, the analyst is responsible for the custody of the sample. Currently the laboratory is not tracking the internal movement of samples because the laboratory is secured and accessible only to chemists.

7 ^ 4 0 0 0 EA QAP-11653.01 Section No.: 6 Revision No.: 1 Date: November 30, 1990 Page: 1 of 9

CALIBRATION PROCEDURES AND FREQUENCY

6.1 CALIBRATION PROGRAM

Instruments and equipment used in the Contract Laboratory will be controlled by a formal calibration prograun. The program verifies that equipment is of the proper type, range, accuracy, and precision to provide data compatible with specified requirements. All instruments and equipment which measure a quantity, or whose performance is expected to be a stated level, are subject to calibration. Calibration is performed either by Contract Laboratory personnel using reference standards or externally by calibration agencies or equipment manufacturers.

This section prescribes the practices to be used by the Contract Laboratory to implement a calibration program. Development and documentation of the laboratory calibration program is the responsibility of the Laboratory Managers. Implementation is the responsibility of the supervisors amd analysts, and the Quality Assurance Manager (QAM) monitors the procedures.

Two types of calibration are discussed in this section:

Operational calibration, which is routinely performed as part of instrument usage, such as the development of a stamdard curve for use with an atomic absorption spectrophotometer. Operational calibration is generally performed for instrument systems.

Periodic calibration, which is performed at prescribed intervals for equipment, such as balances and thermometers. In general, equipment which can be calibrated periodically is a distinct, singular purpose unit and is relatively stable in performance.

6.2 CALIBRATION STANDARDS

Two types of reference standards will be used for calibration:

Physical standards, such as weights for calibrating balamces and certified thermometers for calibrating working thermometers, refracators amd ovens, which are generally used for periodic calibration.

Chemical standards, such as Standard Reference Materials (SRMs) provided by the National Institute of Standards and Technology (NIST) or the U.S. EPA. These may include vendor-certified materials traceable to NIST or U.S. EPA SRMs. These are primarily used for operational calibration.

o 4 u •,;


Whenever possible, physical reference standards have known relationships to nationally recognized standards (e.g., NIST) or accepted values of natural physical constants. If national standards do not exist, the basis for the reference is documented.

Physical reference standards are used only for calibration and are stored separately from equipment used in analyses. In general, physical reference standards are at least four to ten times as accurate as the requirements for the equipment which they are used to calibrate. In general, physical standards are recalibrated annually by a certified external agency.

Whenever possible, chemical reference standards are directly traceable to NIST SRMs. IF SRMs are not available, compounds of vendor-certified high purity are used to prepare calibration standards.

6.3 CALIBRATION FREQUENCY

Instruments and equipment shall be calibrated at prescribed intervals and/or as part of the operational use of the equipment. Frequency shall be based on the type of equipment, inherent stability, manufacturer's recommendations, values provided in recognized stamdards, intended data use, specified amalytical methods, effect of error upon the measurement process, and prior experience.

Equipment that cannot be calibrated or becomes inoperable during use are removed from service and tagged to indicate it is out of calibration. Such equipment must be repaired amd satisfactorily recalibrated before reuse. For equipment that fails calibration, Nonconformance Record (NCR) is used to record the corrective action and to demonstrate satisfactory calibration (SOP to be provided by Contract Laboratory).

The following are the data generating laboratory instruments which require annual calibration.

a. Analytical Balance

The following are the data generating laboratory instruments which require semiamnual calibration.

a. UV-VIS Spectrophotometer

The following are the data generating laboratory instruments which require calibration before each use.

a. The first group are the instruments for which the calibration procedure is the establishment of a calibration curve.

(1) UV-VIS Spectrophotometer (when used for relative analyses)

u 0 - I


(2) Technicon Autoanalyzer (3) Total Organic Carbon Analyzer (4) Atomic Absorption Spectrophotometer (5) IR Spectrophotometer (6) Selective Ion Meter (7) Inductively Coupled Plasma/Atomic Emission

Spectrophotometer

b. The second group are instruments for which the calibration procedure is the measurement of standard response factors as described in the individual analytical methods. The documentation of the calibration is the record of stamdard concentrations and responses stored in the files of the standard runs.

(1) Gas Chromatograph (2) Gas Chromatograph/Mass Spectrometer

c. The third group are instruments for which the calibration procedure consists of the measurement of one or two stamdards. From the stamdard measurements either the instrument is set to read the appropriate value or a calibration factor is calculated. The results of the standard measurements are recorded on the laboratory data sheets.

(1) pH Meter (2) Selective Ion Meter

(when used for pH measurements) (3) Conductivity Meter (4) Dissolved Oxygen Meter (5) Turbidimeter/Nephelometer

6.4 OPERATIONAL CALIBRATION

Operational calibration is generally performed as part of the analytical procedure. Included may be the analysis of a method blank and the preparation of a stamdard response (standard calibration) curve. Following is a brief discussion of the analysis of method blanks and preparation of standard curves.

6.4.1 General Calibration Procedures

The initial phase of a laboratory testing program requires the selection and certification of the method best suited for an individual parameter. Certification, or verification, is the elimination, or minimizing, of determinate errors which may be due to analyst error or the use of less-than-optimum equipment, reagents, solvents, or gases. The quality of materials, even though they are AR grade or better, may vary from one source to another. The analyst must determine, through the use of reagent and/or solvent blamks, if materials are free from interfeiring

3 4


0 'i u

1990

substances which could affect the analysis. Other steps in certifying the method include the determination of a method blamk and the preparation of a standard calibration curve.

6.4.2 Method Blank

After determining the individual reagent or solvent blanks, the analyst defines the method blank to determine if the cumulative blamk interferes with the analysis. This method blank is prepared by following the procedure step by step, including the addition of all the reagents and solvents, in the quantity required by the method. If this cumulative blank interferes with the determination, steps must be taken to eliminate or reduce the interference to a level that will permit the combination of solvents and reagents to be used. If the blank interference camnot be eliminated, the magnitude of the interference must be considered when calculating the concentration of specific constituents in the saunples analyzed.

A method blamk should be determined whenever am analysis is made. The number of blanks is determined by the method of amalysis and the number of samples analyzed at a given time.

6.4.3 Calibration Curve

For all "relative" analyses, a calibration or standard curve is required to calculate saunple concentrations from the measured instrument responses. A calibration curve is prepared by measuring the instrument responses for a series of standard solutions of the analyte. The sample concentrations are then calculated by interpolating between the standard points. One means to perform these calculations is to use regression amalysis to fit a curve through the standard data. The sample concentrations cam then be calculated using the resulting regression equation. The regression analysis also provides parauneters which can be used to assess the condition of the analysis. The majority of analyses in the laboratory give linear calibration curves or can be transformed to a linear form. Other analyses cam be fitted to a parabolic curve. The following sections discuss specific details of linear and parabolic regression and their uses.

6.4.3.1 Linear Regression

In linear regression analysis, the standard data are fitted to an equation of the form

y = a + bx

0 >...'


where

y X a b

instrument response concentration or amount of analyte y-intercept slope of the line (sensitivity)

After the regression equation has been computed, the sample concentrations (x) are calculated from the response readings (y) by rearranging the regression equation to give x = (y-a)/b. Because of the possibility of nonlinear response outside the range of the stamdards, caution is exercised when sample responses are greater than that of the highest standard. No sample concentration is calculated for final data when the sample response is more than 1.2 times the response of the highest standard. When the saunple response is outside this range, the sample is diluted and reanalyzed, or a higher stamdard can be run to extend the calibration curve.

The correlation coefficient (r), or the square of the correlation coefficient (r ), is a regression parameter which is a measure of how well the equation fitted to the data actually approximates the data. The closer the correlation coefficient is to a value of 1.000, the better the fit. With linear regression analysis, the correlation coefficient is influenced by two factors: (1) how linear the data are, amd (2) how much scatter there is among replicate measurements. For most laboratory analyses, it is possible to obiain correlation coefficients for the calibration curves of 0.995 (r = 0.990)- No analyses should be continued if the r is less than 0.990 (r < 0.980) without consulting the laboratory manager or quality assurance officer.

6.4.3.2 Parabolic Regression

Although curvilinear responses can indicate problems in amalyses which are expected to give linear responses, there are some analyses which routinely give curvilinear responses. Parabolic regression has been found useful for preparing calibration curves for some of these analyses. In parabolic regression, an.equation of the form

y = a. + a.x a x

where

y = instrument response X = aunount or concentration of the analyte

a^, a., a- = parabolic constants

is fitted to :he data. The sample concentrations are calculated from the instrument responses by solving the parabolic equation for x. An equation of the form

5


KJ

,1/2

\ A - U i I ^

X = ^ 2 (y-^0> * l]

2-2

is obtained. (This equation represents only one root of the parabolic equation, corresponding to the leg of the parabola to which the data are fitted.)

For curvilinear response functions, the curve shape beyond the range of the standards cannot be predicted. For this reason, no sample response greater than that of the highest standard can be used to calculate a concentration.

The parabolic correlation coefficient (r) has the same meaning and criteria as discussed above for linear regression. The r values are often not as high as for linear regression because the response is only approximated by a parabola; the actual form is generally unknown.

6.5 TUNING AND GC/MS MASS CALIBRATION

Prior to initiating any ongoing data collection, it is necessary to establish that a given GC/MS meets the standard mass spectral abundance criteria. This is accomplished through the analysis of decafluorotri-phenylphosphine (DFTPP) or p-bromofluorobenzene (BFB). The ion abundance criteria for each calibration compound MUST be met before any samples, blanks, or standards can be amalyzed.

Decafluorotriphenylphosphine (DFTPP)

Each GC/MS system used for the analysis of semivolatile or pesticide compounds must be hardware-tuned to meet the abundance criteria for a 50-ng injection of decafluorotriphenylphosphine (DFTPP). DFTPP may be analyzed separately or as part of the calibration stamdard. The criteria must be demonstrated daily or for each 12-hour period, whichever is more frequent. DFTPP must be injected to meet this criterion. Post-acquisition manipulation of ion abundamce is NOT acceptable. Documentation of the calibration is provided in the form of a mass listing (Table 6-1).

p-Bromofluorobenzene (BFB)

Each GC/MS system used for the analysis of volatile compounds must be hardware-tuned to meet the abundance criteria for a maximum of a 50-ng injection of BFB. Alternately, 50 ng of BFB solution is added to 5.0 mL of reagent or standard solution and analyze. This criterion must be demonstrated daily or for each 12-hour period, whichever is more frequent. Post-acquisition manipulation of ion abundance is NOT acceptable. Documentation of the calibration is provided in the form of a mass listing (Table 6-2).

J ^ U ; IJ J


TABLE 6-1 DFTPP KEY IONS AND ABUNDANCE CRITERIA

Mass Ion Abundance Criteria

51 30.0 - 60.0 percent of mass 198

68 less than 2.0 percent of mass 69


127 40.0 - 60.0 percent of mass 198

197 less tham 1.0 percent of mass 198

198 base peaik, 100 percent relative abundance

199 5.0 - 9.0 percent of mass 198

275 10.0 - 30.0 percent of mass 198

365 greater than 1.0 percent of mass 198

441 present but less than mass 443

442 greater than 40.0 percent of mass 198

443 17.0 - 23.0 percent of mass 442

Note: Whenever the Laboratory takes corrective action which may change or affect the tuning criteria for DFTPP (e.g., ion source cleaming or repair, etc.), the tune is verified irrespective of the 12-hour tuning requirements.

o 4 Ci EA QAP-11653.01 Section No.: 6 Revision No.: 1 Date: November 30, 1990 Page: 8 of 9

TABLE 6-2 BFB KEY IONS AND ABUNDANCE CRITERIA

Mass Ion Abundamce Criteria

50 15.0 - 40.0 percent of the base peak

75 30.0-60.0 percent of the base peak

95 base peak, 100 percent relative abundance

96 5.0-9.0 percent of the base peak


174 greater than 50.0 percent of the base peak

175 5.0 - 9.0 percent of mass 174

176 greater than 95.0 percent but less tham

101.0 percent of mass 174

177 5.0 - 9.0 percent of mass 176

Note: Whenever the Laboratory takes corrective action which may change or affect the tuning criteria for BFB (e.g., ion source cleaning or repair, etc.), the tune must be verified irrespective of the 12-hour tuning requirements.

7 .' '-; '• ,'••.•,

•-) r U i U /


DFTPP and BFB criteria MUST be met before any samples, sample extracts, blanks, or standards are analyzed. Any saunples analyzed when tuning criteria have not been met may require reanalysis at no cost to the client.

Definition: The 12-hour period for tuning amd calibration criteria begins at the moment of injection of the DFTPP or BFB analysis that the laboratory submits as documentation of compliamt tune. The period ends after 12 hours according to the system clock.

6.6 FIELD EQUIPMENT

The procedures and frequencies for the calibration of field equipment are specified in Section 6 of the EPA Region IV Engineering Support Branch Standard Operating Procedures amd Quality Assurance Manual (April 1, 1986).


7. ANALYTICAL PROCEDURES

Analysis of samples is performed using EPA or EPA-approved methods, where such methods exist in accordance with EPA Contract Laboratory Program (CLP) Protocols. For those amalyses that do not have EPA methods the analytical methods used are taken from standard sources. Table 7-1 lists amalytical methods to be used in the analysis of aqueous, tissue, and solid samples. At this time, EPA has not established a standard analytical procedure for methyl mercury. The contract laboratory will identify an appropriate amalytical method to be used and will develop documentation to assure that the proposed method meets the following provisions. Field procedures are listed in Table 7-2.

1. Five point initial calibration curve with linearity and XRSD criteria. 3JRSD criteria for continuing calibration. Retention time window criteria for GC methods.

2. Method blamk criteria consistent with U.S. EPA-CLP requirements if possible.

3. MS/MSD frequency and acceptance criteria consistent with U.S. EPA-CLP.

4. Method precision and accuracy established using a low level stamdard amalyzed four times according to the procedures in U.S.EPA SW 846.

5. Method detection limits study (MDL) study following the procedure in U.S. EPA SW846, Chapter 1 (3rd edition).

6. Written procedure and data packages reviewed and signed by the appropriate Laboratory Manager. Copies of the prodecures amd performance data are kept on file.

Laboratory records are kept for all procedures performed on a sample. These records include the project, date, amalyst, sample identification, and comments, as well as daily instrument calibrations.

Copies of proposed methods for methylmercury and mercury in fish tissue are included in Appendix C.

ofalB^, t' methods table doc. 291

^

Revised: 16-Jan-91

TABLE 7-1 ANALYTICAL METHODS

Page 1 of 6

Parameter Method Method Number Matrix Reference

SAMPLE PREPARATION

Soluble Salts Extraction

Total Metals Digestion (FAA/ICP) Total Metals Digestion (GFAA) Metals Digestion (GFAA) Metals Digestion (FAA/ICP)

Semivolatile Organics Extraction Semivolatile Organics Extraction

Volatiles

ORGANICS

Halogenated Hydrocarbon Pesticides

Organonitrogen Pesticides

Polychlorinated Biphenyls

Thiocarbatnate pesticides

Methylmercury

Volatile Organic Compounds

Acid Extractable Organic Compounds

Aqueous Extraction 10-2

Nitric Acid - Hydrochloric Acid Nitric Acid - Hydrogen Peroxide Nitric Acid - Hydrogen Peroxide Hydrochloric Acid - Hydrogen Peroxide

Continuous Extraction Soxhlet Extraction

Purge and trap 5030

Gas Chromatography - ECD

Gas Chromatography - ECD, and HPLC


Gas Chromatography - NPD


Gas Chromatography/Mass Spectrometry

Gas Chromatography/Mass Spectrometry CLP

SO

W,SO

(3)

CLP CLP CLP CLP

3520 3540

W W SO SO

W SO

(9) (9) (9) (9)

(8) (8)

(8)

CLP

CLP

634

25.146-M

CLP

W,SO W,SO,T

W,SO

W

W,SO

W,SO

(10) (6)

(10)

(11)

(2)

(10)

l -l

cr W,SO (10)

ofal8 p methods table doc. 291 Revised: 16-Jan-91


Page 2 of 6


Base-Neutral Extractable Organic Compounds

METALS

Aluminum

Antimony

Arsenic

Barium

Beryllium

Cadmium

Calcium

Chromium, Total

Cobalt

Copper

Iron

Lead

Gas Chromatography/Mass Spectrometry

Atomic Emission - ICP


Atomic Absorption - Furnace









Atomic Absorption - Furnace

CLP W,SO (10)

200 .7

200 .7

206 .2

200 .7

200 .7

200 .7

200 .7

200 .7

200 .7

200 .7

200 .7

239 .2

CLP-M

CLP-M

CLP-M

CLP-M

CLP-M

CLP-M

CLP-M

CLP-M

CLP-M

CLP-M

CLP-M

CLP-M

W,SO

W,SO

W,SO

W,SO

W,SO

W,SO

W,SO

W,SO

W,SO

W,SO

W,SO

W,SO

( 9 )

( 9 )

( 9 )

( 9 )

( 9 )

( 9 )

( 9 )

( 9 )

( 9 )

( 9 )

( 9 )

( 9 )

_r-.

ofalL p methods table doc. 291 Revised: 16-Jan-91


Page 3 of 6

Parameter

Atomic

Atomic

Atomic Atomic Atomic

Atomic

Atomic

Atomic

Atomic

Atomic

Atomic

Atomic

Atomic

Method

Emission -

Emission -

Absorption Abosrption Abosrption

Emission -

Emission -

Absorption

Emission -

Emission -

Absorption

Emission -

Emission -

ICP

ICP

- Cold - Cold - Cold

ICP

ICP

Vapor Vapor Vapor

- Furnace

ICP

ICP

- Furnace

ICP

ICP

Method Number

200.7

200.7

245.1 245.2

200.7

200.7

270.2

200.7

200.7

279.2

200.7

200.7

CLP-M

CLP-M

CLP-M CLP-M

CLP-M

CLP-M

CLP-M

CLP-M

CLP-M

CLP-M

CLP-M

CLP-M

Matrix

• W,SO

W,SO

W SO T

W,SO

W,SO

W,SO

W,SO

W,SO

W,SO

w,so

w,so

Reference

(9)

(9)

(9) (9) (5)

(9)

(9)

(9)

(9)

(9)

(9)

(9)

(9)

Magnesium

Manganese

Mercury Mercury Mercury

Nickel

Potassium

Selenium

Silver

Sodium

Thallium

Vanadium

Zinc

ofalb-i«/p methods table doc. 291 Revised: 16-Jan-91


Page 4 of 6


INORGANIC NONMETALS

Chloride

Total Cyanide

Total Hardness

Sulfide

PHYSICAL DETERMINATIONS

pH pH

Total Filterable Residue

Colorimetric - Automated Ferricyanide

Colorimetric - Automated U.V.

Calculation - Mg+Ca as Carbonates

Titrimetric

Potentiometric (Liquid) Potentiometric (Solid)

9250

335.2 CLP-M

314A

9030

W,SO

W,SO

W

W,SO

(8)

(9)

(1)

(8)

Gravimetric 180C

9040 9045

160.1

W SO

(8) (8)

(4)

Matrix codes: A - Air W - Estuarine water, ground water, leachates, ocean water, surface water, and wastewater DW - Drinking water SO - Soils, sludges, sediments, wastes T - Animal tissue, plant tissue

LJ- ]

ofalb-iwp methods table doc. 291 Revised: 16-Jan-91


Page 5 of 6


References

1 American Public Health Association, American Water Works Association, Water Pollution Control Federation. 1985. Standard Methods for the Examination of Water and Wastewater, 16th edition. APHA, Washington, D.C.

2. Association of Official Analytical Chemists. Arlington, Virginia.

1984. Official Methods of Analysis, 14th edition. AOAC,

3. Page, A.L., R.H. Miller, and D.R. Keeney, eds. 1982. Methods of Soil Analysis, Part 2: Chemical and Microbiological Properties, 2nd edition. American Society of Agronomy, Madison, Wis.

4. United States Environmental Protection Agency. 1983. Methods for Chemical Analysis of Water and Wastes. EPA-600/4-79-020. U.S. EPA, Cincinnati, Ohio.

5. United States Environmental Protection Agency. 1981. Interim Methods for The Sampling and Analysis of Priority Pollutants in Sediments amd Fish Tissue. EPA-600/4-81-055. U.S. EPA, Cincinnati, Ohio.

6. United States Environmental Protection Agency. 1984. Characterization of hazardous Waste Sites, A Methods Manual. Volume III. Available Analytical Methods. EPA-600/4-84-038. U.S. EPA, Las Vegas, Nevada.

7. United States Environmental Protection Agency. 1984. The Determination of Inorganic Anions in Water by Ion Chromatography. EPA-600/4-84-017. U.S. EPA, Cincinnati, Ohio.

ofal -/p methods table doc. 291 Revised: 16-Jan-91


Page 6 of 6

8. United States Environmental Protection Agency. 1986. Test Methods for Evaluating Solid Waste. Physical/Chenical Methods. EPA SW-846, 3rd edition. U.S. EPA, Washington, D.C.

9. United States Environmental Protection Agency. 1987. U.S. EPA Contract Laboratory Program. Statement of Work for Inorganics Analysis. U.S. EPA, Washington, D.C.

10. United States Environmental Protection Agency. 1987. U.S. EPA Contract Laboratory Program. Statement of Work for Organics Analysis. U.S. EPA, Washington, D.C.

11. United States Environmental Protection Agency. No date. Determination of Thiocarbamate Pesticides in Industrial and Municipal Wastewater by Gas Chromatography, Method 634, draft. U.S. EPA, Cincinnati, Ohio.

12. Association of Official Analytical Chemists. 1984. Mercury (Methyl) in fish an shellfish, Gas Chromatographic Method First Action. ACAC, Arlington, VA.

3 ' t


TABLE 7-2 FIELD PROCEDURES

Parameter Method Method Number

Reference

pH

Temperature

Specific

Conductance

References:

Electrometric

Thermometric

Wheatstone

Bridge

150.1

4500-H"^B •

170.1

2550B

120.1

2510

U.S. EPA 1979

Standard Methods

U.S. EPA 1979

Standard Methods

U.S. EPA 1979

Standard Methods

1989

1989

1989

United States Environmental Protection Agency. 1983. Methods for Chemical Analysis of Water and Wastes. EPA-600/4-79-020. U.S. EPA, Washington, D.C.

American Public Health Association. 1989. Standard Methods for the Examination of Water and Wastewater, 17th edition. APHA, Washington, D.C.

3


8. DATA REDUCTION, VALIDATION, AND REPORTING

8.1 DATA COLLECTION

For inorganic and general organic analyses where the instruments are not directly coupled to computerized data systems, the raw data are instrument responses in the form of meter, recorder or printer output. The technician performing the analysis enters the bench-generated data into a bound laboratory workbook specific for each parameter. All entries are made in ink. These data consist of instrumental responses (absorbances, percent transmittances, etc.), standard and spike concentrations, sample numbers, amd any other pertinent information. The workbooks are under the control of the group supervisor/manager who is responsible for their security. For computerized instruments the output is in the form of printer output amd files on magnetic disks, which are filed by sample delivery group.

For chromatographic organic amalyses, the raw data are instrument responses in the form of chromatograms, integrator output, or computer-generated data files. The chromatograms and printer output are stored in project-specific files. The data files are archived on magnetic tape.

8.2 DATA REDUCTION

For general "relative" analyses, a calibration or standard curve is used to calculate sample concentrations from the measured instrument responses. The calibration curve is prepared by measuring the instrument responses for a series of stamdard solutions of the amalyte. Regression analysis is used to fit a curve through the standard data (Section 6). The saunple concentrations can then be calculated using the resulting regression equation. The regression amalysis also provides parameters which can be used to assess the condition of the analysis. The regression analyses are performed using verified calculator or computer programs.

For gravimetric and titrimetric analyses, the calculations are performed according to equations given in the stamdard operating procedures for the method.

For chromatographic analyses, the unknown concentrations are determined using response factors with either internal or external standardization. Use of the internal standard method requires the determination of response factors (RF), which are calculated from the following:

RF = (A C. )/(A. C ) ^ s is' ^ IS s'

where

A = area of the characteristic ion of the standard for the target compound

0 4


A. = area of the characteristic ion of the internal standard IS

C. = aunount of the in ternal stamdard IS C = amount of the target compound standard

When the compound has been identified, the quantitation of that compound is based on the integrated abundance of the primary ion(s). If the saunple produces an interference for the primary ion, a secondary ion is used to quantify. The concentration in the sample is calculated using the response factor (RF).

Concentration (ug/L) = (A C^g)/(A^^)(RF)

where

A = area of the characteristic ion for the target compound

A. = area of the characteristic ion for the internal standard IS

C. = concentration of the internal standard IS

Quantitation by the external standard technique involves calculation of the concentrations of the target compound from the saunple response and the response of a standard solution of the compound.

Concentration (ug/L) = (A^C Vj)/(AgV^)

where

A. = peak size of target compound

A = peak size of matching standard

V. = initial volume of sample extracted (mL)

C = concentration of standard (ug/L)

V, = final volume of extracted sample (mL)

The calculations are generally performed by the associated computerized data systems. The data are tramsferred to summary tables which are given to the data management group.

8.3 REPORTING

After all analyses are completed, the data are collected from summary sheets, workbooks, or computer files by the laboratory report group and transferred to a draft report. The assembled data and the raw data are then examined for nonsense, computational, and transcriptional errors.

• /

3 4 EA QAP-11653.01 Section No.: 8 Revision No.: 1 Date: November 30, Page: 3 of 12

V.> i ', 1 i

1990

The data package is then formatted to be consistent with the requirements of the project amd is incorporated into the final analytical data report.

A QA Summary is completed and signed by the designated reviewers, usually the amalyst, Supervisor and Quality Assurance Manager. An example of a typical QA summary form is shown in Figure 8-1. The actual QA summary form shall be provided by the Contract Laboratory. Any problems discovered during the review and correction actions necessary to resolve data problems are communicated to the responsible Laboratory Manager, who discusses their findings with the Quality Assuramce Manager for final data approval.

After completion of the review of the data report for compliance with all project requirements, the Laboratory Director for the Contract Laboratory shall sign off on the data report, amd the report will be forwarded to the project manager.

8.4 DATA VALIDATION

Validation of the field data is the prime responsibility of the project manager who addresses the following areas:

Proper chain-of-custody, sample handling, and decontamination procedures followed

Samples collected according to specified methods

Field instrumentation calibrated according to specified methods

Quality control samples (e.g., blanks, replicates) collected as required

Field data sheets and logbooks completed amd in agreement with sample container labels and chain-of-custody forms

Validation of the laboratory data is the prime responsibility of the laboratory supervisors/managers who address the following areas:

Proper chain-of-custody and saunple hamdling procedures followed

Parametric holding times met

Samples prepared and amalyzed according to specified methods

Instrumentation calibrated according to specified methods

Spike (surrogate or standard) recoveries within specified ranges

Blanks prepared and analyzed as required

Calculations performed correctly and verified

•7 .'J Li


Transcription of raw and final data correct

Detection limits determined correctly and within required limits

A reviewer designated by the project manager examines the final laboratory data for consistency with previous data and the hydrogeo-logical characteristics of the site. Compliance with study plan requirements are also reviewed. Final validation is the responsibility of the corporate quality assuramce officer or designated quality reviewers.

0 4


BA LABORATORIES

QUALTtT ASSURANCE SUMMART

POR SV-846 ANALTSES Page 1 of 2

Project: Analysis: Voiaclles

EA Laboratories Report No. Mettiod: U.S. EPA 8240

Reviewed by: Date:

1. The 14-day holding time requireoent froa saaple collection to analysis vas met for ail samples.

Tes No

2. The 12-hour tuning period for BFB vas set for all saaples.

Tes No

3. Initial calibration criteria vere net for all saaples: tha RSD is <30Z for all CCC compounds, and the RKP for SPCC compounds is >0.300 (0.230 for bromoform).

Tes No

4. Continuing calibration criteria vere net for all saaples: the response factor percent deviation from the mean initial calibration response factor for all CCC coapounds vas <25Z, and the RRP for SPCC compounds is >0.300 (0.2S0 for bromoform).

Tes No

5. Surrogate recovery limits vere met for all saaples.

Tes No

6. HS and HSD criteria vere net for all samples.

Yes No

7. Method blank criteria vere met for all samples: all comoounds are <PQL.

Tes No

(Revised September 1990)

Rgure 8-1. Quality Assurance Summary Form.

7 n '• - I


EA LABORATORIES

QOALITT ASSURANCE SUMMART

POR SV-846 ANALTSES Page 2 of 2

Project:

GA Laboratories Report No.

Reviewed by:

Analysis: Volatiles

Method: U.S. EPA 8240

Oate:

8. Laboratory control saaple criteria vere met for all saaples.

Tes Ne

Cooaents:



.•fl>

EA LABORATORIES


FOR SV-8A6 ANALTSES

3 4 0122


Page 1 of 2

Project :

EA Laboratories Report No.

Reviewed byi

Analysis: Semlvolatiles

Hetliodi U.S. EFA 8270

DateI

1. All saaples were extracted within 7 days of saaple co l lec t ion and analyxed within 40 days of e x t r a c t i o n .

Tea

2. The 12-hour tualnf period for OPTPP vas aet for all asoples.

Tes

No

No

3. Initial calibration criteria vere mat for all soapiest a five-point calibration curve was run, tha RSD is <30Z for all CCC coapounds, and the nean RRF for SPCC compounds is >0.0S0.

Tes No

4. Continuing calibration criteria vere aet for all saaples: the response factor percent difference froa the mean initial calibration response factor for all CCC coapounds was C5Z, and the RRF for SPCC coapounds is >0.030.

Tes No

5. Surrogate recovery llaits vere oat for all saaples.

6. MS and MSD criteria were met for all samples.

Tes

Tes

No

No

7. Method blank criteria vere net for all samples: all compounds are <PQL.

Tes No

(Revised Septeaber 1990)

Rgure 8-1. Quality Assuranco Summary Form.

.®

3 4 0 ' l23


EA LABORATORIES

QOALITT ASS0RANC8 SOMMART

FOR SV-8A6 ANALTSES Page 2 of 2

Project; Analysis: Sealvelatiles

EA Laboratories Report No. Method: U.S. EPA 8270

Revleved by: ^^^^^^^^^^^^^^^^^__ Date: _^^_^^^^^^^^^

8. Laboratory control sample criteria vere met for all saaples.

Tes No

Cooaents:


Rgure 8-1. Quality Assurance Summary Forni.

.®

3 4 0'! 2 .


EA LABORATORIES

QDALITr ASSORANCB SUMMART

FOR ST-8A6 ANALTSES Page 1 of 2

Project: Analysis: Pesticide/PCBs


Revieved by: Date:

1. All samples vere extracted vithln 7 days of saaple collection and analyzed vithin 40 days of extraction.

Tes No

2. Initial calibration criteria vere aet for each analytical sequence: DDT/endrin breakdown <20Z; linearity as RSD of the response factors for all coapounds of interest <20Z; retention tiaa windows established.

Tes No

3. The 72-hour calibration period vas met for all saaples.

Tes No

4. Continuing calibration criteria vere net for all saaples: the response factor percent difference froa the initial calibration response factor for all coopounds of interest vas <12Z for quantitation, <20Z for confirmation. ~

Tes No

5. Surrogate recoveries vere within advisory limits for a l l saaples.

Tes No

6. Percent recovery and RPD for MS 'and MSD vere vithin advisory limits for all samples.

Tes No

7. Method blank criteria vere met for all saaples: the method blank aust contain <PQL of any single pestieide/PCB coapound.

r«s No



<«

3 4 0125


EA LABORATORIES


FOR S«-aA6 ANALTSES Page 2 of 2

Project: Analysis: Pesticide/PCBs


Reviewed by: Date:

8. Laboratory control saaple criteria were aet for all saaples.

Tes No

9. All tentatively identified coapounds vere conflrood on a second coluan.

Tes No

Coaaents:


Figure 8-1. Quality Assurance Summary Form.

i<S>

3 4 0126


EA LABORATORIES

QOALITT ASSURAKCB SOMMART

FOR SV-S46 ANALTSES Page 1 of 2

Project:


Revieved by;

Analysis: Metals

Method: U.S. EPA S9-846

Date;

Saaples were analyzed within six months of saaplit collection. Hereury was analyzed within 28 days.

Tes Ne

ICF initial calibration: A calibration blank and at least one standard were analyzed daily, and th« initial calibration verification standard was within 90Z to IIOZ recovery.

Tes No

AA calibration: A calibration blank and at least three standards vere used to establish the curve, and tha initial calibration verification standard vas vithin 90Z to llOZ recovery (80Z to 120Z for mercury).

Tes No

4. Calibration verification (CV): A CV standard prepared froa a source other than that of the initial calibration vas used, and the result vas vithin 90 to llOZ of the true value for both ICF and AA vork (80Z to 120Z for aercury). A CV vas run at a frequency of lOZ, or every tvo hours, and at the end of the run.

Tes No

5. A preparation blank vas run with aach batch, and all analytes were belov the detection Halts.

Tes No

6. Matrix spike and duplicate criteria vere met for all saaples.

Yes No


Rgure 8-1. QueUlty Assurance Summary Form.

3 4 012;/

EA QAP-11653.01 Section No.: 8 Revision No.: 1 Date: November 30, 1990 Page; 12 of 12

BA LABORATORIES

QOALITT ASSORANCS SOMMART

FOR SV-8A6 ANALTSES Page 2 of 2

Project:


Revieved by:

Analysis: Metals

Method: U.S. EFA SV-8A6

Date I

7. Laboratory control saaple criteria vere aat for all saaples.

T«s No

Coaaents:


Figure 8-1. Quality Assurance Summary Form.

3 4 0128 EA-QAP-11653.01 Section No.: 9 Revision No.: 1 Date: November 30, 1990 Page: 1 of 4

9. INTERNAL QUALITY CONTROLS CHECKS

A quality control program is a systematic process that controls the validity of analytical results by measuring the accuracy and precision of each method and matrix, developing expected control limits, using these to detect anomalous events and requiring corrective action techniques to prevent or minimize the recurrence of these events.

The accuracy and precision of sample analyses are influenced by both internal and external factors. Internal factors are those associated with sample preparation and analysis. Internal factors are monitored by the use of internal quality control samples.

External factors are associated with sample collection. They are monitored by the use of field quality control samples which are identified as field amd trip blanks.

This section describes the type and information provided by each of the quality control samples analyzed. Steps to be followed in the preparation and spiking of saunples are described in the analytical methods referenced in Section 7 of this QA Plan.

9.1 INTERNAL QUALITY CONTROL SAMPLES

9.1.1 Method (Reagent) Blank

The method (reagent) blanks is used to monitor laboratory contamination. This is usually a saunple of laboratory reagent water or soil matrix treated with all the reagents and in the same manner as the sample (i.e., digested, extracted, distilled). One method blamk is prepared and analyzed every day that saunples are prepared.

The method blank must contain less than the method quantitation limit for the compounds of interest. If this criteria is not met, then all sample processing will be halted until corrective measures are taiken and documented. All samples processed with the out-of-control method blamk will be reprocessed amd reamalyzed.

9.1.2 Fortified Method Blank Spike (Laboratory Control Saunple)

Normally, fortified method blank saunples are analyzed with each batch of twenty (20) or fewer samples. These samples generally consist of laboratory reagent-grade water or solid matrix fortified with the amalytes of interest for single-amalyte methods and selected analytes for multi-analyte methods according to the appropriate analytical method. They are prepared and analyzed with the associated sample batch. The analyte recovery from each is used to monitor amalytical accuracy.

3 4 0129

EA-QAP-11653.01 Section No.: 9 Revision No.: 1 Date: November 30, 1990 Page: 2 of 4

The percent recovery will be calculated and plotted onto control charts with warning limits at two (2) standard deviations. These control charts will be updated at least quarterly. Control charts will be used to alert the laboratory of the need to check method procedure, but failure of a spike to fall within the 95% confidence level does not invalidate the sample data.

9.1.3 Fortified Sample (Matrix Spike)

A fortified sample (matrix spike) is am aliquot of a field sample which is fortified with the analyte(s) of interest and analyzed to monitor matrix effects associated with a particular samples. Duplicate fortified samples (matrix spike) will be performed for every batch of twenty (20) or fewer samples for organic amalyses.

9.1.4 Surrogates

Surrogates are orgamic compounds that are similar to analytes of interest in chemical composition, extraction, and chromatography, but are not normally found in environmental samples. These compoimds are spiked into all blamk, standards, samples, and spiked samples prior to amalysis for organic parameters. Generally, surrogates are not used for inorganic analyses. Percent recoveries are calculated for each surrogate. Surrogates shall be spiked into samples according to the appropriate analytical method (Section 6 of this QA Plan). Surrogate spike recoveries shall fall within the control limits set in accordance with procedures specified in the method. Surrogate recoveries will not be calculated if saunple dilution causes the surrogate concentration to fall below the quantification limit.

9.1.5 Laboratory Duplicate Analyses

Saunples requiring duplicate analyses are split into separate aliquots prior to amalysis and the aliquots analyzed separately. This analysis monitors analytical precision but can be affected by sample inhomogenei ty.

9.1.6 Replicate Field Samples

A replicate sample is prepared by dividing a sample into two or more separate aliquots. Duplicate samples are considered to be two replicates. Replicate samples will be collected as specified in Chapter 5 of the Work Plan/Sampling and Analysis Plan.

9.2 OTHER INTERNAL QUALITY CONTROL CHECKS

In addition to the quality control samples described, additional independent types of quality control check samples will be routinely analyzed in the laboratory.

3 4 0130


9.2.1 Standard Reference Mamual

A standard reference material is a solution with a certified concentration that is analyzed as a sample and is used to monitor analytical accuracy.

There shall be, at a minimum, one analysis of an EPA or an NIST standard reference material of soil-sediment or water (if available) with one batch of samples. The stamdard material shall be provided by the contractor. Analytical results shall be compared to the performance specifications provided by EPA or NIST. If the standard does not fall within these specifications, then all the analytical data for these Scimples in the associated batch shall be considered questionable. If other quality control data with this batch are met, then the contractor shall notify ICI and AKZO of this situation and recommend, based on the data quality objectives defined in this QA Plam, whether or not the analytical results are useful and should be reported.

9.2.2 Blind Performance Sample

This is a QC sample of known concentration obtained from EPA or NIST and submitted for analysis by the QA Coordinator. These samples are blind to the analyst amd the results monitor analytical accuracy.

9.2.3 Known Performamce Samples

These are obtained from the same source as those described in 9.2.2 except that the analyst uses these to check the accuracy of an analytical procedure prior to amalysis of any samples. These are particularly applicable when a minor revision has been made to an amalytical procedure or instrument.

9.3 FIELD BLANK QUALITY CONTROL SAMPLES

These samples are not included specifically as laboratory quality control samples but are analyzed when submitted. Data for these QC samples are reported vith associated samples. The folloving sections pertaining to field blamks are generalized definitions. Field blamk quality control samples are specifically discussed and vill be collected as specified in section 3.8 of this QA Plan.

9.3.1 Field Blank

A field blank is a sample of laboratory reagent vater vhich is treated in the same mamner as a field sample. The purpose of the field blank is to monitor incidental contamination possibly introduced during sample collection. A field blamk is collected by pouring distilled/deionized vater provided by the laboratory into the requisite sample containers.


9.3.2 Rinsate Blank

Typically, a rinsate blank is generated by pouring the contents of the field blank over the sampling equipment after it has been decontaminated and collecting the rinse. The frequency of the sampling requires that a rinsate blank be taiken vithin each sampling episode.

9.3.3 Trip Blank

A trip blank is a sample of a laboratory reagent vater vhich is placed in the appropriate sample bottle and accompanies the saunple container (cooler) from the time it is shipped to the field until it is returned vith saunples for analysis. The number of trip blanks included in a saunpling episode varies vith the scope of the episode, but in no case should there be less tham one trip blank per episode. The trip blank serves to monitor contamination during the course of sample shipment and sample collection, and is applicable for amalysis of purgeable aromatic hydrocarbons.

9.4 QC MONITORING

Unless otherwise indicated, the analyses of laboratory control samples are tabulated chronologically and entered onto a quality control chart specifically maintained for each amalytical procedure. These control charts will be labelled with upper and lover varning limits, the amalysis vhich is being charted and the value (i.e., precision, accuracy) vhich is being monitored. Control charts are updated quarterly and vill be used to demonstrate method performamce and help identify system anomalies.

3 4 013


10. PROJECT QUALITY ASSURANCE AUDITS

10.1 QUALITY ASSURANCE MANAGEMENT

Quality assurance is attained through utilization of a management system that contains mechanisms vithin its structure to monitor and regulate its performance so that preset standards of quality are maintained amd the objectives of the program are met.

Evaluation or assessment activities, knovn as audits, provide a mechamism for both a qualitative amd a quantitative reviev of the system vhich must be in place to ensure that all of the data generated are of acceptable quality vith comparability. Audits take the form of systems and performance audits. System audits provide an onsite inspection amd an overall reviev of the quality control systems. Performance audits constitute an evaluation of the data produced amd are considered a check on the performance of the laboratory analysts.

10.2 AUDITS

10.2.1 Responsibility, Authority, and Timing

Quality assuramce audits to be conducted for the project vill include system, performance, and data audits. Audits vill be conducted at appropriate intervals, but at a minimum on an annual basis. The audits may be conducted more frequently for a specific task or activity. The project QA manager vill keep on record a tentative schedule that details the number amd types of audits, both scheduled and unscheduled, for the current year and a current list of the dates of completed audits.

All audits may be conducted by teams that vill consist of, at a minimum, an audit team leader and an auditor. The audit team leader vill be responsible for all the activities of a specific audit including organization, implementation, completion, amd reporting. The audit team may also include a technical assistant vho vill provide technical expertise and assistance to the teaun on a specific task or function. Members of the auditing teaun vill have auditing experience or vill be trained in the use of the auditing procedures.

Specific audits vill be planned, organized, amd clearly defined before they are initiated. Procedures for the auditing activities vill be identified prior to implementation of the audit, and vill be designed to meet all requirements for the specific audit. In general, auditors vill identify nonconformances or deficiencies, report amd document them, initiate corrective action through appropriate chaimels, and follov up vith a compliance reviev.

Records vill be kept of all auditing tasks and findings.

3 4 0133


10.2.2 Reports and Distribution

Folloving each system, performance amd data audit, a report vill be prepared to document the findings of the specific audit. In general, the format of the audit quality assurance reports vill consist, at a minimum, of the folloving:

Description and date of audit;

Name of auditor;

Copies of completed, signed, and dated audit form and/or checklist;

Summary of findings of the audit including any nonconformance or deficiencies;

Where appropriate, photograph or further illustrate situations;

Specific distribution list;

Date of report and appropriate signatures; amd

Description of corrective action, if necessary.

A signed and dated report on each audit vill be maintained in the project files.

10.2.3 Forms amd Checklists

To ensure that the previously defined scope of the individual audits is accomplished and that the audits follov established procedures, a checklist vill be completed during each audit. The checklist vill detail the activities to be executed and ensure that the auditing plan is accurate. Audit checklists vill be prepared in accordamce vith the QAPP and vill be available for reviev. At a minimum, the checklist vill allov space for the folloving information:

Data and type of audit;

Naune and title of auditor;

Description of task or facility being audited;

Names of lead technical personnel present at audit;

Checklist of audit items according to scope of audit; and

Deficiencies or nonconformances.

3 4 0 1 3 -r


10.2.4 System Audits

A system audit is an overall evaluation of components of the program's data acquisition amd management system to determine that the program meets all quality assurance standards through proper design. This audit vill entail careful checking and evaluation of the project files and documentation relating to both field and laboratory quality control procedures. This vill ensure that the required document sign-offs have been made, indicating the required project QC activities are being performed and the project files are complete. System audits vill include, but are not limited to, reviev amd/or evaluation of the folloving factors:

Technical personnel conducting the project;

Project management structure;

Report amd other documentation including chain-of-custody;

Calculations;

Field and laboratory protocols including SOPs; and

Data entry amd the data management system.

10.2.5 Performance Audits

The objective of a performamce audit is to determine the accuracy of the program's total assessment system or of its components through evaluation of the field amd laboratory activities related to data generation. This audit is conducted by am audit team that goes to the field (or office) and observes that the stamdard operating procedures are being folloved and proper QC vork is being performed. Performance audits vill include, but not be limited to, observation, reviev, amd/or evaluation of the folloving factors:

. Execution of the field and laboratory data generation task such as saunple collection, sample custody, laboratory procedures including use of performance evaluation saunples;

. Compliance vith the field and laboratory analysis protocols;

. Performance of any internal quality control checks that are utilized vithin the sampling and amalysis process or task; and

Documentation of all the above.

Performance audits may be unamnounced to the recipients of the audit and vill be performed in accordamce vith the schedule. Performance audits may be conducted in separate segments to cover field and laboratory activities.

3 4 0 EA QAP-11653.01 Section No.: 11 Revision No.: 1 Date: November 30, 1990 Page: 1 of 9

J D

11. PREVENTIVE MAINTENANCE

This section addresses the procedures for instrument maintenance amd service contracts for test amd measurement systems. Maintenance and service activities vill be documented in equipment log books. Date of service, person performing service, type of service performed, reason for service, and replacement parts vill be recorded. Copies of service records from outside vendors vill be maintained vith the log books.

Field testing equipment employed during this project that requires preventive maintenance and the frequency of routine service required is listed in Table 11-1 of this QAPP. Records of calibration and maintenamce activities for each piece of equipment vill be maintained in log books assigned to that instrument. In the event that a problem develops vith field equipment vhile at the site, field personnel vill obtain a replacement or replacement parts, as required, from the consultamts regional office, or, in the case of rental instruments, from the vendor from vhich the instrument is rented. If a special part is required or the instrument must be submitted to the mamufacturer, the consultant vill provide back-up equipment.

11.1 CHROMATOGRAPHIC INSTRUMENTS

The Hevlett Packard GC/MS/DS is maintained on a service contract vhich provides for four preventive maintenamce visits per year. The services provided on these visits include: chamging the oil and filter/drier on the mechanical pumps; cleaning the heads on the magnetic tape drive; cleaning amd aligning the heads on the disk drive; changing air filters and checking the operation on the disk drive. The oil in the turbopumps is chamged once a year. In-house maintenance includes cleaning the source and the quadrupoles as required. The folloving spare parts are routinely kept on hamd: filaments, electron multiplier, source parts, repeller assembly, 0-ring seals, and pump oils. The maintenance contract assures the malfunctions are addressed in a priority manner, thereby minimizing instrument dovntime and providing greater assurance that sample turnaround requirements are met.

The Finnigan GC/MS is maintained on an in-house service schedule. This service includes: changing mechamical pump oil every three months; changing turbopump oil every six months; changing air filters every three months; cleaning the heads of the nine-track magnetic tape drive and the streamer tape drive every 6 months; checking the cooling fans on the turbopump, printer, chromatograph, electronics module and computer monthly; cleaning the printer head every 6 months; cleaning the source every month or as required; cleaning the quadrupoles every six months or as required. The folloving spare parts are routinely kept on hand: a spare EI Source, filaments, miscellaneous source parts, pump oils, and air filters.


TABLE 11-1 FIELD EQUIPMENT AND RECOMMENDED MAINTENANCE REQUIREMENTS

Conductivity Meters

Meter probes are cleamed before and after each use vith distilled/deionized vater.

Before each use (once daily) the instruments are checked vith a commercial conductibility standard for proper calibration.

The battery is checked for proper charge.

The instrument is inspected on a quarterly basis, vhether used during the quarter or not.

The inspection consists of a general examination of the electrical system (including batteries) amd a calibration check.

Instruments not functioning properly are shipped to the manufacturer for repair amd calibration.

pH Meters

Before each use (daily), the probe should be checked for cracks in the electrode bulb amd complete filling vith electrolyte solution.

At the beginning of amy sampling day, the pH meter must be calibrated using standard pH buffers as referenced in Section 6.0

The battery is checked for proper charge.

Folloving each use, the probe is rinsed vith deionized vater. The probe cap is filled vith electrolyte solution and placed on the probe tip. Excess electrolyte is rinsed off and the probe dried vith a paper tovel. The instrument is then placed in its carrying case.

The instrument is inspected on a quarterly basis, vhether or not is has been used.

The inspection consists of a general examination of the probe, vire, electrical system (battery check) and a calibration check.

Any malfunctioning equipment is returned to the manufacturer for repair and recalibration.

3 4 0137


TABLE 11-1 (Cont.)

TheraoBeters

Before each use, thermometers are visually checked for cracks amd mercury separation.

After use, thermometers are rinsed vith deionized or distilled vater and replaced in their protective case to prevent breaikage.

Monthly, thermometers are visually inspected as described above, vhether used or not. They are checked against an NIST certified thermometer for accuracy.

38

EA QAP-11653.01 Section No.: 11 Revision No.: 1 Date: November Page: 4 of 9

30, 1990

Gas chromatograph maintenance is performed as follovs:

Area or Assembly Type of Maintenance Interval

Conditioning Moisture Trap

Moisture Trap

Carrier Gas

Injection Port

Septum

Electron Capture Detector (ECD)

ECD

ECD

ECD

ECD

Repacking

Leaik Check

Cleaming

Replacement

Frequency Check

2 months, or vhen gas source is changed

Every 10 conditionings

As required

As required

As required

1 day

Carrier Gas Evaluation When carrier gas is changed

Leak Check When column is chamged

Thermal Clean I month or as required

NRC Wipe Test 6 months

Spare parts for the gas chromatographs include; ferrules, septa, injection port liners, syringes and needles, column packing materials.

11.2 ANALYTICAL BALANCES

Analytical balances are maintained on a service contract vhich includes annual servicing amd calibration by a qualified service organization. A calibration status label is affixed to each balance after calibration, amd an NIST-traceable calibration certificate is provided. The calibration of the analytical balances is checked veekly vith tvo Class S veights. With each use, the balance is checked vith quality control veights vhich are calibrated against the Class S veights.

11.3 TEMPERATURE CONTROL SYSTEMS

Accuracy amd stability of temperature control for ovens, refrigerators, freezers and incubators are specified in analytical SOPs (EAL-SOP-042). Working thermometers used to monitor laboratory equipment are calibrated annually (EAL-SOP-174, EAL-SOP-175).

For all other laboratory equipment or instrumentation, amy time a temperature control device requires calibration, temperatures throughout the chamber or bath must be checked and compared to nominal temperatures. The need for calibration is to be derived from reviev of temperature grid


data in the respective equipment notebook. Grid data should be checked for obvious drifts, especially drifts resulting in nominal temperature isolines approaching the center of vails of the chamber (or both if applicable).

11.4 ATOMIC ABSORPTION SPECTROPHOTOMETER

11.4.1 General Considerations

For every analytical setup, the folloving precautions must be considered.

1. Perform launp alignment vith great care, as it is possible to achieve a false optimization (peak lamp energy) vith totally erroneous alignment.

2. It is alvays preferable to use single-element lamps rather than multi-element launps due to the potential for signal drift, noisy baselines, short lamp lifespam (multielement), and reduced overall sensitivity.

3. Where possible and vhenever detection limits may be at issue, use electrodeless discharge lamps (EDLs) because of their generally lover noise/signal ratios relative to hollov cathode lamps (HCLs).

4. Detection limits are also much lover, generally speadcing, for analyses using the graphite furnace as compared to flame aspiration amalyses. Any method using am open flame (even inductively coupled arc plasma) vill have a baseline noise component due to the relative instability of the flaune (compared to the partially closed conditions in a graphite tube).

5. Follov the manufacturer's recommendations for lamp currents (HCLs) and vattages (EDLs) as closely as possible, vith close attention paid to cautionary notes.

6. Whenever a nev lamp is received, record the date of receipt on the launp level.

7. Inspect lamps closely, before installation, for possible daunage betveen uses.

8. Excessive "silvering" of lamps (HCLs) may occasionally serve as an indicator of shortening lifespans, although this is by no means a definitive guideline. Increased baseline noise, reduced sensitivity, large chamges in background corrector (BC) balance settings, or the inability to achieve BC balance are definite indicators of lamp deterioration.

J 4 0 i -10


9. As a rule, if high metal concentrations are anticipated or knovn to exist in certain saunples, the better choice vill be flame aspiration due to the reduced sensitivity and concurrent smaller dilution ratios necessary. The large dilution ratios frequently encountered vhen determining sodium, potassium, magnesium, calcium, and zinc vill result in reduced precision and accuracy unless extreme care is taiken in the dilution process.

10. The Perkin-Elmer spectrophotometers are double-beaun instruments and therefore are not greatly subject to lamp and electronic varm-up problems, but it is still advisable to allov a fev minutes varm-up. This is not lost time because alignment and instrument settings for the analysis to be performed must still be made after the instrument is povered up.

11. Never assume that the vavelength dial Indication is correct; peak lamp output (energy) must be determined at every setup. This precaution eliminates errors due to minor misadjustments in dial/vavelength alignments. The program reference card file is to be consulted for the proper vavelength setting amd that vavelength double-checked before analysis begins.

12. Exercise care in the alignment of burners and furnaces; a small misalignment can seriously reduce overall system energy and analytical sensitivity.

11. Perform alignment of the AS-1 automatic injection system for the HGA-2100A graphite furnace vith extreme care, as inconsistent placement of the sample aliquot in the tube, due to the injection tube brushing the graphite tube opening, can result in major reductions in precision. The tube can also be damaged by heat or abrasion, resulting in sudden, unnoticed shifts in response due to redirected injection.

14. If there is any aspect of instrument operation vith vhich the analyst is unfamiliar, this should be remedied by consulting the instruction manual, the laboratory director, or, in possible cases of malfunction, the mamufacturer's maintenance representative.

11.5 TECHNICON AUTOANALYZERS

Because Technicons are composite systems, quality control procedures appropriate to individual components, as veil as the total system, are necessary.

3 4 0 i 4


1. Colorimeter electronics amd optics. The major area of internal colorimeter adjustment is in optical alignment. This also, by virtue of influences on the tvo photocells, is the major internal electronic adjustment. The procedures for these adjustments are available in instruction manuals. The folloving adjustments are checked monthly and the results logged into appropriate notebooks.

a. When flov cells must be replaced

b. When light sources must be replaced

c. When colorimeters must be transported or exchanged

d. When repairs involving partial or complete dismamtling of colorimeter optical "bench" are necessary

2. Before every analysis, the analyst should double check that the proper optical filters are used.

3. The amalyst must clear the flov cell of small air bubbles. This is done by pinching the outlet tube for 5 seconds and quickly releasing it.

4. The folloving recorder-related checks are performed before amd after each day's amalyses

a. Colorimeter zero

b. Colorimeter full scale

c. Recorder zero

5. The filters can be "traced" on the Beckman 24/25 spectrophotometer and the traces compared to the nominal vavelengths.

6. Properly place reference photocell covers to eliminate stray light input.

7. Check flov cells for cleamliness or defects.

8. Leave the colorimeter on continuously, especially during regular use periods, as temperature stability vithin the upper housing vill control photocell stability.

9. Check pump tubes at least veekly for pinch-vear, scuffing, reduced resiliency, imminent perforation, or other damage and replaced as needed.

3 4 0142 EA QAP-11653.01 Section No.: 11 Revision No.: 1 Date: November 30, 1990 Page; 8 of 9

10. Leave heating baths on continuously and maintain at temperature unless extended dovntime is expected. Allov a minimum of 24 hours to reach a stable temperature.

11. The analyst double checks the presence of the proper cam in the autosaunpler.

12. The analyst should be familiar vith the recorder trace form and peak shapes pertinent to the analysis to be performed; often, a change in peaik shape can serve as an indicator of a change in system performance.

11.6 HYDROGEN ION (pH) METERS

The most common cause of problems vith pH meters is a faulty electrode, especially the reference electrode. To prevent "death" or malfunction of an electrode, the folloving practices should be adhered to.

1. Immerse the electrode continually in pH 7.00 buffer vhen not in use.

2. Inspect the reference electrode vick or junction amd clean of debris, if necessary, (vith extreme caution not to injure the glass electrode membrane) before each day's use.

3. Check electrode resistance.

4. Never leave the electrode in very alkaline solutions and thoroughly rinse vith a squirt bottle immediately after each use to prevent poisoning of the glass membrame.

5. Keep the reference electrode full of the appropriate KCl solution.

6. When the sensitivity of am electrode begins to decrease, it can often be revived by immersion in a hot 1-M trisodium phosphate solution for 5-10 minutes. If the sensitivity of the electrode is still lov, a 1-2 minute immersion in 0.1 M ammonia bifluoride folloved by rinsing and soaking in distilled vater for 3-4 hours should restore electrode sensitivity; if not, the electrode must be replaced.

7. The sensitivity of the electrode can be readily assessed by immersion in serial 10:1 dilutions of pH 10.00 buffer and comparing the drift from a reading of 10 to that previously recorded (significant drift before 10 :1 suggests the need for electrode replacement).

8. Spare electrodes should alvays be on hand.

3 4 O'i 4 3


Rapid checks can be made to identify or isolate a potential problem.

1. With shorting strap inserted and meter in pH mode, turn calibration knob from one extreme to the other and determine if equal deflection from 7.0 results in both directions.

2. With calibration set to yield a 7.0 reading, turning the temperature compensation knob should produce no needle movement.

3. With calibration set to yield amy value 4-5 units avay from 7.0, turning the temperature compensation knob should produce a pronounced deflection.

Additional general use notes should be kept in mind vhen making pH measurements.

1. Alvays be certain the solution to be measured is aqueous.

2. Alvays measure pH vith sample stirring, but be sure to isolate the saunple from heat sources such as hot plates and overheating stirrer motors. A thin asbestos pad is a good idea.

3. The filling hole must be open vhen making measurements.

4. A 2-point calibration is alvays best (e.g., pH 7.0 and pH 4.0).

5. Most commonly used electrodes exhibit a "sodium error" at pH values above 10.0. Generally, electrode manufacturers include correction information vith electrodes. This correction must be made for very alkaline saunples.

3 4 0144


12. DATA ASSESSMENT

12.1 APPLICATION OF CONTROLS

The statistical tests necessary to verify proper analytical function are performed as soon as practicable after the measurements on vhich they are based are available. The results of the tests are compared vith the control limits to determine if the data can be used. If the limits are exceeded, the amalyst's supervisor is notified and a decision is made concerning the appropriate action to be taken. If the problem cannot be corrected, the laboratory manager is consulted.

12.2 CONTROL CHARTS

Quality control charts are graphical plots that are used to determine vhether a process is in a state of statistical control. The vertical axis of the control chart is tbe value of the parameter being measured, and the horizontal axis is the time or sequence of the measurements. A control chart is characterized by a central line, varning limits, amd control limits. The central line is the mean, theoretical, or most probable value for the measured parauneter. The limits are values on either side of the central line vith vhich are associated probabilities that am observed value vill be vithin the limits. The varning limits are the 2iT or 95Z limits; that is, if the process is operating correctly amd only ramdom scatter is being observed, nineteen out of tventy points should fall inside the varning limits. The control limits are the 3a or 99Z limits; only one point in a hundred should fall outside these limits by chance alone.

12.2.1 Accuracy amd Precision Charts

The control charts used in the laboratory are generated from the analysis of laboratory control samples (LCS), vhich are used to demonstrate that a method is in control, apart from sample matrix effects (NEESA 1988). The data from the LCS measurements are plotted on tvo Shevhart control charts. One is for the accuracy of the method (Figure 12-1), vhich determines vhether bias is developing in the parauneter being monitoring. The other is for the precision (Figure 12-2), vhich demonstrates vhether the variability of the method is vithin acceptable limits. The parameter that is plotted on the accuracy chart is the percent recovery of the LCS measurement, calculated from:

/VB\ found concentration .nn. percent recovery {XR) = — x 100

expected concentration

The moving ranges betveen each successive pair of percent recoveries are calculated amd plotted on the precision chart:

PERCENT RECOVERY FOR Pyrene by CCMS (Solid)

Meun = 103 36

UCL = MO. 165 LCL = i.ti. 'A5t\^

Ua. o( Points = 31

UWL = 128, 092

LUL = 78, 6275

3 to c 3

i? § •o

o Q

I

s

p e r c e n t R e c 0 V e r y

IfcO 1 1 1 -I — I — I -

150

140

J 30

120

110

100

90

80

70

60

50

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- I — -I 1- -I 1-

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u- i

MOVING RANGE EOR PyreiKJ hy CCMS (Solid)

Mcnn - 13 9173

UCL = 45. 5725

No II r I'll 111 (i: = 30

UWL = 35. 0268

s c 3 to I

ro m X % -a S o, »

I i o

^

5

M 0 V 1 n 0 R R n 0 e

55

50

45

40

35

30

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20

15

10

5

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3 4 0 ^


moving range (R.) = ZR. . — AR.

1+1 1 12.2.2 Calculation of Chart Limits

for i » 1,2,3,...(n-1)

To calculate the varning and control limits for the charts, 20-30 values of the percent recoveries are collected. From these data the mean percent recovery, XR, and the mean moving range, R, are calculated. The central line of the accuracy chart is the mean percent recovery, ^ . For control charts based on the moving ramge of tvo measurements, the upper and lover varning and control limits of the accuracy chart are given by;

Upper control limit (UCL)

Upper varning limit (UWL)

Lover varning limit (LWL)

Lover control limit (LCL)

XR + 2.660 R

fR + 1.773 R

!SR - 1.773 R

JR - 2.660 R

The central line of the precision chart is the meam moving range, R. varning and control limits for the precision chart are given by:

The

UCL

UVL

LWL LCL

SB

=

=

3

3.

2.

0

0

267

511 S R

The limits are updated at least quarterly or vhen the method is changed significamtly.

12.2.3 Hov the Charts are Used

As the value for the control sample is calculated it is compared against the established limits. If the value is vithin the limits, the amalysis is in control and data generated can be used. The percent recovery and the aissociated run information are entered into the LIMS data base from vhich they can be retrieved to plot control charts and to update the limits.

12.2.4 Out-of-Control Situations

The folloving three conditions are used vith the control charts to indicate that a possible out-of-control situation exists:

1) any point outside the control limits; 2) amy tvo consecutive points betveen the varning and control

limits; or 3) seven successive points on the same side of the central line.

3 4 014 8


When one of these conditions exists, the method and the calculations must be investigated to determine if a cause for the condition can be found. When an analyst observes that am out-of-control situation has occurred, the analyst's supervisor is notified, and the appropriate corrective action procedures are initiated. No further analyses are performed until the situation is remedied. If the problem cannot be identified or corrected, the laboratory manager or QC officer is notified.

12.2.5 References

American Society for Testing and Materials. 1976. ASTM Manual on Presentation of Data and Control Chart Analysis. STP 15D. ASTM, Philadelphia.

Duncam, A.J. 1974. Quality Control amd Industrial Statistics, 4th edition. Irwin, Homewood, 111.

Naval Energy and Environmental Support Activity. 1988. Sampling and Chemical Analysis Quality Assurance Requirements for the Navy Installation Restoration Program, 2nd rev. NEESA 20.2-047B. NEESA, Port Hueneme, Calif.

United States Environmental Protection Agency. 1979. Handbook for Analytical Quality Control in Water and Wastewater Laboratory. EPA-600/4-79-019. U.S. EPA, Cincinnati, Ohio.

12.3 QUALITY ASSURANCE (QA)

Four general areas of QA documentation are addressed

In-house documentation

• In-house data checks

• Interlaboratory comparison

• Existing database comparisons

Database comparisons indicate general representativeness of the data.

In-house documentation includes all aspects of the analytical process from reagent preparation to statistical summaries amd control charts. The bulk of this section deals vith these procedures amd subsequent in-house data checks.

3 4 014 9


12.3.1 Reagent and Titrant Preparation

The procedure for each analysis includes the procedures for reagent/titrant preparation, including concentration, storage, and discard information. After a reagent/titramt is prepared, information regarding (1) its intended use, (2) concentration, (3) preparation date, (4) storage, (5) discard date, and (6) preparer is entered on a label affixed to the storage bottle. For titrimetric analyses, the procedure includes directions for standardizing the titrant, and the laboratory data sheets include space for titrant standardization data.

12.3.2 Standards Preparation

The preparation of the stock, intermediate, and vorking standard solutions is recorded in standard preparation logbooks. These are also used for the preparation of stamdard solutions against vhich titrants are standardized (e.g., potassium biiodate for sodium thiosulfate standardization). These forms are completed by the appropriate analyst.

12.3.3 Data Workup

Data generated in the laboratory is either mamually transfered to laboratory data sheets or captured by data systems attached to the instruments.

Much of the calculation of gas chromatography amd GC/MS data is performed by associated data systems. Data are derived from the printed reports accompanying individual GC traces. Due to the bulk of printouts, GC data are tramsferred to summary sheets vhich are then entered into project files.

Data vorkup sheets and summary tables are given to the group supervisor for checking and signoff. All computer and recorder output is placed in into the appropriate parameter or project file.

12.3.4 Outlier Identification

There are no absolute guaramtees against nonrepresentative data points. Therefore, all personnel involved in sampling, sample handling, analysis, and data mamagement must be alert to potential contamination amd procedural errors. Hovever, if nonrepresentative data points appear in the final stages of analysis, there is a mechamism for identifying apparently or obviously erroneous or nonrepresentative data (outliers). The folloving procedures are primary methods for outlier identification and represent the type of logic to be applied to situations or parameters not specifically dealt vith here.

12.3.4.1 Interrelated Data Cross Checks

1. Inorganic carbon species and pH. The carbonate equilibrium dictates that (1) belo^ Lov a pH of 8.2-8.3, bicarbonate is

3 4 O l O O EA QAP-11653.01 Section No.: 12 Revision No.: 0 Date; November 30, 1990 Page: 7 of 8

completely dominant vith only undetectable amounts of carbonate (and hydroxide) present, and (2) belov a pH of 4.2-4.5, only C0» should exist in detectable amounts.

These interactions are used as cross-checks for alkalinity determinations involving speciation.

2. Phase change speciations. Any suite of analyses involving total, particulate, or dissolved speciation vill generally be subject to comparisons betveen parameters (e.g., total vs. dissolved metals concentrations). Obviously, dissolved concentrations should not exceed total concentrations (disregarding combined precision effects vhen true total and dissolved concentrations are the same or very similar).

All such speciation analyses must be checked for such impossible situations before final data sign-off. For all parameters vith short holding times, these determinations must be made as soon as possible. For this reason, it is often advisable for the analyst(s) to perform certain amalyses concurrently (e.g., ammonia and total Kjeldahl nitrogen, total and dissolved phosphorus, and total oxidized nitrogen amd nitrate). Frequently, similarity of variamces is increased, thus improving the reliability of comparisons (and differences).

3. Residue amalyses. Analyses for total dissolved residue and similar analyses are also a type of speciation and are therefore subject to comparisons similar to those mentioned above. For instance, total residue should exceed all other species values, at least vithin the combined effects of individual analysis precisions.

4. Biological/toxicity data. When a project is multidisciplinary (i.e, involves biological, chemical, and possibly hydrological data), literature values for toxicity of specific amalyses to specific organisms can be used to identify impossible concentrations. Obviously, this applies only to toxics for vhich toxicity data are sufficient to make such judgements.

12.3.4.2 Comparison to Existing Databases

Often, rather extensive databases are available for the system studied (previous environmental studies, STORET data, NAWDEX data, USGS publications, EPA publications, academic literature). These data may be useful in "flagging" questionable or nonrepresentative data points before such data points are incorporated into models or are used as major decision tree components.

Analytical Services has accumulated a considerable amount of such data for interpretation and verification purposes. The analyst is urged to

3 4 010


consider this availability amd use the data as a cross-check vhen possible (and vhen agreed to by the appropriate project mamager).

12.3.4.3 Correction/Elimination Procedures

If simple errors (i.e., miscalculations) cannot be identified, the analysis must be performed again (vith the project manager's knovledge). Obvious corrections due to miscalculation may be made vith the knovledge of the laboratory manager.

3 4 EA-QAP-11653.01 Section No.: 13 Revision No.: 1 Date: November 30, Page: 1 of 3

0'

1990

02

1 3 . CORRECTIVE ACTIONS

13.1 OBJECTIVES

The objectives of the corrective action procedures presented belov are to ensure that recognized errors in performance of sample and data acquisition leads to effective remedial measures and that those steps required to correct am existing condition are documented to provide assurance that any data quality deficiencies are recognized in later interpretation and are not recurrent in the course of the project.

13.2 RATIONALE

Mamy times corrective measures are undertaken by project staff in a timely amd effective fashion but go undocumented. Such incidents may be of a recurrent type that might not be recognized by other staff performing the same activity. In other cases, corrective actions are of a complex nature and may require scheduled interactions betveen departmental groups. In either case, documentation in a formal or informal sense can reinforce the effectiveness amd duration of the corrective measures taken.

13.3 CORRECTIVE ACTION METHODS

Corrective action are of tvo kinds: immediate amd long-term.

13.3.1 Immediate Corrective Actions

Immediate corrective actions are of a minor or routine nature such as correcting malfunctioning equipment, correction of data transcription errors, and other such activities routinely made in the field, laboratory or office by technicians, analysts amd other project staff. These should be documented as prescribed in the project quality control procedures, as required. Specific documentation should be limited to notations in logbooks, notebook or on data sheets or other such forms. Such notations should be initiated amd dated by the person performing the corrective action.

13.3.2 Long-Term Corrective Actions

Long-term corrective action shall be used to identify and eliminate causes of nonconformamces vhich are of a complex nature and that are formally reported betveen mamagement groups. A formal system for reporting amd recording these corrective actions shall use the folloving procedure.

13.3.3 Corrective Action Steps

For either immediate or long-term corrective actions, steps comprising closed-loop corrective action system are as follovs;

13.3


Define the problem

Assign responsibility for investigating the problem

Investigate and determine the cause of the problem

Determine a corrective action to eliminate the problem

Assign and accept responsibility for implementing the corrective action

Establish effectiveness of the corrective action and implement the correction amd

Verify that the corrective action has eliminated the problem.

4 Audit Based Non-Conformances

Internal auditing of saunple collection through data analyses activities may result in the discovery of non-conforming materials or procedures that, left uncorrected, could jeopardize the quality and integrity of project data and results. When such auditing is part of a project and a non-conformance is found, corrective action is initiated by documenting the audit finding and recommended corrective action on an Audit Finding Report (Figure 13-1). The corrective action undertaken by the designated responsible party is documented vith an implementation schedule and management approval. The implementation is verified by the auditor on the same form vhich is then made part of the project audit report record. Other means of documenting long-term corrective action are equally acceptable if the seven (7) elements listed above are addressed.

13.4 CORRECTIVE ACTION REPORT REVIEW AND FILING

Immediate and long-term corrective actions require reviev to assure that, during the time of non-conformamce, erroneous data vere not generated or that, if possible, correct data vere acquired instead. Such confirmation and reviev is the responsibility of the supervisor of the staff implementing the corrective action. Confirmation shall be acknovledged by notation amd dated signature on the affected data record or appropriate form or by memorandum to cognizant project management. Such corrective action forms and memorandum shall be retained on file by responsible task leaders and filed centrally by the project manager.

13.5 CORRECTIVE ACTIONS REPORTS TO MANAGEMENT

The Project QA Officer shall provide project mamagement vith corrective action reports as described in Section 2.

6 0154

EA E I M G > M E £ ? 4 U M G . s a e / M C S . AAJO TECa-KMC.jOGY. BMC.

EA-QAP-11653.01 Section No.: 13 Revision No.: 1 Date: November 30, 1990 -i Page: 3 of 3

MJOCTOR aatMTURI

AUDIT FINDING REPORT

AUCXTOAH

M0MDUAU8)00KTACm AfMA pnojscrmPAfnMENT NUMBtn

RSQune iB r r s

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AUDnOR snNATVira DOCUMBfTUaBTORCUMIOUr OATH

Figure 13-1.

3 4 0 1 5 5


14. QUALITY ASSURANCE REPORTS

Quality Assurance reports vill be prepared by the Project Quality Assurance Officer amd submitted to the Project Manager and the manager of the audited group, to ensure that QA and QC objectives are met. Items to be included in the QA reports are the summary of results for the performamce or the system audit and, vhere applicable:

An assessment of adherence to vork scope amd schedule for the audited task

An assessment of the precision, accuracy, and completeness of saunple batches and subsequent status of data processing and analyses

Significant quality control problems and the status of any ongoing corrective actions

Any changes to the QA program plan, and

. The status of the implementation of the QA project plan.

The audit-reporting process vill include a summary of audit results that vill be developed from audit reports by the Project Manager, Project Officer, or a designee specified for a given project task. These summaries may be distributed monthly or quarterly to clients or as othervise specified in QA project plams during periods vhen sampling and laboratory amalyses are undervay. These reports should be centrally filed as documentation of project quality assurance activities.

3 4 0156 EA QAP-11653.01 Section No:Appendix C-l Revision No.: 1 Date: November 30, 1990 Page; 1 of 1

ANALYSIS OF METHYL MERCURY IN SOIL AND WATER SAMPLES

At the present time, the USEPA has not yet established a standard method for the analysis of methyl mercury in soil or vater samples in accordance vith CLP protocols. Several commercial and academic analytical laboratories have developed and documented analytical methods for this procedure through modification of tvo scientifically accepted analytical procedures.

Association of Official Analytical Chemists Method Number 25.146 "Mercury (Methyl) in Fish and Shellfish Gas Chromatographic Method First Action," AOAC, 1984.

Electric Paver Research Institute Method EPRI EA-5197, "Measurement of Bioavailable Mercury Species in Fresh Water and Sediments," Battelle, Pacific Northvest Laboratories, 1987.

Most of the commercial analytical laboratories that have developed methods for methyl mercury in soil and vater have used modifications to the AOAC method. This method employs an extraction folloved by gas chromatography. Most methods use a GC vith and electrolytic conductivity detector (ECD), although some methods have been developed to use an atomic emission detector to achieve lover detection limits.

The specific method to be used vill be identified by the Contract Laboratory and vill be documented as descried in Section 7 of this QAPP.

3 4 01b?

m - /

APPENDIX A f'^^Vy ^

( 9 ^ PROJECT QUALITY ASSURANCE STAFF RESUMES

(To Be Provided Upon Final Selection of (Ontract Laboratory)

• ;r"X-"-ta'«»^^

3 4 0 1 5 8

APPENDIX B

STANDARD OPERATING PROCEDURES

(To Be Provided Upon Final Selection of Contract Laboratory)

3 4 0159

APPENDIX C

ANALYTICAL METHODS FOR NONSTANDARD ANALYSES

C-l Analysis of methyl mercury in soil and vater saaples

C-2 Analysis of total mercury in biological tissue saaples

3 4 0160

APPENDIX C

Section C-l

Analysis of Methyl Mercury in Soil amd Water Samples

3 4 0161 EA QAP-11653.01 Section No:Appendix C-l Revision No.: 0 Date: September 27, 1990 Page; 1 of 1

ANALYSIS OF METHYL MERCURY IN SOIL AND WATER SAMPLES

At the present time, the USEPA has not yet established a standard method for the amalysis of methyl mercury in soil or vater samples in accordance vith CLP protocols. Several commercial and academic analytical laboratories have developed and documented analytical methods for this procedure through modification of tvo scientifically accepted amalytical procedures.

Association of Official Analytical Chemists Method Number 25.146 "Mercury (Methyl) in Fish and Shellfish Gas Chromatographic Method First Action," AOAC, 1984.

Electric Paver Research Institute Method EPRI EA-5197, "Measurement of Bioavailable Mercury Species in Fresh Water and Sediments," Battelle, Pacific Northvest Laboratories, 1987.

Most of the commercial analytical laboratories that have developed methods for methyl mercury in soil and vater have used modifications to the AOAC method. This method employs an extraction folloved by gas chromatography. Most methods use a GC vith amd electrolytic conductivity detector (ECD), although some methods have been developed to use am atomic emission detector to achieve lover detection limits.

The specific method to be used vill be identified by the Contract Laboratory amd vill be documented as descried in Section 7 of this QAPP.

3 4 016.-!

OFFICIAL METHODS OF ANALYSIS

OFTHE

ASSOCIATION OF OFFICIAL ANALYTICAL CHEMISTS

EDITED BY SIDNEY WILLIAMS

FOURTEENTH EDITION, 1984

PUBLISHED BY THE

ASSOCIATION OF OFFICIAL ANALYTICAL CHEMISTS, INC.

1111 NORTH NINETEENTH STREET

SUITE 210

ARLINGTON, VIRGINIA 22209 USA

472 METALS AND OTHER ELEMENTS

3 4 0163 AOAC OFFICIAL Mrrooos OF ANALYSIS (1984)

Prep, working curve of required range, starting with blank and extending to final ud of range, with 4 intermediate increments. Add appropriate amts of Hg to 50 mL 0.1^ HQ in separator. Add 5 mL HjNOH.HQ reagent and S mL CHO,. and shake vigorously I min. Let layers sep., drain off CHCl,, and discard, being carefiil to remove as completely as possible all droplets of CHO,. Add 3 mL 30% HOAc and appropriate vol. dithizone soln, shake vigorously 1 min, and let layers sep. (HOAc aids in stabilizing mercuric dithi-zofiate.) Insert cotton pledget into stem of sepa/atbr and collect dithizone ext (discarding first mL) in test tube for transfer to appropriate cell. Make photometer readings at 490 nm. (Since both dil. dithizone aod mercuric dithizonate are somewhat unstable, read immediately.) Plot A against |Lg Hg.

-Ref.: JAOAC 35, 537(1952).

CAS-7439-97-6 (mercury)

Mweury (Methyl) in Rsh and SMff ish

G M Chromatographic Method

First Action

(Caution: Ste 51.045 and 5I.046.)

2S.146 Mt thod P*rtotmmnc»

Av. rec. at 0.15-1.37 ^ Hg/g • 108% (5. - 0.017-0.30, S. -0.017-0.23)

^.147 Prrndplm

Org. interferences are removed from homogenized sample by acetone wash followed by benzene wash. Protein-bound Me Hg is released by addn of HG and extd into benzene. Benzene ext is coned and analyzed for CHjHgG by GC.

25.148 /?Mff«Ttl

(a) Solvents.—Acetone, benzene, and isopropanol are all distd in glass (Burdick & Jackson Laboratories, Inc.; MCB Manu&cturing Chemists, Inc.). Note: Benzene is a possible carcinogen.

(b) Hydrochloric acid soln (I + /).—Add coned HCl to equal vol. of distd or deionized H,0 and mix. Ext HQ soln 5 times with V* Its vol. of benzene by shaking vigorously 15 sec in separator. Discard benzene exts. Sohi may be mixed in advance but must be extd immediately before use.

(e) Carrier gas.—(X. quality Ar-CH. (95 + 5). (d) Sodium sulfate.—Heat ovemight in 600* (iimace, cool, and

store in capped brown bottle. Line cap with Al foil to prevent contamination from cap.

(e) Methyl mercuric chloride std solns.—Keep tightly stoppered. U) Siocic std jo/n.—1000 )ig Hg/mL. Weigh 0.1252 g CHiHgO (ICN-K&K Laboratories, Inc.. Plainview. NY 11803) into 100 mL vol. fiask. Dil. to vol. with benzene. (2) High intermediate std soln.—*0 |jLg Hg/mL. Dil. 10.0 mL stock soln to 250.0 mL with benzene. (J) Low intermediate std soln.—2.0 M4 Hg/mL. Dil. 10.0 mL high intermediate std soln to 200.0 mL with benzene. (4) Worldng std j<Ww.—0.010-0.30 iig Hg/mL. Prep, monthly by dflg with benzene io vol. flasks as follows: Dil. 15 mL of 2.0 |ig Hg/mL std to 100.0 mL. 10.0 mL to 100.0 mL, and 10.0 mL to 200.0 mL for 0.30, 0.20, and 0.10 ng Hg/mL, resp. Dil. 20 mL of 0.10 M Hg/ -'L std to 25.0 mL. lO.O mL to 25.0 mL, 10.0 mL to 50.0 mL. and

.0 mL to 100.0 mL for 0.080, 0.040, 0.020, and 0.010 )i« Hg/mL, resp.

(0 Mercuric chloride column Irealmeni soln.—1000 ppm HgQ,. Dissolve 0.1 g HgQ, in IOO mL benzene.

25.149 - Apparatua

Wash all glassware with detergent (Micro Laboratory Cleaner, Intemational Products, Trenton, NJ 08601, or equiv.) and rinse thoroly with hot tap H]0 followed by distd or deionized H]0.

(a) Centrifuge.—Model UV (International Equipment Co., Needham Heighu, MA 02194), or equiv.

(b) Centrifuge tubes.—^50 mL capacity with ground glass or Teflon-lined stoppers.

(c) Kudema.Danish [K-D) concentrators.—250 mL flask (No. K570001, Kontes Glass Co.) and 10 mL graduated concentrator tube (No. K570050, size 1025, Kontes Class Co.).

(d) Modified Snyder distilling column.—Modify Snyder column (No. K503000 size 121, Kontes Glass Co.) in either of 2 ways: (!) Shorten 3-section, 3-baU column to 2-section, 2-ball column by cutting off top at uppermost constriction, (ii) Insulate 3-section, 3-bail column by wrapping glass wool around top section and holding it in place wilh Al foil. Glass wool and foil must surround only top section above top ball.

(c) Carborundum boiling chips.—20 mesh, HCI-washed. (0 Graduated cylinders.—Gaa A, 25 mL capacity, with ground-

glass stopper (Kimble 20036, or equiv.). (g) Transfer pipets.—Disposable glass, Pasteur-type 5y4 in. long

(No. I3-678-6A, Fisber Scientific Co., or equiv.). (h) Dropping pipets.—5 mL capacity (No. 13-710B, Fisher Sci

entific Co., or equiv.). (I) Gas chromatograph.—Hewlett-Packard Mode] S710A or equiv.,

equipped with linear *'Ni electron capture detector and 6 ft x 2 mm id <il«ni7rd glass column packed with 5% DEGS-PS on 100-120 mesh Supelcoport (Supelco, Inc.). Pack eolumo no closer than 2.0 cm from injection and detector port nuts and hold packing in place with 2 cm high quality, silanized glass wool at both ends. Install oxygen scrubber and molecular sieve dryer (No. HGC-145, Analabs, North Haven, CTT 06473, or equiv.) between carrier gas supply and column. Condition column according to manufacturer's instructions as follows: Flush column 0.5 h with carrier gas flowing at 30 mL/min at room temp. Then heat 1 b a 100*. Next, heat column to 200° at programmed heating rate of 4*/inin and hold at 200* ovemight. Do not connect column to detector during this conditioning process. Maintain 30 mUmin carrier gas fiow at all times during conditioning, treatment, and use. Operating conditions: column 155*; ii jector 200°; detector, 300*; carrier gas flow 30 mU min; and recorder chan speed 0.5-1.0 cm/min. Under these conditions and with HgCli column treatment procedure described below, CH>HgCl peak will appear 2-3 min after sample injection.

25.150 Mareun'e Chlerid* Column Trmatmtnt

5% DEGS-PS conditioned according to manufacturer's instructions can be used to det. CHiHgQ only after treatment by HgOi soln, (I). Treat column any time column has been heated to 200°. Because column perfonnance degrades with time, also treat column periodically during use. Perform appropriate HgCli treatment procedures described below. Procedure (b) produces most stable baseline and is recommended over procedure (c) for routine use.

(a) Following 20Cr column conditioning.—If column has just been conditiooed ovemight at 200*, use this procedure. Adjust column temp, to 160* and connect detector. When baseline is steady, treat column by injecting 20 tiL HgQ] treatment soln 5 times at 5-10 min intervals. (Change in column performance may be monitored by iiuecting 5 i&L 0.010 )ig Hg/mL std sohi before and between HgO: treatment soln iiyections.) During treatment procedure, large broad peaks will elute. (CH,HgCl peak retention time will decrease and peak ht will increase.) Approximately IWIV* h after last HgCIi treatment soln injection, a final large peak will elute. (CH,HgCl peak ht and retention time will be stable.) This broad peak and CH>HgCl peak ht stability signal completion of treatment process. Adjust

3 4 0164

m AOAC OFFICIAL METHODS OF ANALYSIS (1984)

column temp, to 155° and wait for steady baseline: then column is ready for use.

(b) On day preceding sample extract analysis.—If column has been treated by procedure (a) or used at 155° to analyze sample exts, column may be treated at end of working day for next day's use as follows: Lower column temp, to 115° and inject 20 |iL HgCl: treatment soln one time. Broad peaks will elute between 11 and 15 h after HgCl, injection. Next working day, increase column temp, to operating temp. When baseline is steady (ca 15-30 min), column is ready for use.

(c) During sample extract analysis at ISS*.—If column has been used at 155* fcr ext analysis and eolumo perfonnance has degraded enough to require HgOi treatment, increase column temp, to 160°, inject one 20 \LL aliquot of HgO] treatment solo, and monitor baseline. Large, broad peaks will elute 1-1 V% h after HgO] injection, signaling completion of treatment process. Decrease column temp, to 155* and wait for steady baseline; then column is ready for use.

25.151 Extraction of Mat/iy/ Marcury Chlorida

Perform all operations, except weighing, in laboratory hood. Accurately weigh 2 g homogenized sample into 50 mL centrf. tube. Add 25 mL acetone, stopper, and shake vigorously 15 s. Remove stopper, cover with foil, and centrf. 2-5 min at 2000 rpm. Carefully decant and discard acetone. (Use dropping pipet to remove acetone, if necessary.) Repeat 25 mL acetone wash step twice more. Break up tissue with glass stirring rod before shaking, if necessary. Add 20 mL benzene, stopper, and shake vigorously 30 s. Remove stopper, cover with foil, and centrf. 2-5 min at 2000 rpm. Carefully decant (or draw off with dropping pipet) and discard benzene. Extraneous peaks in final GC anal, chromatograms indicate that more vigorous shaking with acetone and benzene is required.

Add 10 mL HCl sobi to centrf. tube contg acetone and benzene-washed sample. Break up tissue with glass stirring rod, and ext sample by adding 20 mL benzene and shaking gently but thoroly 2 min. Remove stopper, cover with foil, aod centrf. 5 min at 2000 rpm. If emulsion forms, add 2 mL isopropanol and gently stir benzene layer to break emulsion, taking care not to disturb aq. phase, and recentrf. Carefully transfer benzene layer to K-D concentrator, using 5 mL dropping pipet. Rinse centrf. tube walls with 3-4 mL benzene and transfer rinse to K-D concentrator. Repeat extn step twice more, adding 20 mL benzene and shaking / min each time. Combine all 3 benzene exts in K-D concentrator.

Place 4-6 boiling chips in K-D concentrator, connect Snyder column, wet Snyder column bubble chambers with 3-4 drops of benzene, and immediately place tube in steam bath or vigorously boiling H]0 bath. Evap. so that 8 mL remains when cooled to room temp. Cool. Discoimect concentrator tube and quant, transfer soln to 25 mL g-s graduate using Pasteur-type transfer pipet. Dil. to 20.0 mL with benzene and mix. Add 4 g Na,SO. and mix again. NaiS04 must be added to 20 mL coned sample ext within 10 h of fint acetone wash. Tightly stoppered exts may be held ovemight at this point. Analyze by GC.

25.152 OtromatograithY

Verify that system is operating properiy by iiyecting 5 yil. vols of 0.01 |ig Hg/mL working std soln into chromatogiaph. Difference between CH,HgO peak hts for 2 iiyectioos should be «4%. Check detector linearity by chromatographing all 0.01-0.30 iig Hg/mL working std solns.

Inject duplicate 5 |iL vols, (equiv. to 0.5 mg sample) of ext. Difference between (:H,HgO peak hts for 2 iiyections should be «4%. Next, inject duplicate 5 \tX. vols, of std soln with CH,HgO concn approx. equal to or slightly greater than ext CH>HgO concn. Because column perfonnance and peak ht slowly decrease with time, calc. each sample concn by comparison to std soln iiyected immediately after sample.

SELENIUM 473

Calc. Me Hg conlent of homogenate in \t.% Hg/g (ppm Hg) by comparing av. CH,HgCl peak ht of duplicate sample injections with av. CHjHgCl peak ht of duplicace std injections.

ppm Hg = (RIR') X ( C I O X 20 where R = av. peak ht of duplicate sample injections; R' = av. peak ht of duplicate std injections; C «> g sample; C " concn of Hg in CH,HgO std soln (pig Hg/mL).

Ref.: JAOAC 66, 1121(1983).

CAS-7439-97-6 (mercury)

Nickal in T M

Atomic Absorption Spoctrophotomatric Mathod

Rnal Action

25.153 5«ff 25.031-25.035.

Selenium in Food

Ruorometrie Method

Rnal Action

25.154 Apparatu*

(a) Fluorometer.—.Filter fluorometer or spectrophotofluorometer capable of excitation at 366 nm and detection of fluorescence at 525 nm. (Caution: See 51.008.)

(b) Cuvels or tubes.—Pyrex culture tubes, 12 x 75 mm, selected by matching, are suitable for fluorometer.

(c) Wrist-action shtiker.—Model BB (Burrell Corp.), or equiv., set at max. speed.

(d) Separators.—C\asi, 250 and 125 mL, with Teflon stopcocks.

25.155 Raaganta

(Use anal, grade reagents and glass-distd HjO thruout except as noted.)

(a) Nitric acid.—Distil from glass, discarding first and final 10%. (b) Dilute sulfuric add.—SN. Dil. 140 mL H,SO. to 1 L with

H]0. (c) Ammonium hydroxide soln.—Approx. 6M Dil. 400 mL NH.OH

to I L with HjO. (d) Disodium EDTA soln.—Q.OlM. Dissolve 7.445 g

Na]H,EDTA.2H,0 and dU. to 1 L with H]0. (c) 2J.Diaminonaphlhalene (DA^f) soln.—1 mg/mL. Pulverize

DAN (purest grade available; product from Aldrich Chemical Co. has been found satisfactory) in clean mortar to fine powder. Insen glass wool plug in stem of 250 mL separator and add 150 mL 5A/ H]S0.. Transfer 0.150 g DAN to separator and place on shaker 15 min to dissolve. Add 50 mL cyclofaexane and shake 5 min. Let phases sep. 5 min, drain lower phase into another separator, and discard cyclobexane (upper) phase. Repeat cyclohexane extn twice more; after third extn, drain lower phase into low-actinic g-s flask, add 1 cm layer hexane, and store in cold. Soln is stable several weeks.

(0 Selenium std soln.—(l) Stock soln.—100 pig/mL. Dissolve 0.1000 g black Se (purity »99.9%) in ca 5 mL HNO,, (a), and warm to dusolve. Dil. with H,0 and 20 mL 5N H,S0. to 1 L. (2) Working soln.—Dil. stock soln with H]0 and 5 ^ H,S04 to give Se concns in 0.1 A/ HtS0« appropriate for level <A Se expected in sample. Store all solns in all-glass containers. Sohu are stable indefinitely.

25.156 PraparaHon of Standard C u m and Ftuofomatrie Blank

Conduct appropriate vols of Se std sohu (< 10 mL contg «800 ng Se) and 10 mL H]0 each thru entire detn, including digestion, along with samples. Zero fluorometer against blank soln and read

APPENDIX C

Section C-2

Analysis of Total Mercury in Biological Tissue Samples

3 4 016b

3 4 0166

APPENDIX C

Section C-2

Analysis of Total Mercury in Biological Tissue Samples

3 4 0167 £?A €00/4-31-053

United States environmental Protection Agencv

4>EPA Research and Deveiopment

Intarim Methods For The SdnspUng and Analysis of Prforfty Pollutants In Sediments

and Fish Tissue

Prepared for Regional Guidance

Prepared by Physical and Chemical Methods Branch Environmental Jtonltoring and Supoort Laboratory Cincinnati , Ohio 45268

m Analysis of Fish for Mercury

3 4 016« \

I I I

1. Scope and Application ^

1.1 This method is used for detennination of total mercury (organic and I

Inorganic) In fish. A weighed portion of the sainple Is digested

\

\

I

with sulfuric and nitric acid at 58°C followed by overnight

oxidation with potassium permanganate at room temperature. Mercury

1s subsequently measured by the conventional cold vapor technique.

1.2 The range of the method Is 0.2 to 5 ug/g but may be extended above

or below the normal Instrunent and recorder control.

2. Sample Preparation I

2.1 The sample may be prepared as described under "Sample Handling" or

the special metal procedure may be used. A 0.2 to 0.3g portion |

should be taken for each analysis. The sample should not be

allowed to thaw before weighing.

3. Preparation of Calibration Curve

3.1 The calibration curve is prepared frora values for portions of

spiked f1sh tissue treated in the manner used for the tissue

samples being analyzed. For preparation of the calibration

standards, choose a 5g portion of f1sh and blend In a Waring j

blender.

3.2 Transfer accurately weighed portions to each of six dry BOO

bottles. Each sainple should weigh about 0.2 grams. Add 4 ml of

cone. H-SO^ and 1 ral of cone. HNO3 ^ ° ^^'^^ bottle and place

1n water bath at 58°C until the tissue Is completely dissolved

(30 to 60 min.).

7 /. r. • ,-

( •

3.3 Cool and \TZi\%izT 0-, 0.5- 1.0-, 2.0-, 5.0- and 10.0- ml aliquots

of the working mercury solution containing 0 to 1.0 ug of irercury

to the BOO bottles. Cool to 4* 0 In an 1ce bath and cautiously

add 15 ml of potasslua permanganate solution. Allow to stand

overnight at room temperature under oxidizing conditions.

3.4 Add enough distilled water to bring the total volume to

approximately 125 ml. Add 6 ml of sodium chloride-hydroxylamine

sulfate solution to reduce the excess permangante.

3.5 Walt at least 30 sec. after the addition of hydroxylamine.

Treating each bottle individually, add 5 ml of the stannous sulfate

solution and inmediately attach the bottle to the aeration

apparatus.

3.6 Continue with the procedure as given in Method 245.1 for water (7).

The calibration curve Is prepared by plotting the peak height

versus the mercury concentration. The peak height of the blank is

subtracted frora each of the other values.

4. Sample Procedure

4.1 Weigh 0.2 to 0.3g portions of the sample and place in the bottom of

a dry BOO bottle. Care must be taken that none of the sample

adheres to the side of the bottle. Add 4 ml of cone. H-SO. and

1 ral of cone. HNO^ to each bottle and place in a water bath

maintained at SS^C until the tissue is completely dissolved (30

to 60 minutes).

4.2 Cool to 4°C in an ice bath and cautiously add 5 ml of potassium

permanganate solution in 1 ml ineranents. Add an additional 10 ml

of more of permangante, as necessary to maintain oxidizing

35

i;

m

conditions. Allow to stand ovemight at room temperature (see

NOTE). Continue as described under 3.4. I

PTOTE: As an altemate to the ovemight digestion, the

solubilization of the tissue may be carried out in a water bath at |

aO^C for 30 rain. The sanple is then cooled and 15 ml of

potasslin permanganate solution added cautiously. At this ooint, I

the sample 1s retumed to the water bath and digested for an ]

additional 90 rain, at 30°C (9). If this method is followed, the

calibration standards must also be treated in this manner. | I

Continue as described under 3.4.

5. Calculation j

5.1 Measure.the peak height of the unknown frora the chart and read the

mercury value from the standard curve.

5.2 Calculate the mercury concentration in the sample by the formula: .

ug Hg/gram - ug Hg in aliquot wg ng/gram wt. Of aliqUOt in gmS

5.3 Report mercury concentrations as follows:

Below 0.1 ug/gn, < 0.1 ug; between 0.1 and 1 ug/gm, to nearest 0.01

ug; between 1 and 10 ug/gm, to nearest 0.1 ug; above 10 ug/gm, to

nearest ug.

6. Quality Assurance

6.1 Standard quality assurance protocols should be employed, including

blanks, duplicates, and spiked samples as described in the

"Analytical Quality Control Handbook" (4).

6.2 Report all quality control data when reporting resaults of sample

analyses.

36

7. Precision and Accuracy

7.1 The fol lowing standard deviations on repl icate f i sh samples were

recorded at the Indicated levels: 0.19 ug/gni±0.02, 0.74

ug/gn±0.05, and 2.1 ug/gra±0.06. The coeff ic ients of variat ion at

these levels were 11.9t, 7.OX, and 3.6S, respectively. Recovery of

mercury at these levels, added as methyl mercuric chloride, was

112S, 93X, and 86X, respectively.

37

-)«»«ftWi9«S^.|*^ taHf.. r.-a WM .awij«BM4iJHP.ai

#

•7 ' / o 4 U i / ,

EPA 500/4-81-0!55 United States Environmantal Protection Agencv

^EPA Research and Development , 5 ; ..v.rj

I n te r im Methods For The Sampling and Analysis o f P r i o r i t y Pol lu tants i n Sediments

and Fish Tissue

Prepared for Regional Guidance

Prepared by Physical and Chemical Methods Branch Environmental Monitoring and Support Laboratory Cincinnati, Ohio 45268

G^U^B

-7

0 4

#

Spread the other half of the sample uniformly in the tray

and allow to dry at room temperature for four or five days

In a contaalnant-free environment. When dry - less than 10<

water - grind the sample with a large mortar and pestle to a

uniform particle size. Discard any foreign objects found

during grinding and t n n s f s r the powdered sediment into a

wide-mouthed glass Jar and seal with a Teflon-lined lid.

This air-dried sample will be used for those analyses

requiring an air-dried sample.

3.2 Fish

3.2.1 To prepare the fish sample for analytical pretreatment,

unwrap and weigh each fish. Combine small fish by site and

species until a rainimura combined weight of 250g is

obtained. Chop the sample into 1-inch chunks using a sharp

knife and mallet.

3.2.2 Grind the sample using a large commercial meat grinder that

has been precooled by grinding dry ice. Thoroughly mix the

ground material. Regrind and mix material two additional

times. Clean out any material remaining in the grinder; add

this to the sample and mix well.

3.2.3 Weigh five 10.Og portions of the sample into separate 125-ml

vials. Using a crii^jer, tightly secure a septum to aach

bottle with a seal. Store these sample aliquots in a

f r^^ZQT until ready for volatile organics analysis.

3.2.4 Transfer the remaining fish sample to a glass container and

store in a freezer for later subsampling and analysis.

3

i ; .

APPENDIX D

CONTAINERS, PRESERVATION, AND HOLDING TIMES

APPENDIX D RECOMMENDED SAMPLE CONTAINERS, SAMPLE PRESERVATION, SAMPLE HOLDING TIMES,

AND PERMISSIBLE SAMPLE TYPES

Paraaeter

Concentrated Waste Saaplea

Container

Organic Compounds

Metals and Other Inorganic Coapounds

KP ToKlclty

Flash Point and/or Heat Content

Fish Saaples

Organic Coapounds

Metals and Other Inorganic Coapounds

8-oz. wldeaouth glass with Teflon liner




Wrap In alumtnua full

Place In plastic zip-lock bag

Liquid - Low to Medlua Concentration Saaples

Alkalinity 500-al or l-Ilter poly-' ethylene with polyethylene or polyethylene IIned closure

A c i d i t y

H;irt.«-i lol(>(>i<-Hl

3 ( ) 0 - a l o r l - l I t e r p o l y - l e t h y l e n e w i t h p u l y e t i i y -l e i i e o r p o l y e l i i y I e i ie I i i i e i l c l o H u r e

2SI ) - in l gl . ' is.s w i t h i ;L i .ss

r l i i H i i r e o r p l < i s t i i : ( '<i| i-

. ' i l t io u f l i o l i i K a n l IK ' I .iv/i>(l

Preservative

None

None

None

None

Freeze

Freeze

Cool, A*C

Cool , 14'C

Holding Time

ASAP

ASAP

ASAP - NS

ASAP - NS

ASAP

ASAP

14 days

14 (lays

ll lirs,

PeriRlsRihIe Sampl <; Type

C or C

Referenc

0 ot C

(J or C

r- APPENDIX D

RECOMMENDED SAMPLE CONTAINERS, SAMPLE PRESERVATION, SAMPLE HOLDING TIMES AND PERMISSIBLE SAMPLE TYPES

Paraaeter Container Preservative

Liquid - Low to Medlua Concentration Saaples (Continued)

Static Bloassay

Blocheaical Oxygen Ocmand (BOD)

Cliloride

1-gal. aaber glass Cool, A'C (not solvent rinsed)

l/2-gal. polyethylene' Cool, A"C with polyethylene closure

5U0-al or l-l Iter poly-' None ethylene with polyethylene or polyethylene lined closure

Holding Tiae

48 hrs.

AB hrs.

28 days

PermlsKihIe Sample Type

C or C

G or C

G or C

Ref erein:e

Chlorine Residual

Color

C o n d u c t I v i t y

('lironiiira. Hexavalent

CyanIde

I n - s i t u , beaker o r bucke t None

5 0 0 - a l o r l - l l t e r p o l y - ' C o o l , A ' c e t h y l e n e w i t h p o l y e t h y lene o r p o l y e t h y l e n e l i n e d c l o s u r e

5 0 0 - a l o r 1 - l i t e r p o l y - ' C o o l , 4*C e t h y l e n e w i t h p o l y e t h y lene o r p o l y e t h y l e n e I Ined c l o s u r e

1 - l i t e r p o l y e t h y l e n e w i t h C o o l , A"C p o l y e t h y l e n e c l o s u r e

i - l l t e r o r l / 2 - g a l l o i i A s c o r h i c A c l d ^ . ^ pol y e t h y l e i i e w i t h p o l y - .Sodium H y d r o x i d e , e t i i y l e i i e o r po l y<>t tiy I (MIO pH > I2 l i n e d c loHure C o o l . 4°C

Ana lyze Immed ia te l y

48 h r s .

28 days (determine on

site if possible)

24 hrs.

I 4 d.lys

C or C

G or C

4-

APPENDIX D

RECOMMENDED SAMPLE CONTAINERS, SAMPLE PRESERVATION, SAMPLE HOLDING TIMES AND PERMISSIBLE SAMPLE TYPES '



Dissolved Oxygen

(Probe)

Dissolved Oxygen

(Winkler)

EP Toxicity

Fluoride

Hardness

U S

Metals

Hotals, Dissolved

In-situ, beaker or bucket

300-al glass, BOD bottle

l-gal. glass (aaber) with Teflon liner

l-llter polyethylene or'

l/2-gal. polyethylene with

polyethylene or polyethy

lene lined closure

500-ml or l-llter poly

ethylene with polyethy

lene or polyethylene

lined closure

None

Fix on site,

store in dark

Cool, 4*C

None

50X Nitric^

Acid. pH <2

500-al or l-llter polyethylene with polyethylene or polyethylene IIned closure

l-liter polyethylene with polyethylene lined c. losure

| - l i t e r p o l y e t h y l e n e w i t h p o l y e t h y l e n e l i n e d c I osi i r e

• Cool, 4"C

50X Nitric^

Acid, pH <2

Fl I ter-on-slte2 501 Nitric •

Arhl, pH <2

Holding

Time

Determine

On Site

Permissible

Sample

Type

8 hrs. (determine on site if possible)

ASAP NS

28 days

G or C

G or C

6 aonths G or C

48 hrs. G or C

h months

6 rooiith.s

G or C

Reference

APPENDIX D RECOMMENDED SAMPLE CONTAINERS, SAMPLE PRESERVATION, SAMPLE HOLDING TIMES

AND PERMISSIBLE SAMPLE TYPES ' Permissible

Holding Sample Paraaeter Container Preservative Tiae Type Reference


Nutrients* i-llter polyethylene or 50X Sulfuric^ 28 days G or C C l/2-gal. polyethylene A d d , pH <2 with polyethylene or poly- Cool, 4*C ethylene lined closure

Oil and grease l-llter wldeaouth glass 50Z Sulfuric^ 28 days G C with Teflon liner Acid, pH <2

Cool, A'C

Organic Coapounds - C Extractable and Pesticide Scan

No Residual Chlorine l-gal. aaber glass or Cool, 4*C 47 days^ G or C C Present 2 l/2-gal. aaber glass

with Teflon liner

Residual Chlorine l-gal. aaber glass or Add 3 al lOX 47 days^ G or C C Present 2 1/2-gal. aaber glass sodiua thiosulfate

with Teflon liner per gallon Cool, 4*C

Organic Compounds -Purgeable (VOA) Os!

No Residual Chlorine 2 40-al vials with 4 drops cone, hydro- 14 days G C .represent Teflon lined septum caps chloric acid,

Cool, 4"C

No Residual Chlorine 2 40-ml vials with Cool, 4 "C 7 d.iys G <-' " ' Present Tiff lon lined septum imps

K I ' N I ' I I I . I I ( I I I K I l i i f 2 4U-n i l v l a l H w i t l i F n t i t i i o t e 6 14 d . i ys (.' <• " "

I 'f s t i l l l i - l j l l l l l l l K ' l l S C | > ( | | I I I l ' . l | < S

r>.





Organic Coapounds -Specified and Pesticides (Non-Priority Pollutants such as Herbicides)

l-gal. glass (aaber) or 2 l/2-gal. glass (aaber) with Teflon lined closure

Footnote 7

Holding Tiae

47 days'

Permissible

Sample

Type

G or C

Reference

Organic Hal Ides Total (TOX)

250-al aaber glass with Teflon lined septua closure

Cool, 4'C ASAP - NS

pH In-situ, beaker or bucket

None Analyze Immediately

Pheno ls l - l l t e r aaber g l a s s w i t h T e f l o n l i n e d c l o s u r e

50Z S u l f u r i c A c i d , pH <2

C o o l . 4"C

28 days

Phosp t ia te -Or tho 5 0 0 - a l o r l - l i t e r p o l y e t h y l e n e w i t h p o l y e t h y lene o r p o l y e t h y l e n e I i n e d c l o s u r e

F l l t e r - o n - s l t e C o o l , A 'C

48 hrs.

C..'-J

Phospiiorus, Total Dissolved

500-al or l-llter polyethylene with polyethylene or polyethylene lined closure

Fi Iter-on-site 50Z Sulfuric Acid, pH <2 Cool, 4"C

28 days

Solids. Settleable l/2-gal. polyethylene with polyethylene r I iisiire

Cool. 4°C 4H hrs. (; or C

o

APPENDIX D RECOMMENDED SAMPLE CONTAINERS, SAMPLE PRESERVATION, SAMPLE HOLDING TIMES

AND PERMISSIBLE SAMPLE TYPES '


Liquid - Low to Medluea Concentration Saaples (Continued)

Cool, k'C Sol Ids (Total and Suspended, etc.)

Sulfates

Sulfides

500-K51 or l-liter poly-' ethylene with polyethylene or polyethylene lined closure

500-C91 or l-Hter poly-B ethylene with polyethylene or polyethylene lined closure

500-B1 or l-llter poly-2 ethylene with polyethylene or polyethylene lined closure

In-sltu, beaker or bucket

500-al or l-Hter poly-H ethylene with polyethylene or polyethylene lined closure

Soil. Sediaent or Sludge Samples - Low to Medluia Concentration

E. P. Toxicity 8-oz. wldereouth glass Cool, 4°C with Teflon* lined closure

Temperature

Turbidity

Cooa„ 4*C

2 E I Z i nc A c e t a t e ^ Cone. Sodluca

Hyd iron ide t o pH >9 Coo l , k°C

None

C o o l , 4°C

H e l ; i i s H-07.. wl i lemoi i th gla.ss w i t h r e f i l l 11* I Ined «• lo.si ire

Cool , 4"C

H o l d i n g TiEse

7 days

28 days

7 days

Deteriaine On S i t e

48 h r s .

A.SAP - NS

(t mont lis

Per iD l ss lh le Saiapl e

Type

G or C

G or C

G or C

G or C

G o r C

Reference

4::.-.

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Parameter Container Preservative Holding Tlcae

Soil, Sediaent or Sludge SaEipleB - Low to MedluB Concentrationa (Continued)

Nutrients Including: 5(X)-B1 polyethylene with Nitrogen, Phos- polyethylene closure or phorus, Cheaical 8 oz. uideoouth glass Oxygen Deraand with Teflon lined closure

Cool, 4°C ASAP

Permlsslble Sample Type

G or C

Reference

Organics -Extractable

Organics -Purgeable (VOA)

8-oz. wldeegouth glass Cool, A°C with Teflon liner

A - o z . ( 120 «!!> wKoworH:!:; C o o l , A 'C g l a s s w i t h Te.Oc.'F, i l t ne r

ASAP

ASAP

G or C

G or C

Otlier inorganic Coapounds -Including Cyanide

500-al |io .yethylene with polyethylene cBosure or 8-oz. wOde-Qouth glass with Teflon lined closure

Cool. k°C ASAP G or C

Abbreviations: C - Grab C " Coraposflte ASAP " As Soon As Possible NS - Not Specified

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Footnotes: AND PERMISSIBLE SAMPLE TYPES

1. Use Indicated container for single parameter requests, l/2-gallon polyethylene container for multiple paraiaeter requests except those Including BOD, or l-gallon polyethylene container for aultlple parameter request which include BOD.

2. Must be preserved in the field at tiae of collection.

3. Use ascorbic acid only if the saaple contains residual chlorine. Test a drop of sample with potasRlma Iodide-starch test paper; a blue color Indicates need for treatment. Add ascorbic acid, a few crystals at a tiae, until a drop of saaple produces no color on the Indicator paper. Then add an aildit lonal 0.6 g of ascorbic acid for each liter of saaple voluae.

4. May Include nitrogen series (aaaonla, total Kjeldahl nitrogen, nitrate-nitrite), total phosphorus, chemical oxygen demand and total organic carbon.

5. Saaples aust be extracted within seven days and extract aust be analyzed within 40 days.

6. Collect the saaple in a A oz. soil VOA container which has been pre-preserved with four drops of 10 percent sodiua thiosulfate solution. Gently aix the saaple and transfer to a AO al VOA vial that li;is been pre-preserved with four drops concentrated HCl, cool to A'C.

7. See Organic Coapounds - Extractable (page 4 of 8 ) . The Analytical Support Branch should be consulted for any special organic coapound analyses in order to check on special preservation requirements and or extra sample voluae.

References;

A. US-EPA, Region IV, Environaental Services Division, "Analytical Support Branch, Operations and (^lallty Control Manual," June 1, 1985 or latest version.

B. EPA Method 1310, Extraction Procedures, "SW 846," US-EPA, Office of Solid Wastes. Washington, DC, l ' iH2.

C. 40 CFR Part 136, Federal Register, Vol. 49, No. 209, October 26, I9H4. cS.

D. US-F.PA, Region IV, Environmental Services Division, "Ecological Support Brancli, Standard (IperatliiK Procedures Q ^ Manual,' latest version. \ .

K. KPA Interim Method 450.1, "Total Organic Hal Ide " IIS-KPA, OKI). KHSI., Physical ami Chemical Hetlii Hramli. 'nclnnati, Ohio, Novemlier 19110.

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