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F I N A L

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.

5 Loveton Circle Sparks, Maryland 211.52

10785384

December 1990

EA Project 11653.02

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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.

5 Loveton Circle Sparks. Maryland 21152

December 1990

EA Project 11653.02

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 I.A 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 Mamager Responsibilities

2.2 Contractor Laboratory Organization

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 Organics 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 Seunpling

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 and 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

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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 Saraples

9.2 Other Internal Quality Control Checks

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

9.3 Field Blank Quality Control Sanples

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 Performemce 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 Inimediate 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 and Filing

13.5 Corrective Actions Reports to Mamagement

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 Svamp 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 Swaunp.

2-1 Project orgamization.

2-2 Laboratory organization.

5-2 Chain-of-custody form.

5-3 Laboratory log.

8-1 Quality assurance summary form.

12-1 Example of am 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 saunple 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 Sununary of saunples, amalytical procedures, holding time, amd containers for Stage I soil/sediment contauninant 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 saunples, analytical procedures, holding time, amd containers for Stage II soil/sediment contaminamt characterization.

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

amd containers for Stage II bioaccessible contaminant.

6-1 DFTPP key ions amd abundance criteria.

6-2 BFB key ions and abundamce 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 riverbottom 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 tvo chemical processing facilities. The LeMoyne Plant produces industrial chemicals and 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 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, Maryland) 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 understamding of current site conditions at Cold Creek Swamp to be able to develop and scope the strategy for data collection for this supplemental RI/FS.

Project Plams

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 and analysis, health and safety, quality assurance/ quality control, contaunination and 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 Plan/Sampling and Analysis Plam.

Work Plan/Sampling and Analysis Plan (WP/SAP) Site Health and Safety Plan (SHSP) Quality Assuramce Project Plam

The Work Plsm/Sampling and Analysis Plan describes objectives of the RI/FS; data quality objectives, data collection rationale; number and location of samples and amalyses; field sampling procedures, contamination and risk assessment approach; and RI/FS report development. Potential hazards, levels of protection, and other considerations affecting the health amd 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 swaunp, including key wetland plants amd animals, and endangered or threatened species.

Delineating vetland boundaries and the extent of upland in the Cold Creek Svamp.

Characterizing the nature and extent of contaunination present in svaunp soil, sediment, surface vater, and biota, including screening representative samples for Target Compound List analytes amd thiocarbamates and qusmtifying mercury speciation both at depth and in biotically active zones.

Characterizing contaunination upstreaun, dovnstream, and vithin Cold Creek Svamp, and the interaction of the surface vater system vith the ground-vater 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 amd verifying quamtitative risks to human health and the environment due to site-related contauninants by modeling exposure amd toxicity and measuring tissue concentration in key receptors.

Evaluating potential remedial alternatives.

Approach

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

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

Data generated during Stages I and II vill be used to develop a preliminary ecological risk assessment and to conduct ecological risk modeling. Results of ecological risk modeling vill be used to select representative numbers and types of biological species to be sampled and analyzed during Stage III. This staged approach vill 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, vill be selected for Stage III saunpling.

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

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

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

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

1. PROJECT DESCRIPTION

Cold Creek Svamp is a freshvater cypress svamp that drains into the Mobile River near Axis, Alabama, 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 Compamy (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 contamination on the biological community in Cold Creek Swamp. 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 amd extent of contamination in Cold Creek Swaunp and to further examine potential impacts of swamp contamination on the biological conununity 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 Swamp.

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 hardvood svamp encompassing several hundred acres along the Mobile river. The upper portion of the svaunp originates on property formerly ovned by the Stauffer Chemical Company. The former Stauffer property Includes tvo chemical processing facilities. The Lemoyne Plant produces industrial chemicals amd is currently ovned by Akzo Chemicals Inc. (Chicago, Illinois). The Cold Creek Plant manufactures agricultural chemicals and is ovned by ICI Americas Inc. (Wilmington, Delavare). Akzo and ICI have been designated by EPA as potentially responsible parties (PRPs) vith respect to environmental contamination 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 Svamp. On 16-17 August 1990, EA conducted a preliminary reconnaissance to examine site conditions. The site visit included intervievs vith key plant personnel, reviev of plant historical records, a site valk-through, and a site overflight.

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EA QAP-11653.01 Section No.: 1 Revision No.: 1 Date: November 30, 1990 Page: 2 of 10

Guif<tf Mexico:

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

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Rgure 1-2. Cow C r e ^ Sw«mp sita showtng •(J)«*nt St«uffw Ch«cnte«l F»««nt».

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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 Svaunp is mercury. Potential impacts from mercury exposure are primarily to the biological community in and around the svamp. Previous studies have not characterized potential ecological impacts of swamp contamination to an extent that satisfactorily allays the concerns of various reviev agencies, including the EPA, USFWS, and NOAA.

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

To ensure the quality of the field and 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 amd Specifications for Preparing Quality Assurance 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 reviev. All field sampling and analytical chemical activities or this project vill be performed in accordance with current EPA guidance and with provisions of EPA Region IV Engineering Support Branch Standard operating Procedures and Quality Assurance Mamual (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 pollutant-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 am informed risk mamagement alternatives amalysis for remedial actions to be evaluated in the Feasibility Study (FS).

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

1.3 SITE DESCRIPTION

Cold Creek Swamp is located in the northeast section of Mobile County, Alabama, 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 swaunp lamd and other wetlands (Figure 1-3).

The Mobile River in Mobile County is an importamt 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 Svamp are the chemical production plants to the west amd south and a coal fired electrical power generating plant to the north (Alabama Pover 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 contaminamts associated with the Cold Creek/LeMoyne site, much of the sampling effort to date has focused on contaunination 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 analyses amd depth-composite cores taken in 1986 for the original RI/FS (ERT 1988). While composite samples do not provide sufficient information to document the vertical extent of contamination, existing saunple 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, amd toxicity for the initial RI/FS were carbon tetrachloride, carbon disulfide, cyamide, mercury, thiocarbamates, orgamophosphates, chloride, and thiocyanate. Of these, only mercury was detected at significant levels in Cold Creek Swamp.

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Thiocarbamates vere present at lov levels. Inorganics (chromium, copper, lead, and zinc) were observed in some soil saunples 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 and biota. While there is reason to believe that sulfide in swamp sediment reduces mercury bioavailability, samples 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 humam health associated with contamination in Cold Creek Svamp are for potential toxicity to ecological receptors and for potential food-veb-based exposure to humans. Because of these concerns amd based on existing data, the folloving exposure pathvays are of potential ecological or human health concern:

Ecological Pathvays

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

exposure to contaminated upland soils

exposure to contaminated aquatic sediments

food-veb exposure

Human Health Pathvays

food-veb exposure

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

exposure to contauninated aquatic sediments

Figure 1-4 illustrates a conceptual model of potential exposure pathvays in Cold Creek Svamp.

Primary Sources

Primary ReSease Mechanisms

Secondary Sources

Secondary Releasa Mechanisms

Contaminated Medum

aquatic sediments

erosion and

sediment

transport

aquatic

sediment

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dissolution and water

transport

terrestrial

soils B>-

erosion

and soil

transport

/

terrestrial

soil

surface

wotar

exposure route

direct contact

direct ingestion

food web

direct contoct

direct

ingestion

food

web

direct

contact

ingestion

human

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terrestrial

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aquatic

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1.5 DURATION OF PROJECT

Table 1-1 shovs the performance schedule and schedule of deliverables for project activities associated vith the Cold Creek Svamp Operable Unit Supplemental RI/FS.

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

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

Tvo reviev conferences vith all regulatory agencies have been scheduled. The first reviev conference vill be held approximately 6 veeks after submission of the draft RI report. The second reviev conference vill be held approximately 9 veeks after submission of the draft FS report. Both reviev conferences vill 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 reviev the Work Plans. This meeting should be held at EPA Region IV headquarters in Atlanta.


TABLE 1-1 PROJECT SCHEDULE

1 Oct 90 Submit Work Plans to EPA 26 Oct 90 Receive EPA reviev comments 6 Nov 90 EPA reviev 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 reviev 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 Reviev Comments from EPA 25 Mar 92 RI Reviev Conference (vith regulators) at

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

Region IV 16 Sep 92 Final FS to EPA

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

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

U U S :7 EA QAP-11653.01 Section No.: 2 Revision No.: 1 Date: November 30, 1990 Page: 1 of 8

PROJECT MANAGEMENT AND RESPONSIBILITIES

2.1 GENERAL

Management of this project vill require flexibility in the organization of a teara of scientific and engineering personnel and technical resources in order to conduct an RI/FS vhich examines the chemical contaunination at the Cold Creek Svamp. The field investigation vill be implemented in three stages and vill employ pre-approved field procedures, sampling techniques, and analytical methods to accomplish data collection objectives. Effective prograun organization vill accommodate these requirements for both flexibility amd consistency vhile maintaining a manageable degree of control over all activities.

Figure 2-1 illustrates the proposed orgamization for accomplishing this effort. The core of the technical organization is the Project Manager and the assigned Project Teaun. Additional individuals cam be made available if varranted.

2.1.1 Project Director Responsibilities

The Project Director is responsible for oversight of all contractual activities and provides direction and guidance to the Project Mamager in contractual matters. The Project Director is responsible for revieving and approving any and all contractual submittals, including negotiation of contractual rates, submission of fee proposals, negotiation of fee proposals and project scopes, selection of specialty subcontractors (vith 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 vith contractual requirements amd in accordance vith the corporate Hazardous Waste Prograun 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 Mamager serves as the primary technical point of contact vith Akzo and ICI and coordinates management of project subtasks. Specific responsibilities of the Project Manager include (1) management of all technical activities; (2) preparation of vork flov diagrams, schedules, labor allocations, and survey plans; (3) management of all funds for labor and materials procurement; (4) reviev and administration of all vork-order changes; (5) successful accomplishment of all contractual obligations, including costs, schedules, and technical performance; (6) mamagement of the Project Teaun tovard a unified, productive project accomplishment; (7) format and quality control of all documents and data reports; and (8) technical leadership.

AZKO CHEMICALS INC. ICI AMERICAS INC.

HEALTH & SAFETY

PROJECT DIRECTOR

PROJECT MANAGER

QUALITY ASSURANCE

FIELD ACTIVITIES MANAGER

SITE MANAGER

1 1

ECOLOGICAL RISK EVALUATION

1 FEASIBILITY

STUDY

1 CHEMICAL ANALYSIS

Figure 2-1. Project organization.

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6 ^ U J L) :;• EA QAP-11653.01 Section No.: 2 Revision No.: 1 Date: November 30, 1990 Page: 3 of 8

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 Consultamt'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 and sampling prograuns; engineering design; and construction quality control. The QA Officer is responsible for development and 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 and 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 amd 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 saunpling teams amd assurance of quality data collection. The Field Activities Manager is responsible for implementation of the provisions of the Work Plan/Sampling and Analysis Plam, the Quality Assurance Project Plan, and the Site Health and Safety Plan during data collection activities, and for coordination with the analytical chemistry laboratory for sample handling and transport.

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 performamce of specified analyses for projects at prescribed levels of quality; custody control, amd traceability responsibility from saunple delivery to results reported to clients; amd responsibility for implementing and maintaining quality control procedures and documentation for those samples amalyzed according to approved, written instructions and methods. The functional responsibilities for each position shown in Figure 2-2 are described belov.

2.2.1 Vice President

1. Ensures laboratory data quality.

2. Maintains laboratory staffing.

EA LABORATORIES VICE PRESIDENT

PURCHASMQ SPECIALIST

QA/CC MANAQER

L M 8 SVSTEM MANAQER

AOMMISTRATIVE MANAGER

OC SPECIALIST

SENIOR CHEMIST

AOMMIVmATIve ASSISTANT

OnOANtCS MANAQER

REPORTS SUPERVISOR

NOROANICS MANAOBR

TECHNICAL SUPPORl SPECIALIST

CHnOMATOQRAPHY SUPERVISOR

EXTRACTIONS SUPERVISOR

SPECIAL PROJECTS SUPPORT MANAQER

TECHNICAL SUPPORT SPECIAUST

A C T M a W t T CHEMISTRY SUPCRVI80F

METALS SUPERVISOR

MASS SPECTROMETRY SUPERVISOR

SAFETY & HEALTH COORDMATOR

Figure 2-2. Laboratory organization.

•AMPLE MANAGER OFFICER

1

QLASSWARE LAB SUPPORT

13 o 50 w cn W (U

oq r t ID (D • • ••

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o < l-h ID

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3. Develops laboratory budget.

4. Ensures laboratory safety.

5. Approves laboratory equipment acquisition.

6. Promotes laboratory marketing and client interface.

7. Sets amalytical priorities.

2.2.2 Quality Assurance Manager

1. Selects, revievs, amd troubleshoots analytical methods.

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

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

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

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

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

7. Revievs quality control procedures and criteria for compliance vith 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 prograuns for all laboratory personnel on QA/QC issues, updates to regulatory or other quality matters.

2.2.3 Administrative Manager

1. Manages the analytical flov 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.


3. Maintains active contact vith outside clients and internal project managers vith regard to: supplying technical information, regulatory assistance in regard to analytical needs, and sample status updates; amsvering 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 and scheduling of client needs.

2.2.4 Data Manager

1. Responsible for the site preparation, and onsite configuration of hardvare and softvare 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 knovledge in overall computerization of laboratory functions, including data mamagement, scheduling, mamagement reports, amd financial reports.

2.2.5 Inorganics and Organics Managers

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

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

3. Responsible for data reviev 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 vork.

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

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

S -EA QAP-11653.01 Section No.: 2 Revision No.: 1 Date: November 30, Page: 7 of 8

0 0 6.-.'

1990

2.2.6 Supervisors

1. Participate in planning laboratory programs on the basis of specialized knovledge of problems and methods and 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 finamcial budgeting and planning.

3. Troubleshoot problems regarding analytical procedures and equipment performance.

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

5. Fully competent amd 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, and QA/QC requirements.

8. Provide advice to Laboratory Mamagers in budgetary and personnel matters.

2.2.7 Sample Management Officer

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

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

3. Responsible for sample 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 glassvare.

5. May assist in training amd supervising techniciams in analyses and quality control procedures for sample tracking.

6. Follovs all laboratory safety rules.

4 U u 6


2.3 ANALYTICAL LABORATORY

An analytical laboratory vill be selected for this project after EPA reviev of the Work Plan. The laboratory selected for this project must meet EPA CLP requirements amd vill be submitted for acceptance by EPA.

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

The laboratory Quality Assurance Officer vill be responsible for establishment of quality assurance program vithin the laboratory to provide consistency, accuracy and precision in the analysis of samples. The laboratory Quality Assuramce Officer vill also be responsible for internal laboratory data validation programs and quality assurance audits.

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

O 4 OGr


3. QUALITY ASSURANCE OBJECTIVES

3.1 DATA QUALITY/QUANTITY NEEDS

The folloving 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 Svamp Operable Unit. It should be noted that the number and 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 belov quamtitation limits to 690 mg/kg in saunples collected from shallov soil cores throughout Cold Creek Svamp. Other observed compounds included arsenic (5 mg/kg), chromium (130-180 mg/kg), lead (belov detection level to 31 mg/kg), nickel (32-56 mg/kg), zinc (171-561 mg/kg), and several thiocarbaunate pesticides (not detected to 1.8 mg/kg). Concentrations of all observed compounds vere vithin order of magnitude levels typical of natural soils (Table 3-1) vith the exception of mercury and the thiocarbamates. Previous data collection did not characterize contaminant concentrations at discrete vertical depths and did not differentiate betveen total and orgamic (methyl) mercury. The vertical distribution of contaminants is needed to identify vhether contamination is concentrated in the biologically active zone of svamp sediments or is distributed throughout the soil matrix. Differentiation of total and organic (methyl) mercury is needed to indicate hov much mercury is inorganic amd hov much is organic. Table 3-2 identifies sampling requirement*; for investigation activities for this supplemental RI/FS. Available data indicate that mercury vill be the primary contaminamt of concern in svamp soil/sediment. As such, Stage II sampling is designed to focus on refining mercury characterization. If additional contaminants of concern are identified during Stage I, Stage II vill be modified, as appropriate.

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

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

Concentration Average Average Concentration No. of Locations Range Concentration on Natural Soils^

Compound sampled (mg/kg) (mg/lcg) (mg/lcg)

VOC's 3 ND ** ND NA * ^ Semivolatiles 3 ND ND NA PCB's/Pesticides 3 ND ND NA

Netals Mercury 34 ND-690 54.7 .03 Arsenic 3 5-5 5 5 Beryllium 3 .31-.81 0.53 6 Ciiromium 3 120-180 150 100 Copper 3 14-35 27.7 30 Lead 3 ND-31 19 10 Nicliel 3 32-56 46.9 40 Zinc 3 171-561 348 50

Thiocarbamates EPTC (Eptam) 3 .1-1.0 .4 NA Butylate (Sutan) 3 ND-1.8 .7 NA Vernolate (Vernam) 3 ND-1.1 .4 NA Pebulate (Tlllara) 3 ND-.3 .1 NA Molinate (Ordram) 3 .1-.9 .5 NA Cycloate (Ro neet) 3 ND-1.8 .8 NA

Chloride 3 ND-50 33.3 NA

(a) = Reference: USEPA Office of Solid Uaste 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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7i) 4


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

Number of Compound Sample Locations

Stage I

TCL Volatile Orgamics 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 amalyzed for during Stages II and III may be modified pursuant to assessment of data results from previous stages.

•- .- U U O / EA QAP-11653.01 Section No.: 3 Revision No.: 1 Date: November 30, 1990 Page: 4 of 19

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

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

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

Section 121 (d) of CERCLA, as amended by the Superfund Amendments and Reauthorization Act (SARA), requires that remedial actions at Superfund sites comply vith requirements or standards under Federal or State environmental lavs that are "applicable" or "relevant and appropriate" to the hazardous substamces, pollutants, or contaminamts at a site or the circumstamces 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, pollutant, contauninant, remedial action, location, or other circumstances at a hazardous vaste site. Relevant amd appropriate requirements, vhile not applicable, address problems or situations sufficiently similar to those encountered at a hazardous vaste site so that their use is veil 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; hovever, certain technical documents may be revieved to assess potential exposure (including a March 1990 publication by NOAA entitled "The Potential for Biological Effects of Sediment-Sorbed Contaminamts Tests in the National Status amd Trends Program," amd documents related to AET, EP, and sediment toxicity testing).

3.1.1.2 Critical Samples for Soil/Sediment Analysis

Critical samples are those samples for vhich scaled data must be obtained to satisfy the objectives of the sampling and amalysis task. They are as follovs:

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 Blamk—to be collected one per site per saunpling event to demonstrate field sampling decontamination procedure effectiveness. Rinsate blanks vill not be collected on dedicated sarapling devices.

-- 4 Uuoa 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 saraples vill be collected from upland locations beyond the limits of the svamp and vill 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 sampling vas conducted in the vicinity of Cold Creek Svamp as a component of the original RI/FS. Tvo surface vater samples vere collected from unnamed tributaries t o 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 vater saunples did not exhibit concentrations of priority pollutants above detection levels, vith the exception of mercury (0.0002 mg/L) and zinc (0.31 mg/L) in one of the tvo samples.

Surface vater data collection for this project is proposed to characterize surface vater quality vithin the Cold Creek Svamp, vithin vaters discharging to Cold Creek Svamp, at the mouth of Cold Creek and vithin the Mobile River, upstreaun and dovnstream of the svaunp discharge location. The objectives of surface vater data collection are to characterize contaraination upstreaun, dovnstream, and vithin the Cold Creek Svamp; and to characterize contauninamt tramsport via surface vater and the potential for ground-vater contamination through surface vater aquifer recharge. Table 3-3 shovs the proposed sampling program for investigation activities for this supplemental RI/FS.

Since surface vater quality data vill be used in ecological modeling and risk assessment, and since the site is an operable unit for tvo NPL sites, EPA Level III analytical data levels vill be utilized.

3.1.2.1 ARARs for Surface Water Sampling

The Cold Creek/LeMoyne Superfund sites RI/FS concluded that surface vater exposure at the Cold Creek and LeMoyne plamts does not constitute a human health exposure pathvay, based upon site use amd limited site access. Cold Creek Svamp, hovever, represents an excellent habitat for vildlife, and potential receptors are the native plant and animal species. Water


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

Compound Number of Saraples

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

6 6 6 6 6 6 6

O ^ l! U


Quality Criteria (WQC) values established under the Federal Water Pollution Control Act, as amended by the Clean Water Act of 1977, amd the Water Quality Act of 1987, vill be probable ARARs governing surface vater quality.

3.1.2.2 Critical Samples for Surface Water Analyses

The samples that vill 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 vater sampling locations are intended for use as background vater quality assessment. Background samples vill be taken upstream of the project site along Cold Creek south and vest of the site, and along the Mobile River north of the site.

3.1.3 Biological Tissue Sampling Data Requirements

Biological tissue sampling vas conducted in Cold Creek Svamp in 1986 (1988 RI Report by CDM) and in 1988 (1989 Biota Study by BCM). Five species-composite samples of finfish vere analyzed for vhole-body mercury concentrations in 1986, and species-specific analyses including invertebrates vere conducted in 1988. Some samples, including one taken above Cold Creek Svamp at a reservoir outfall in the headvaters of Cold Creek, carried mercury body burdens above those that vould be expected in uncontaminated areas.

Samples to support quantitative risk estimates vill be based on mercury food veb amd bioaccumulation model calculations. These models vill incorporate information on resources present in the svamp, trophodynaunics of the svamp ecosystem, amd key receptor species chosen on the basis of scientific and regfulatory requirements. Criteria to support selection of key receptors vill include (1) potential risk of contaminamt uptake and associated population effects, (2) unique value or regulatory status, and (3) potential for community or ecosystem-level effects. Samples vill 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 svaunp populations, and maximizes the value of each saunple by providing a mechanistic basis for understanding mercury dynaunics in the ecosystem.

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

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

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support quantitative estimation of risks to human health and ecological resources. Saraples to characterize temporal trends vill reproduce as closely as possible the sampling that vas conducted in 1986. Reports, notes, and intervievs vith and direction by personnel present at the past sampling vill be employed to locate nev samples in the vicinity of the old. Collection, analysis, and reporting methods vill be similar, maximizing the comparative value of these saraples.

3.1.3.1 ARARs for Tissue Samples

Consistent vith EPA guidance (EPA 1989b), criteria vill be identified vhich serve as potential ARARs. In general, tissue ARARs are limited and vary among states and regions. For Cold Creek Svamp, 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 vill be assessed for each potential ARAR, based on study findings relating to human amd environmental exposure, nature and extent of contaunination, amd contauninamts potentially present.

3.1.3.2 Critical Saunples for Tissue

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

3.2 QA OBJECTIVES FOR MEASUREMENT DATA

This section presents the QA objectives for the chemical data in terms of precision, accuracy, completeness, representativeness, amd 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 and analysis. The sampling precision is assessed by collecting field duplicates. The analytical precision is determined by preparing and analyzing duplicate subsamples. Precision cam be expressed in several different vays, each of vhich has its uses; for multiple measurements these include the standard deviation, the relative standard deviation, and the range, and for duplicates the relative percent difference.

..) 1-


TABLE 3-4 DATA QUALITY OBJECTIVES

Parauneter

Volatile Organics

Matrix'

Semivolatile Organics

Halogenated hydrocarbon pesticides

Thiocarbamate pesticides

Methylmercury

Metals

Mercury

Inorganics

Chloride

Sulfide

Physical Total dissolved solids (TDS) pH eH

(1) Matrix codes: (2) Method codes:

W = I =

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

vater; S = soil; ICP; F = furnace

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 (X)

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

T = tissue. ; V = CO Id vapor; G

Completeness (Z)

90 90

90 90

90

90 90

90

95 95 95 95 95 95 95

95 95 .95 95

95 95 95

= GC;

(3)

M = GC/MS; R = infrared; G = gravimetric; E ^ electrometric; IC = ion chromatography; T = titrimetric Limits are to be determined during the method performance study.

« ; ,; \ 'I I " ' I


3.2.2 Accuracy

Accuracy is the degree of agreement of a measured value vith 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 saunpling process, field amd laboratory contaunination, sample preservation amd handling, sample matrix, sample preparation methods, and calibration and amalysis procedures. Sampling accuracy is assessed by evaluating the results of field/trip blanks, amalytical accuracy through the use of calibration and method blamks, calibration verification saunples, laboratory control samples, amd matrix spikes.

3.2.3 Representativeness

Data representativeness is the degree to vhich data accurately and precisely represent a characteristic of a population, parauneter variations at a sampling point, or an environmental condition. Representativeness is a quantitative parameter that is most concerned vith the proper design of the sampling program. The sampling program has been designed so that the samples collected are as representative as possible of the medium being sampled and that a sufficient number of samples vill be collected. Representativeness is addressed by the description of the saunpling techniques amd the rationale used to select the saunpling 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 saunple loss through accidents or inadvertence. Accidents during sample transport or lab activities vhich cause the loss of the original sample vill result in irreparable loss of data. Collection of sufficient sample allovs reanalysis in the event of an accident involving a saunple aliquot. The assignment of a set of continuous laboratory numbers to a batch of samples vhich have undergone chain-of-custody inspection makes it more difficult for the amalyst to overlook samples vhen setting up a batch of samples for analysis. The continuous laboratory numbers also make it easy during the data compilation stage to pick out the samples vhich 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 vith vhich one data set can be compared to another. It cannot be described in quamtitative terms, but must be considered in designing the sampling plams, analytical methodology, quality control, and data reporting. The use of standard sampling techniques and validated, EPA-approved analytical methods

I ' f ' i ' ' ' t .1

J H U U / -


assures that the parameters being measured are comparable vith 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 meam percent recovery plus and minus the three standard deviation (99X) limits for the amalysis of laboratory control samples (see Section 12). The precision is the mean moving range betveen successive measurements of the laboratory control samples.

3.3 ANALYTICAL DETECTION LIMITS

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

3 4 Ou


TABLE 3-5 METHOD DETECTION LIMIT

INORGANIC TARGET ANALYTE LIST (TAL)

Contract Required ( 1 2"i 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 Cyanide 10

(1) Subject to the restrictions specified in the first page of Part G, Section IV of Exhibit D (Alternate Methods - Catastrophic Failure) any amalytical 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 folloving circumstamce;

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 belov:

•j H U 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

* (JRDLs are not available for tissue. Detection limits appropriate to the level of resolution necessary for the study vill be applied to tissue samples. For methyl mercury, detection limits betveen 10 amd 100 ppb vill provide appropriate resolution.

L; U /

TABLE 3-5 (Cont.)


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

Water Quantitation Limits**

Lov Soil/Sediraent*

1. 2. 3. 4. 5.

6. 7. 8. 9. 10.

11. 12. 13. 14. 15.

16. 17. 18. 19. 20.

21. 22. 23. 24. 25.

26. 27. 28. 29.

Volatiles

Chloromethane Bromomethane Vinyl Chloride Chloroethane Methylene Chloride

Acetone Carbon Disulfide 1,1-Dichloroethene 1,1-Dichloroethane 1,2-Dichloroethene (total)

Chloroform 1,2-Dichloroethane 2-Butanone 1,1,1-Trichloriethane Carbon Tetrachloride

Vinyl Acetate Bromodichloromethane 1,2-Dichloropropane cis-1,3-Dichloropropene Trichloroethene

Dibromochloromethane 1,1,2-Trichloroethane Benzene trams-1,3-Dichloropropene Bromoform

4-Methyl-2-pentanone 2-Hexanone Tetrachloroethene Toluene

CAS Number

74-87-3 74-83-9 75-01-4 75-00-3 75-09-2

67-64-1 75-15-0 75-35-4 75-34-3 540-59-0

67-66-3 107-06-2 78-93-3 71-55-6 56-23-5

108-05-4 75-27-4 78-87-5

10061-01-5 79-01-6

124-48-1 79-00-5 71-43-2

10061-02-6 75-25-2

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

pg/L

10 10 10 10 5

10 5 5 5 5

5 5 10 5 5

10 5 5 5 5

5 5 5 5 5

10 10 5 5

Ug/Kg

10 10 10 10 5

10 5 5 5 5

5 5 10 5 5

10 5 5 5 5

5 5 5 5 5

10 10 5 5

(continued)

•7 • . J l-l- 0 0 7 ..>


TABLE 3-5 (Cont.)

30. 31. 32. 33. 34.

Volatiles

1,1,2,2-Tetrachloroethane Chlorobenzene Ethyl Benzene Styrene Xylenes (Total)

CAS Number

79-34-5 108-90-7 100-41-4 100-42-5

1330-20-7

Quantitation Water Ug/L

5 5 5 5 5

Lov Soi Limits** 1/Sediment"^ Ug/Kg

5 5 5 5 5

**

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

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

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

' i ' 0 U : :'


TABLE 3-5 (Cont.)

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

Quantitation Limits** . Water Lov Soil/Sediment"

Semivolatiles CAS Nuraber ug/L ug/Kg

35. Phenol 108-95-2 10 330 36. bis(2-Chlorethyl) ether 111-44-4 10 330 37. 2-Chlorophenol 95-57-8 10 330 38. 1,3-Dichlorobenzene 541-73-1 10 330 39. 1,4-Dichlorobenzene 106-46-7 10 330

40. Benzyl alcohol 100-51-6 10 330 41. 1,2-Dichlorobenzene 95-50-1 10 330 42. 2-Methylphenol 95-48-7 10 330 43. bis(2-Chloroisopropyl)

ether 108-60-1 10 330 44. 4-Methylphenol 106-44-5 10 330

45. N-Nitroso-di-n-dipropylamine 621-64-7 10 330

46. Hexachloroethane 67-72-1 10 330 47. Nitrobenzene 98-95-3 10 330 48. Isophorone 78-59-1 10 330 49. 2-Nitrophenol 88-75-5 10 330

50. 2,4-Dimethylphenol 105-67-9 10 330 51. Benzoic acid 65-85-0 50 1600 52. bis(2-Chloroethoxy)

methane 111-91-1 10 330 53. 2,4-Dichlorophenol 120-83-2 10 330 54. 1,2,4-Trichlorobenzene 120-82-1 10 330

55. Napthalene 91-20-3 10 330 56. 4-Chloroaniline 106-47-8 10 330 57. Hexachlorobutadiene 87-68-3 10 330 58. 4-Chloro-3-methylphenol

(para-chloro-meta-cresol) 59-50-7 10 330 59. 2-Methylnapthalene 91-57-6 10 330

60. Hexachlorocyclopentadiene 77-47-4 10 330 61. 2,4,6-Trichlorophenol 88-06-2 10 330 62. 2,4,5-Trichlorophenol 95-95-4 50 1600 63. 2-Chloronaphthalene 91-58-7 10 330 64. 2-Nitroaniline 88-74-4 50 1600

.J


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.

Semivolatiles

Dimethylphthalate Acenaphthylene 2,6-Dini trotoluene 3-Nitroaniline Acenaphthene 2,4-Dinitrophenol 4-Nitrophenol Dlbenzofuram 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 Pentachlorophenol Phenanthrene Anthracene

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

Benzo(a)anthracene Chrysene bis(2-Ethylhexyl)phthalate Di-n-octylphthalate 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** u 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

Lov Soil/Sediment Ug/Kg

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

5 f


u ••:.

TABLE 3-5 (Cont.)

95. Benzo(k)fluoranthene 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 Quamtitation Limits (CRQL) for Semivolatile TCL Compounds are 6() times the individual Lov Soil/Sediment CRQL.

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

** Quantitation limits listed for soil/sediment are based on vet veight. The quamtitation limits calculated by the laboratory for soil/sediment, calculated on dry veight basis as required by the contract, vill be higher.

7 • ' i J u u

TABLE 3-5 (Cont.)


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

Pesticides/PCB's 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

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

Quantitation Limits** Water Lov Soil/Sedimenl^

100. 101. 102. 103. 104.

105. 106. 107. 108. 109.

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

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

110. Endrin 111. Endosulfan II 112. 4,4'-DDD 113. Endosulfan sulfate 114. 4,4'-DDT

115. Methoxychlor 116. Endrin ketone 117. alpha-Chlordane 118. gamma-Chlordame 119. Toxaphene

120. Aroclor-1016 121. Aroclor-1221 122. Aroclor-1232 123. Aroclor-1242 124. Aroclor-1248

125. Aroclor-1254 126. Aroclor-1260

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

.0

.0 80. 16. 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 Lov Soil/Sediment CRQL.

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

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

< , I " : I • " ' .

"••' f \J U 0


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 am NPL-listed RI/FS. A detailed discussion of the number and location of samples; saunpling equipment and procedures; sample containers, preservation, amd holding time; amd decontamination and vaste handling procedures for soil borings, shallov soil samples, surficial soil/sediment saraples, suqface vater samples, and biological tissue saunples during the three stage field sampling effort for this project is presented in Chapter 5 of the Work Plan/Sampling and Analysis Plan (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

Total Number of Contains rs

4 oz wid* BOUth glass jac with Teflon liner

Conta iners

42<^'

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

Nuaber of Nuaber Field . Saaple of Dupli- Field Trip Total Analytical

Pa raaete r Locations Saaples catea Blanks Blanks Saaples Procedures Preservation Holding Tiae

Volatile 13 18 1 1 1 21 CLP Hold 9 4 C 14 days Organics (2/88 |

Seaivolatile- 13 18 1 1 0 20 CLP Hold 9 4 C 7 days extraction 8 oz wide-aouth 20 Organics (2/88) 40daysextract glassjarwith

Teflon 1ine r

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

Teflon 1ine r

Metals 16 21 1 1 0 24 CLP Hold g 4 C (£) 8 oz wide-mouth 24 (TAL) (7/88) glass jar with

Teflon 1ine r

Methyl 13 18 1 1 0 20 (e) Hold # 4 0 7 days extraction 8 oz wida-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 wide-mouth 20 Carbaaate 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 wide-aouth 20 glass jar with Teflon 1ine r

(a) Trip blanks taken for volatile organics analysis only. (b) All aethods are EPA SW-S46 unless otherwise noted. (c) No cheaical preservatives added to soils. (d) Froa tiae of saaple collection. (e) Method for aethyl aercury analysis is described in the QAPP. (f) Holding tiae foe all aetals is 6 aonths, with the exception of aercury whose holding tiae is 28 days. ' ^ - ' (g) Two containers per saaple. (h) See Table 7-1 . r-

c

TABLE 4-2 SUMHARY OF SAMPLES, ANALYTICAL PROCEDURES, HOLDINO TIME, AMD COMTAINERS FOH STAGE I SOIL/SEDIMENT CONTAMINANT CHARACTERIZATION

Muaber of Nuaber Piled , . .^^. Total Saaple of Dupli- Field Trip' ' Total Analytical' Nuaber of

Paraaeter Locat ion« Saaples catea Blanka Blanks Saaplea Procedures Preservation Holding Tiae Containers Containers

Methyl aercury 3 30 2 1 0 33 (e) Hold 9 4 C 7 daya extraction S os 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 glass jar with Teflon liner

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

Teflon liner

(a) Trip blanks taken for volatile organics analysis only. (b) Unless otherwise noted, aethods will b* froa USEPA SW-S46. (c) No cheaical preservatives added to soils. (d) Proa tiae of saaple collection. (e) Method for aethyl aercury analysis is described in th* QAPP.

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oq rt (D ID

.. ..

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o < rtl rt>

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ID

n OJ O

>-' vo VO O

w n> < t - l .

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o 3

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.

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(-> l -> CTl I n l o

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1165301 Doc. 67

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

Pa raaeter

Total dissolved solids

Ha rdness

pH

Chlo rides

Sulfides

Total dissolved aercury

Total ae rcury

Methyl aercury

Volatile Organics

Seaivolatile Organics

Pesticides/PCBs

Metals (TAL)

Nuaber of Saaples and Fie Locations Dupli

d at<

Fie Bla

d Total Analytical ks Saaples Procedure

(a)

8 EPA 160.1

8 APHA 314A

8 9040

9250

9030

Prese rvation Holding Tiae (b)

Hold @ 4 C

Hold e 4 C HNO, to pH<2

None

None

Hold 0 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-

-H

-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 aonths

Analyze iaaediately

28 days

7 days

28 days

28 days

Containers

P, a

P, G

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 extract

5 days extract G 40 days extract

(d) P,

U-

(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 tiae for all aetals is 6 aonths, with the exception of aercury whose holding tiae is 28 days P a plastic G ' glass

C'Z

TABLE 4-4 SUMMARY OF SAMPLES, ANALYTICAL PROCEDURES, HOLDING TIHE, AMD COMTAINERS FOR STAGE II SOIL/SEDIMENT CONTAMINAMT CHARACTERIZATION

(b) Nuaber of Huabec Piled . . Ana- Total Saapl* of Dupli- Field Rinsate Trip Total lytical Nuaber of

Paraaeter Locations Saaples catas Blanks Blanks Blanks Saaples Procedures Preservation Holding Tiae Containers Containers

Total aercury 45 91 S 1 2 0 101 24S.2-CLP Hold 9 4 C 28 days 8 os wide-aouth 99 99 glass jar with

Teflon liner

Methyl aercury 12 36 2 1 2 0 41 (e) Hold 0 4 C 7 days extraction 8 oi wida-aouth 41 40 days extract glass jar with

Teflon liner

Sulfide 45 91 5 1 2 0 99 9030 Hold 0 4 0 7 days 8 os wide-aouth 99 glass jar with Teflon liner

pH 45 91 S 1 2 0 99 9045 Hon* Analya* 8 os wide-aouth 99 iaaediately glass jar with

Teflon liner

(a) Trip blanks taken for volatil* organics analysia only. (b) Analytical proc*dur*s Iwll b* in accordanc* with EPA SW-a4fi unl*ss oth*rwi8* not*d. (c) Mo cheaical preservativas add*d to soils. (d) Froa tia* of saapl* coll*ction. (*) Method for aethyl aercury analysis is d*scrib*d in th* QAPP.

•TJ O P) pi oq rt (B (D

Ol Z O

O < l-h (D

3 CT> c r

(D f-l

OJ o

I-* vo vO o

po t / l (D < i->-M H-O 3

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1' :•..',

o •-' > *\) 1 . J r ' : •

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

(b) Nuab*r of Nuabar Pllad , . Ana- Total Saapl* of Dupli- Pl*ld Rinsat* Trip' Total lytical Nuaber of

Paraaeter Locations Saaples cates Blanks Blanks Blanks Saaples Procedures Preservation Holding Tia* Containars Containers

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

Teflon liner

Total aercury 60 60 3 1 2 0 66 24S.2-CLP Hold 0 4 C 28 days 8 os wide-aouth 66 glass jar with Teflon liner

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

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

glass jar with Teflon liner

pH 60 60 3 1 2 0 66 9045 Non* Analys* 8 os wide-aouth 66 r*quir*d iaa*diat*ly glass jar with

Taflon lin*r

Eh 20 20 1 1 2 0 24 Non* Analys* 8 oz wid*-aouth 24 iaa*diat*ly glass jar with

Taflon liner

(a) Trip blanks taken for volatile organics analyals only. (b) Analytical procedures ara in accordance with EPA SW-846, unless otberwls* not*d. (c) No ch*aical pr*s*rvat1vas add*d to soils. (d) Proa tia* of saapl* coll*ction. (*) N*thod for a*thyl a*rcury analysis is d*8crib*d in th* QAPP.

•T3 O po pi pi ro

oq rt < (D ID t-i-•• •• W

M -

o ON Z 3 O

O < 2 rtl (B O

3 • ON cr ••

(D l-l

•-• UJ o

I-J vo vO o

c / i n ' - " ' (D > " r-rt O -T: • M. > O T l a 1

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.-.. . > - - • • - .

6 4 EA QAP-11653.01 Section No.: 5 Revision No.: 1 Date: November Page: 1 of 10

1

30,

Ub-

1990

• )

5. SAMPLE CUSTODY

5.1 FIELD SAMPLING OPERATIONS

5.1.1 Sample Bottle Preparation

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

5.1.2 Sampling

The samples are collected by trained, experienced teams vho vill be alerted to amy special considerations necessary to ensure collection of representative samples. After the samples are collected, they are split as necessary among containers and preservatives appropriate to the parameters to be determined. Each container is provided vith 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, and returned to the laboratory by the most expedient means to ensure that holding times vill be met. The chain-of-custody form is signed amd dated as necessary as the saunples pass from the collectors to those persons responsible for their transportation.

5.1.3 Sample Labeling

The importamce of saunple labeling camnot be overstated. Improperly or inadequately labeled samples are of little value in a monitoring program. Improperly labeled saunples lead to questions vith regard to location, project, saunpling station, date sampled, and saunpler. All of this information is essential for proper sample handling. The use of vater-proof ink vhen filling out the label is essential to prevent the loss of information during sample shipment.

The folloving information, at a minimum, is required on each saunple 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 vith clear tape. Pre-printed pressure-sensitive labels are available from the laboratory.

"7 0 oi;


TABLE 5-1 CLEANING PROCEDURES FOR SAMPLE CONTAINERS

Parameter Group Material Cleaning

Unpreserved inorganics

Nutrients

Pesticides

Metals

Cyanide

Sulfide

Volatile organics

Semivolatile organics

Plastic

Plastic

Glass

Plastic

Plastic

Plastic

40-mL glass

Amber glass

Detergent & hot vater vash Deionized vater rinse

Detergent & hot vater vash HCl soak Deionized vater rinse

Detergent & hot vater vash Acetone and deionized

vater rinse Dry at 400 C

Detergent & hot vater vash HNO3 soak Deionized vater rinse

Detergent & hot vater vash HCl soak Deionized vater rinse

Detergent & hot vater vash Deionized vater rinse

Detergent & hot vater vash Deionized vater rinse Methamol rinse Bake at 400 C

Detergent & hot vater vash Acetone and deionized

vater rinse Dry at 400 C Methanol rinse

J •-t uu

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 12ra/82

Rgure 5-1. Sample bottle label.

,(g)

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&

6

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j ^ B B ^ ^ I ^ EA Labora lo i l a i

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

fi (•• -'i

1 U ;•'

30, 1990

Failure to provide the requested information may result in vasted time and resources if it is necessary to discard saraples 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 and checking the sample integrity and the custody seal, logging samples into the laboratory system, and controlling the handling and storage of samples vhile 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 folloving:

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 vith samples (i.e., air bills, chain-of-custody records, etc.).

Verifying and recording agreement or nonagreement of information on saraple 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 papervork for sample amalyses on appropriate laboratory documents (including establishing case and sample files amd inventory sheets) as required for analysis or according to laboratory standard operating procedures.

Marking or labeling samples vith laboratory sample numbers as appropriate and cross-referencing laboratory numbers to client numbers and sample tag numbers as appropriate.

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

3 4 0 U 9 -' 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 folloved vhen samples are removed from and returned to storage.

Monitoring chain of custody of samples in the laboratory. Saunples are physical evidence and should be handled according to certain procedural safeguards. For the purposes of some types of legal proceedings, a shoving to the court that the laboratory is a secure area may be all that is required for the analyzed evidence to be admitted. Hovever, it is amticipated that in some cases, the court may require a shoving of the hand-to-hand custody of the saunples vhile they vere 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 folloving vays:

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

or It vas in your possession amd then you locked or sealed it up to prevent taunpering; or

- It is in a secure area.

• Assuring that sample tags are removed frora 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 vere disposed due to suspected contaraination.

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

• Returning shipping containers to the proper saunpling teams.

5.2.2 Sample Receipt amd 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, vhich is an analytical task order form. This form provides sample-specific information amd a listing of the parameters required on each sample, along vith 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 vater-tight plastic envelope and shipped vith the samples to the laboratory.

3 4

EA QAP-11653.01 Section No.: 5 Revision No.: 1 Date: November 30, Page: 7 of 10

0U9

1990

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 amd 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 nuraber is affixed to each saunple bottle. The custodiam then enters the sample and analysis information into the laboratory computer system. The original of the chain-of-custody form is given to the data management group, vith a copy to the laboratory operations manager.

5.2.3 Saraple Storage and 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 organics 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 shovn in the folloving table:

Refrigerator Type Location Sample Type

Walk-in Sample receiving area Organic extractables

Walk-in

Under-the-counter

Under-the-counter

Saunple receiving area

GC laboratory

GC/MS laboratory

Inorganics amd organics

Orgamic VOA

BNA extracts amd standards

Similarly, there are refrigerators designated for extracts and standards. Saunples that are required to be frozen are stored in a freezer. The sample storage areas are vithin the laboratory to vhich access is limited to laboratory chemists and controlled by doors vith 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 forvarded to the client so that any analytical problems can be addressed. The saraples are discarded at the end of 30 days.

NOTE: Do not obHtsral* anocs-c ros i out wllh a (Ingle I n * only.

1991 ANALYTICAL CUSTODY AND PRESERVATION Page No.

Job No.

Client Project Code or P.O. No. Matrix

Received

Dale Time

EA Sample NqsJ Start End

Locator Code

Aliquot Preservation {

A B C F G H 1 J P«H Ji § Olhei ' ^ . i

Yes No

• —

Logger's Initials

Billing Date

-

Figure 5-3. Laboratory log.

C J 13 o po CO ra

mm.®

:zjj.

to P oq rt ID ID

• • •• 0 3

2 O O rtl <

ID I - ' 3 o o-

rt> f- l

W O

I - ' vo vO O

fD < H -

u M -

o 3

(D O rt l - « .

O 3

2 2 O O . .. (-•

• .. Ln

> O > >\1 1

i -« t - ' ON

Ln O J

. O l - l

C"

3 4 EA QAP-11653.01 Section No.: 5 Revision No.: 1 Date: November 30, 1990 Page: 9 of 10

Specific tasks for saraple storage are the folloving:

Samples and extracts are stored in a secure area.

The secure area is designed to comply vith 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 saraple 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 vith the contract or until instructed othervise by the Project Manager.

The location of stored extracts is recorded.

VOA samples are stored separately from other samples.

Standards are not stored vith samples or sample extracts.

The sample storage area is described.

So that the laboratory raay satisfy sample chain-of-custody requirements, the folloving standard operating procedures for laboratocy/saunple security are implemented:

- Saunples 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 vhile 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

saraple preparation or analysis. - All transfers of saraples into and out of storage are

docuraented on an internal chain-of-custody record.

6 4

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

30,

V.J U ..' 1.)

1990

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 raoveraent of samples because the laboratory is secured and accessible only to chemists.

7 U 4 0U9:-J


CALIBRATION PROCEDURES AND FREQUENCY

6.1 CALIBRATION PROGRAM

Instruments and equipment used in the Contract Laboratory vill be controlled by a formal calibration program. The program verifies that equipment is of the proper type, range, accuracy, and precision to provide data compatible vith specified requirements. All instruments and equipment vhich raeasure a quantity, or vhose 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 prograun is the responsibility of the Laboratory Managers. Implementation is the responsibility of the supervisors and analysts, and the Quality Assurance Manager (QAM) monitors the procedures.

Tvo types of calibration are discussed in this section:

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

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

6.2 CALIBRATION STANDARDS

Tvo types of reference standards vill be used for calibration:

Physical stamdards, such as veights for calibrating balances amd certified thermometers for calibrating vorking thermometers, refracators amd ovens, vhich 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.

•:) 4 0

EA QAP-11653.01 Section No.: 6 Revision No.: 1 Date: Noveraber 30, 1990 Page: 2 of 9

Whenever possible, physical reference standards have knovn 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 amd 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 vhich 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 amd 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, amd prior experience.

Equipment that camnot be calibrated or becomes inoperable during use are removed from service amd tagged to indicate it is out of calibration. Such equipment must be repaired and 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 folloving are the data generating laboratory instruments vhich require annual calibration.

a. Analytical Balance

The folloving are the data generating laboratory instruments vhich require semiannual calibration.

a. UV-VIS Spectrophotometer

The folloving are the data generating laboratory instruments vhich require calibration before each use.

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

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

v3 4 0 •; 0 ;


(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 vhich 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 standard 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 vhich the calibration procedure consists of the measurement of one or tvo standards. From the standard raeasurements 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

(vhen used for pH measurements) (3) Conductivity Meter (4) Dissolved Oxygen Meter (5) Turbidiraeter/Nepheloraeter

6.4 OPERATIONAL CALIBRATION

Operational calibration is generally perforraed as part of the amalytical procedure. Included may be the analysis of a method blank and the preparation of a standard response (standard calibration) curve. Folloving is a brief discussion of the amalysis of method blanks amd 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 vhich may be due to analyst error or the use of less-than-optiraura equipraent, reagents, solvents, or gases. The quality of materials, even though they are AR grade or better, may vary from one source to another. The amalyst must determine, through the use of reagent and/or solvent blamks, if materials are free from interfeiring

3 4 GiU.-^ EA QAP-11653.01 Section No.: 6 Revision No.: 1 Date: November 30, 1990 Page: 4 of 9

substances vhich could affect the analysis. Other steps in certifying the method include the determination of a method blank 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 vith the analysis. This method blank is prepared by folloving 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 vith the determination, steps must be taken to eliminate or reduce the interference to a level that vill permit the combination of solvents and reagents to be used. If the blank interference cannot be eliminated, the magnitude of the interference must be considered vhen calculating the concentration of specific constituents in the saunples analyzed.

A method blank should be determined vhenever an analysis is made. The number of blamks 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 betveen 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 can then be calculated using the resulting regression equation. The regression analysis also provides parameters vhich 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 amalyses cam be fitted to a parabolic curve. The folloving sections discuss specific details of linear and parabolic regression amd their uses.

6.4.3.1 Linear Regression

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

y = a + bx

3 4 U : U EA QAP-11653.01 Section No.: 6 Revision No.: 1 Date: Noveraber 30, 1990 Page: 5 of 9

vhere

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

After the regression equation has been coraputed, 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 ramge of the standards, caution is exercised vhen saraple responses are greater than that of the highest standard. No sample concentration is calculated for final data vhen the sample response is more tham 1.2 times the response of the highest standard. When the sample response is outside this ramge, 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 parauneter vhich is a measure of hov veil 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 amalysis, the correlation coefficient is influenced by tvo factors: (1) hov linear the data are, amd (2) hov much scatter there is among replicate measurements. For most laboratory analyses, it is possible to obtain 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) vithout consulting the laboratory manager or quality assurance officer.

6.4.3.2 Parabolic Regression

Although curvilinear responses cam indicate problems in analyses vhich are expected to give linear responses, there are some amalyses vhich 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 = aQ + a^x + a2X

vhere

y = instrument response

X = aunount or concentration of the analyte a^, a., a2 = parabolic constants

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

3 4 IJ 'i 0 '


.1/2

I / •• U ' 1 1 ''

X = ^ 2 ^y-^0^ * ^i]

2-2

is obtained. (This equation represents only one root of the parabolic equation, corresponding to the leg of the parabola to vhich 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 unknovn.

6.5 TUNING AND GC/MS MASS CALIBRATION

Prior to initiating amy 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 decafluorotriphenylphosphine (DFTPP) or p-bromofluorobenzene (BFB). The ion abundance criteria for each calibration compound MUST be met before any saraples, blanks, or stamdards can be analyzed.

Decafluorotriphenylphosphine (DFTPP)

Each GC/MS systera used for the analysis of seraivolatile or pesticide compounds must be hardvare-tuned to meet the abundance criteria for a 50-ng injection of decafluorotriphenylphosphine (DFTPP), DFTPP may be amalyzed separately or as part of the calibration stamdard. The criteria must be demonstrated daily or for each 12-hour period, vhich-ever is more frequent. DFTPP must be injected to meet this criterion. Post-acquisition manipulation of ion abundance is NO'T 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 hardvare-tuned to meet the abiondance 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, vhichever 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).

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

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

70 less tham 2.0 percent of mass 69

127 40.0 - 60.0 percent of mass 198


198 base peak, 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 vhich 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.

3 4 EA QAP-11653.01 Section No.: 6 Revision No.: 1 Date: November 30, Page: 8 of 9

r

1990

TABLE 6-2 BFB KEY IONS AND ABUNDANCE CRITERIA

Mass Ion Abundance 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 peadc


174 greater tham 50.0 percent of the base peak

175 5.0 - 9.0 percent of mass 174

176 greater than 95.0 percent but less than

101.0 percent of mass 174

177 5.0 - 9.0 percent of mass 176

Note: Whenever the Laboratory takes corrective action vhich 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.

' ' ' r. , 'ii) 4 ij i


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

Definition: The 12-hour period for tuning and calibration criteria begins at the moment of injection of the DFTPP or BFB analysis that the laboratory submits as documentation of compliant 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 Bramch Standard Operating Procedures amd Quality Assuramce Manual (April 1, 1986).

^ I- U i U o


7. ANALYTICAL PROCEDURES

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

1. Five point initial calibration curve vith linearity and XRSD criteria. ZRSD criteria for continuing calibration. Retention time vindov criteria for GC methods.

2. Method blank criteria consistent vith U.S. EPA-CLP requirements if possible.

3. MS/MSD frequency amd acceptance criteria consistent vith U.S. EPA-CLP.

4. Method precision and accuracy established using a lov level standard analyzed four times according to the procedures in U.S.EPA SW 846.

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

6. Written procedure and data packages revieved and signed by the appropriate Laboratory Mamager. Copies of the prodecures and 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 veil as daily instrument calibrations.

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

ofal8<. ,> 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

Thiocarbamate 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)

o>

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










CLP W,S0 (10)

200 .7

2 0 0 . 7

206 .2

2 0 0 . 7

2 0 0 . 7

2 0 0 . 7

2 0 0 . 7

2 0 0 . 7

2 0 0 . 7

2 0 0 . 7

2 0 0 . 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 , S 0

W , S 0

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 )

C-Ni

-T-.

• ^ - '

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


Page 3 of 6

Parameter Method 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 1

• W,S0

W,S0

W SO T

W,S0

W,SO

U,SO

W,SO

W,SO

W,SO

W,SO

W,SO

leferen

(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



Atomic Absorption - Cold Vapor Atomic Abosrption - Cold Vapor Atomic Abosrption - Cold Vapor









Gv!

ofalb-Ttfp methods t ab le doc. 291 Revised: 16-Jan-91


Page 4 of 6

Parauneter Method Method Number Matrix Reference

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,S0

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 vater, ground vater, leachates, ocean vater, surface vater, and vastevater DW - Drinking vater SO - Soils, sludges, sediments, vastes T - Animal tissue, plant tissue

O-J

CD

ofal6-,vp 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 Wastevater, 16th edition. APHA, Washington, D.C.

2. Association of Official Analytical Chemists. 1984. Official Methods of Analysis, 14th edition. AOAC, Arlington, Virginia.

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.

O l

CD

ofal j 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/Chemical Hethods. 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 Wastevater 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.

ONi

CZ:

3


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

Stamdard 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 Wastevater, 17th edition. APHA, Washington, D.C.

7 -• f' -I -• -


8. DATA REDUCTION, VALIDATION, AND REPORTING

8.1 DATA COLLECTION

For inorganic and general organic analyses vhere 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 vorkbook specific for each parameter. All entries are made in ink. These data consist of instrumental responses (absorbances, percent transmittamces, etc.), standard and spike concentrations, sample numbers, amd amy other pertinent information. The vorkbooks are under the control of the group supervisor/mamager 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 standard solutions of the analyte. 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 analysis 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 amalyses, the calculations are performed according to equations given in the standard operating procedures for the method.

For chromatographic analyses, the unknown concentrations are determined using response factors vith 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'

vhere

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

3 4 0 '! "i 7


A. = area of the characteristic ion of the internal stamdard is

C. = aunount of the internal 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 am 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) = (AgC^^)/(A^g)(RF)

vhere

A = area of the characteristic ion for the target compound

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

C. s 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^CgV^)/(AgVp

vhere

A. = peak size of target compound

A s peak size of matching standard

V. = initial volume of sample extracted (mL)

C = concentration of standard (ug/L)

Vr = final volume of extracted sample (raL)

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

8.3 REPORTING

After all analyses are completed, the data are collected frora suramary sheets, vorkbooks, or computer files by the laboratory report group and transferred to a draft report. The assembled data and the rav data are then examined for nonsense, computational, and tramscriptional errors.

3 4 G 'i "i 7i


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

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

After completion of the reviev of the data report for compliance vith all project requirements, the Laboratory Director for the Contract Laboratory shall sign off on the data report, and the report vill be forvarded to the project mamager.

8.4 DATA VALIDATION

Validation of the field data is the prime responsibility of the project manager vho addresses the folloving areas:

Proper chain-of-custody, sample hamdling, and decontamination procedures folloved

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 vith sample container labels amd chain-of-custody forms

Validation of the laboratory data is the prime responsibility of the laboratory supervisors/mamagers vho address the folloving areas:

Proper chain-of-custody and saunple hamdling procedures folloved

Paraunetric holding times met

Samples prepared and amalyzed according to specified methods

Instrumentation calibrated according to specified methods

Spike (surrogate or standard) recoveries vithin specified ranges

Blanks prepared and analyzed as required

Calculations performed correctly and verified

3


Transcription of rav and final data correct

• Detection limits determined correctly and vithin required limits

A reviever designated by the project manager examines the final laboratory data for consistency vith previous data and the hydrogeological characteristics of the site. Compliance vith study plam requireraents are also revieved. Final validation is the responsibility of the corporate quality assurance officer or designated quality revievers.

"- 4 •J LJ


BA I.ABOSATORISS

QUALTTT ASSURANCE SUMHART

FOR SV-846 ANALTSES Page 1 of 2

Project:

EA Laboratories Report No.

Revieved by;

Analysis: Volatiles

Hethod: U.S. EFA 8240

Date:

1. The 14-day holding tine requirenent froa saaple collection to analysis vas oet for all saaples.

Tes No

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

Tes No

3. Initial calibration criteria vere met for all saaplea: the RSD is <30Z for all CCC coapounds, and the RRF for SFCC coapounds is >0.300 (0.220 for broBoform).

Tes No

4. Continuing calibration criteria vere aet for all saaples: the response factor percent deviation froa the mean initial calibration response factor for all CCC coapounds vas <2SZ, and the RRF for SPCC compounds is >0.300 (0.220 for brooofora).

Tes No

5. Surrogate recovery llaits vere met for all saaples.

6. HS and HSD criteria vere met for all saoples.

Tes

Yes

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

Tes

No

No

No

(Revised Septeaber 1990)

Rgure 8-1. Quality Assurance Summary Form.

7 3 4 0 1 '7 '\


EA LABORATORIES

QOALITT ASSURANCE SUMMART


Project: Analysis: Volatiles

EA Uboratories Report No. Method: U.S. EPA 8240

Revieved by; Date:

8. Laboratory control saaple criteria vera oet for all saaples.

Tas Ne

Co^Mnts:


Rgure 8-1. Quality Assurance Summary Forni.

.<B>

O 4 fl •• O -;


EA LABORATORIES

QUALTTT ASSURAMCE SUMMART

FOR SV-fi46 ANALTSES Page 1 of 2

Project:

EA Laboratories Raport No.

Revieved by:

Analysis: Seaivolatlles

Hethod: U.S. EPA 8270

Date:

I. All saaples vere extracted vithin 7 days of saaple collection and analyzed vithin 40 days of extraction.

Tes No

2. The 12-hour tuning period for DPTFP vas aet for all saaples.

Tes No

3. Initial calibration criteria vere aet for all saaples: a five-point calibration curve vas run, the RSD is <30Z for all CCC coapounds, and the mean RRF for SPCC coapounds is >0.050.

Yes No

4. Continuing calibration criteria vere met for all saaples: the response factor percenc difference from the aean Initial calibration response factor for all CCC coapounds vas <2SZ, and the RRF for SPCC coapounds is >0.050.

Tes No

5. Surrogate recovery Holts vere oet for all saaples.

6. HS and HSD criteria vere met for all saaples.

Tes

Yes

No

No

7. Hethod blank criteria vere met for all samples: all compounds are <PQL.

Tes No


Rgure 8-1. Qualfty Assurance Summary Form.

7 .J t


EA LABORATORIES

QOALITT ASSURAMCE SUMMART

FOR SV-846 ANALTSES P a g e 2 o f 2

Project; Analysis: Seaivolatlles

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

Revieved by: Date:

8. Laboracory concrol saaple criceria vere met for all saaples.

Tes No

Coaaents:



7 /. r.. ., ,• •.) 4 u

.1 '•!

EA QAP-11653.01 Section No.: 8 Revision No.; 1 Date: November 30, 1990 Page: 9 of 12

EA LABORATORIES

QUALTTT ASSURANCE SUMMART

FOR SV-«46 ANALTSES Page 1 of 2

Project: Analysis: Pesticide/PCBs

EA Laboratories Report No. Hethod: U.S. EPA 8080

Revieved by; Date;

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

Tes No

2. Initial calibration criteria vere met for each analytical sequence: DVT/en6rin breakdovn <20X-, linearity as RSD ot rhe r taponat taczora for all coapounds of interest <20Z; retention tiae vlndovs escablished.

Tes No

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

Yes No

4. Continuing calibradon criceria vere mec for all saaples; che response faccor percenc difference from che Inicial calibration response factor for all coopounds of Interest vas <12Z for quantitation, <20Z for confirmation. ~

Tes No

2. Surrogate recoveries vere v i th in advisory l imi t s for a l l saap les .

Tes No

6. Percenc recoveiry and RPD for MS and MSD were within advisory limits for all samples.

Yes No

7. Mechod blank criceria vere met for all saaples: che method blank oust contain <PQL of any single pescicide/PCB coapound.

Yes No

(Revised Sepcember 1990)


7 1 f\ •• "'1 ' •J 4 i j ; .' ;•,


EA LABORATORIES

QUALTTT ASSURANCE SUMMART


Projecc; Analysis: Pescicide/PCBs

EA Laboracories Reporc No. Method: U.S. EPA 8080

Revieved by; Data:

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

Tes No

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

Tes No

Cooaents:



,«>

'.J i •• . ) 5 4


EA LABORATORIES

QOAIXTT ASSORANCE SUMMART


Project: Analysis: Metals

EA Laboratories Report No. Method: U.S. EPA SV-846

Revieved by: Date:

1. Saaples vere analyzed vithin six oonths of saaple collection. Hercury vas analyzed vithin 28 days.

Tes No

2. ICP initial calibration: A calibration blank and at least ona standard vere analyzed dally, and the initial calibration verification standard vas vithin 90Z to llOZ recovery.

Tes No

3. 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 Co 120Z for mercury).

Tes No

4. Calibradon verification (CV): A CV standard prepared froa a source othar 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 vith each batch, and all analytes vere belov the detection Holts.

Tes No

6. Hatrix spike and duplicate criteria vere met for all samples.

Yes No


Rgure 8-1. QuaUlty Assurance Summary Form.

(fl>

3 4 7' •: '> "i - 1 '. 1 .


BA LABORATORIES

QUALTTT ASSORAMCE SUMMART

FOR SV-846 ANALTSES P a g e 2 of 2

Projec t : Analysis: Metals

EA Laboratories Report No. Method: U.S. EPA SV-846

Revieved by: Date:

7. Laboratory control saaple c r i c e r i a vere oat for a l l saap les .

Tas No

Cooaonts:



1990

6 4 0 I 2 7

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

INTERNAL QUALITY CONTROLS CHECKS

A quality control program is a systematic process that controls the validity of analytical results by measuring the accuracy amd precision of each method and matrix, developing expected control limits, using these to detect anomalous events amd 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 amd external factors. Internal factors are those associated vith sample preparation and analysis. Internal factors are monitored by the use of internal quality control samples.

External factors are associated vith sample collection. They are monitored by the use of field quality control saunples vhich are identified as field and trip blanks.

This section describes the type and information provided by each of the quality control samples analyzed. Steps to be folloved in the preparation amd spiking of samples 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 raonitor laboratory contaunination. This is usually a sample of laboratory reagent vater or soil raatrix treated vith all the reagents and in the sarae manner as the sample (i.e., digested, extracted, distilled). One method blank is prepared and analyzed every day that samples are prepared.

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

9.1.2 Fortified Method Blank Spike (Laboratory Control Saraple)

Normally, fortified method blank samples are analyzed vith each batch of tventy (20) or fever samples. These samples generally consist of laboratory reagent-grade vater or solid matrix fortified vith the analytes of interest for single-analyte methods and selected analytes for multi-analyte methods according to the appropriate amalytical method. They are prepared amd analyzed vith the associated sample batch. The analyte recovery from each is used to raonitor amalytical accuracy.

o 4 Ll


The percent recovery vill be calculated and plotted onto control charts vith varning limits at tvo (2) standard deviations. These control charts vill be updated at least quarterly. Control charts vill be used to alert the laboratory of the need to check method procedure, but failure of a spike to fall vithin the 95X confidence level does not invalidate the sample data.

9.1.3 Fortified Sample (Matrix Spike)

A fortified sample (matrix spike) is an aliquot of a field sample vhich is fortified vith the analyte(s) of interest and amalyzed to monitor matrix effects associated vith a particular samples. Duplicate fortified samples (matrix spike) vill be performed for every batch of tventy (20) or fever 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 compounds are spiked into all blamk, standards, samples, and spiked samples prior to analysis for organic parauneters. Generally, surrogates are not used for inorgamic 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 vithin the control limits set in accordance vith procedures specified in the method. Surrogate recoveries vill not be calculated if sample dilution causes the surrogate concentration to fall belov the quantification limit.

9.1.5 Laboratory Duplicate Analyses

Saunples requiring duplicate analyses are split into separate aliquots prior to analysis and the aliquots amalyzed separately. This analysis monitors amalytical precision but can be affected by saraple inhomogeneity.

9.1.6 Replicate Field Samples

A replicate sample is prepared by dividing a sample into tvo or more separate aliquots. Duplicate samples are considered to be tvo replicates. Replicate samples vill 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 vill be routinely analyzed in the laboratory.

7 •J fi


9.2.1 Standard Reference Manual

A standard reference material is a solution vith a certified concentration that is analyzed as a saunple 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 vater (if available) vith one batch of saraples. The standard 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 vithin these specifications, then all the analytical data for these samples in the associated batch shall be considered questionable. If other quality control data vith 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 Plan, vhether or not the analytical results are useful and should be reported.

9.2.2 Blind Performance Saunple

This is a QC saunple of knovn concentration obtained from EPA or NIST and submitted for amalysis by the QA Coordinator. These saunples are blind to the analyst amd the results monitor amalytical accuracy.

9.2.3 Knovn Performance 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 am analytical procedure prior to analysis of amy samples. These are particularly applicable vhen a minor revision has been made to am analytical procedure or instrument.

9.3 FIELD BLANK QUALITY CONTROL SAMPLES

These samples are not included specifically as laboratory quality control samples but are analyzed vhen submitted. Data for these QC saraples are reported vith associated samples. The folloving sections pertaining to field blanks are generalized definitions. Field blank 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 blamk is a saunple of laboratory reagent vater vhich is treated in the sarae manner as a field sample. The purpose of the field blank is to raonitor incidental contaraination possibly introduced during saraple collection. A field blank is collected by pouring distilled/deionized vater provided by the laboratory into the requisite sample containers.

0 4 u i J


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 taken 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 saraple container (cooler) from the time it is shipped to the field until it is returned vith samples for analysis. The number of trip blanks included in a sampling 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 analysis of purgeable aromatic hydrocarbons.

9.4 QC MONITORING

Unless othervise indicated, the analyses of laboratory control samples are tabulated chronologically amd entered onto a quality control chart specifically maintained for each amalytical procedure. These control charts vill be labelled vith upper and lover varning limits, the analysis 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 performance and help identify system amomalies.

'-) 4 L; j .'J


10. PROJECT QUALITY ASSURANCE AUDITS

10.1 QUALITY ASSURANCE MANAGEMENT

Quality assurance is attained through utilization of a management system that contains mechamisms vithin its structure to raonitor 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 mechanism for both a qualitative and 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 and an overall reviev of the quality control systems. Performance audits constitute am 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 assurance 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 am 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 nuraber amd types of audits, both scheduled amd 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 orgamization, implementation, completion, and 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 team vill have auditing experience or vill be trained in the use of the auditing procedures.

Specific audits vill be planned, organized, and 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 channels, and follov up vith a compliance reviev.

Records vill be kept of all auditing tasks and findings.

J 'r 'J , iJ


10.2.2 Reports and Distribution

Folloving each system, performance and 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 amd appropriate signatures; and

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 and 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 accordance 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;

Name 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.

1 4 f' 'i '


10.2.4 Systera Audits

A system audit is an overall evaluation of components of the program's data acquisition and management system to deterraine that the program meets all quality assurance standards through proper design. This audit vill entail careful checking amd evaluation of the project files and documentation relating to both field amd 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 and 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 performance audit is to deterraine 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 an audit team that goes to the field (or office) amd observes that the standard operating procedures are being folloved amd proper QC vork is being performed. Performance audits vill include, but not be limited to, observation, reviev, and/or evaluation of the folloving factors:

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

Compliance vith the field amd laboratory amalysis protocols;

Performance of amy internal quality control checks that are utilized vithin the sampling amd analysis process or task; amd

Documentation of all the above.

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

7 ' ("' •• ' 0 't U ! .


11. PREVENTIVE MAINTENANCE

This section addresses the procedures for instrument maintenance and service contracts for test and 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 maintenance 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 consultants 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 manufacturer, 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 maintenance visits per year. The services provided on these visits include: changing the oil and filter/drier on the mechamical pumps; cleaning the heads on the magnetic tape drive; cleaning and aligning the heads on the disk drive; changing air filters and checking the operation on the disk drive. The oil in the turbopumps is changed once a year. In-house maintenance includes cleaning the source and the quadrupoles as required. The folloving spare parts are routinely kept on hand: filaunents, electron multiplier, source parts, repeller assembly, O-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 am in-house service schedule. This service includes: changing mechanical pump oil every three months; chamging turbopump oil every six months; changing air filters every three months; cleaming 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 amd 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.

'1 u


TABLE 11-1 FIELD EQUIPMENT AND RECOMMENDED MAINTENANCE REQUIREMENTS

Conductivity Meters

Meter probes are cleaned 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) and a calibration check.

Instruments not functioning properly are shipped to the mamufacturer for repair and calibration.

pH Meters

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

At the beginning of any 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.

4 O i o ; /


TABLE 11-1 (Cont.)

ThemoBeters

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 breakage.

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

• ' . ) ' • )


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

Leak Check

Cleaning

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 changed

Thermal Clean 1 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 and calibration by a qualified service organization. A calibration status label is affixed to each balamce after calibration, and 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 equipraent are calibrated annually (EAL-SOP-174, EAL-SOP-175).

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

3 4 EA QAP-11653.01 Section No.: 11 Revision No.: 1 Date: November Page: 5 of 9

30,

0 •; 3 i>

1990

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 lifespan (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 speaJcing, for analyses using the graphite furnace as compared to flame aspiration analyses. 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 mamufacturer'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 lamp level.

7. Inspect lamps closely, before installation, for possible damage 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 changes in background corrector (BC) balance settings, or the inability to achieve BC balance are definite indicators of lamp deterioration.

O t I.' ; :• • 1


9. As a rule, if high metal concentrations are anticipated or knovn to exist in certain samples, 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 taken in the dilution process.

10. The Perkin-Elmer spectrophotometers are double-beam 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 and that vavelength double-checked before analysis begins.

12. Exercise care in the alignment of burners and furnaces; a small raisalignraent 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 saraple 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 amy 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 manufacturer's maintenamce 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.

4


1. Colorimeter electronics and 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 amd the results logged into appropriate notebooks.

a. When flov cells must be replaced

b. When light sources raust be replaced

c. When colorimeters must be transported or exchanged

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

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

3. The analyst 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 amd the traces compared to the nominal vavelengths.

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

7. Check flov cells for cleanliness 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 amd replaced as needed.

H


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

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

12. The amalyst should be familiar vith the recorder trace form and peak shapes pertinent to the analysis to be performed; often, a change in peak 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 and cleam 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 membrane.

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 amd 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 Jo that previously recorded (significant drift before 10 :1 suggests the need for electrode replacement).

8. Spare electrodes should alvays be on hamd.

/ .' f'. •J --I u


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 any 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 raaking 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 sample 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 raaking 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 samples.

3


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 analyst'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 aixis of the control chart is the 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, and control limits. The central line is the mean, theoretical, or most probable value for the measured parameter. The limits are values on either side of the central line vith vhich are associated probabilities that an observed value vill be vithin the limits. The varning limits are the 2 a or 95X limits; that is, if the process is operating correctly and only ramdora scatter is being observed, nineteen out of tventy points should fall inside the varning liraits. The control limits are the 3 a 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 saunples (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:

,-rB\ found concentration .-._ percent recovery (XR) = x 100

expected concentration

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

PERCENT RECOVERY EOR Pyrene by CCMS (Solid)

Meun = 103 J b

UCl, = M O . 1 6 5

LCL = l l l l . A ^ I A

No. o f P o i n t s = 31

UWL = 128 . 0 9 2

LWL = 7B. t 2 7 5

3 C i to

m X

« o

3

8 I

p e r c e n t

R e c 0 V e r y

160

150

140

130

120

1 10

100

90

80

Vl)

60

50

hoan

TJ o 50 Crt t n to so ID ID > oq rt < O rD ID M. l-f o

- •• W H- > . M- O 'TJ

NJ o a i rz :^ t- o o 2 t-*

i-<i < 2 : o cr> ID O • u t

00 3 . . . ( j j CP •• • (B I-* O H O to i-«

O

C^-J

S l a r l i n g Date: 01 /10 /0 ' ; Ending Daia: 06 /15 /89 O

MOiyiNC RANGE EOR PyiRiK! hy CCMS ( S o l i d )

Moiin - l.'l V'lVJ

UCL = AS 5 725

No (if To I 11 I u = 30

UWL = 35. 0268

55

3 (Q C

3 . M

M

m

X>

« o »

1 f c

1 ^ s

M 0 V 1 n U R

n fl e

50

45 -

40

35-

30

25-

20

15

10

5

0

UCL

UWL

Moon

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TJ a po W M pi p i

oq rt (D ID

U>

z o o »-h <

ID 0 0 a

o-ID n U ) o

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vO vO o

m ro > < o M- rt O M H - > M- O "TO O 9 1 D t - *

Z H* Z O OV O • t-n . . . OLI

.. . I-- O O N i 1-*

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mov ing range (R^) = ^i.l XR.

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, ZR. For control charts based on the moving range 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)

ZR + 2.660 R

XR + 1.773 R

)?R - 1.773 R

^ - 2.660 R

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

The

UCL

UWL

LWL

LCL

S

^

=S

3

3.

2.

0

0

267

511

R

R

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

12.2.3 Hov the Charts are Used

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

liraits; or 3) seven successive points on the saune side of the central line.

• J '"T ••.-• I r • J


When one of these conditions exists, the method and the calculations must be investigated to determine if a cause for the condition cam be found. When an analyst observes that an 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.

Duncan, A.J. 1974. Quality Control and Industrial Statistics, 4th edition. Irvin, Homevood, 111.

Naval Energy and Environmental Support Activity. 1988. Sampling amd 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 amd Wastevater 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 and control charts. The bulk of this section deals vith these procedures and subsequent in-house data checks.

6 4 U '! -i


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 titramt, 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 standard solutions against vhich titrants are stamdardized (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 tramsfered to laboratory data sheets or captured by data systems attached to the instruments.

Much of the calculation of gas chromatography and 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 guarantees against nonrepresentative data points. Therefore, all personnel involved in saunpling, saunple handling, analysis, and data mamageraent must be alert to potential contamination amd procedural errors. Hovever, if nonrepresentative data points appear in the final stages of analysis, there is a mechanism 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) belov a pH of 8.2-8.3, bicarbonate is

7 i'l.


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 analyses concurrently (e.g., ammonia amd total Kjeldahl nitrogen, total amd dissolved phosphorus, and total oxidized nitrogen and nitrate). Frequently, similarity of variances is increased, thus improving the reliability of comparisons (and differences).

3. Residue analyses. 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 environraental 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

7 •J


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

12.3.4.3 Correction/Elimination Procedures

If simple errors (i.e., raiscalculations) 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 ( ; '! \.i :

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

13. 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 an existing condition are docuraented 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

Many 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 saune 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 and duration of the corrective measures taken.

13.3 CORRECTIVE ACTION METHODS

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

13.3.1 Immediate Corrective Actions

Imraediate 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 and 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 and dated by the person performing the corrective action.

13.3.2 Long-Term Corrective Actions

Long-term corrective action shall be used to identify amd eliminate causes of nonconformamces vhich are of a complex nature and that are formally repprted betveen management 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

7 / i l • . <• ,-•


Define the problem

Assign responsibility for investigating the problem

Investigate and determine the cause of the problem

Determine a corrective action to eliminate the problera

Assign and accept responsibility for iraplementing the corrective action

Establish effectiveness of the corrective action and implement the correction and

Verify that the corrective action has eliminated the problem.

4 Audit Based Non-Conformances

Internal auditing of sample 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-terra 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-conformance, 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 iraplementing the corrective action. Confirmation shall be acknovledged by notation and dated signature on the affected data record or appropriate form or by memorandum to cognizant project management. Such corrective action forms and memorandura 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 management vith corrective action reports as described in Section 2.

I " . • ' C .A

EA eMGiTMeESirsiG.

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A U D I T F INDING REPORT

AUOnOR SIQNA-njM b A t t AUOfT NUMBIR AFRNUMIEn AuorroATv

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Rgure 13-1.

/ -". I 1 • 1

•J) ' t U : 'J


14. QUALITY ASSURANCE REPORTS

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

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

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

Significamt 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 plam.

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 plans during periods vhen sarapling and laboratory analyses are undervay. These reports should be centrally filed as documentation of project quality assurance activities.

"7 ,', r , .. r .. -J 't I M D ' >

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

C !

^'7/ APPENDIX A A A f/ .

PROJECT QUALITY ASSURANCE STAFF RESUMES

(To Be Provided Upon Final Selection of Contract Laboratory)

4 0

APPENDIX B

STANDARD OPERATING PROCEDURES

(To Be Provided Upon Final Selection of Contract Laboratory)

7 L'l.

APPENDIX C

ANALYTICAL METHODS FOR NONSTANDARD ANALYSES

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

C-2 Analysis of total mercury in biological tissue saunples

APPENDIX C

Section C-l

Analysis of Methyl Mercury in Soil and Water Samples

0 '-r U i U

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 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 raethyl 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 liraits.

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.

' . - . • — • • • • • • • • I ' • " » - • ' '

'• 4 J 0 \ 6 A

FFiCBAL ETyODS OF Afi\5ALYi

OFTHE

ASSOCIATIOW OF OFFSCflAL AiMALYTlCAL CHElVliSTS

EDITED BY SIDNEY WILLIAMS

FOURTEENTH EDITION, 1984

PUBLISHED BY THE

ASSOCIATION OF OFFICIAL ANALYTICAL CHEMISTS, INC.

l l l l NORTH NINETEENTH STREET

SUITE 210

ARLINGTON. VIRGINIA 22209 USA

472 METALS AND OTHER ELEMENTS

0 u.^ AOAC OFFICIAL METHODS OF ANALYSIS (1984)

Prep, working curve of required range, starting with blank and extending to final std of range, with 4 intermediate increments. Add appropriate amts of Hg to 50 mL O.IN HCl in separator. Add 5 mL H I N O H . H C I reagent and 5 mL CHCl], and shake vigorously I min. Let layers sep., drain off CHCl,. and discard, being careful to remove as completely as possible all droplets of CHCl,. Add 3 mL 30% HOAc and appropriate vol. dithizone soln, shake vigorously 1 min, and let layers sep. (HOAc aids in stabilizing mercuric dithizonate.) Insert cotton pledget into stem of separator and collect dithizone ext (discarding first mL) in test tube for transfer to appropriate cell. Make photometer readings at 490 tun. (Since both dil. dithizone and mercuric dithizonate are somewhat unstable, read immediately.) Plot A against )ig Hg.

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

CAS-7439-97-6 (mercury)

Mercury (Mathyt) in Fish and Shellfish

G«s Chromatogrtphic Mathod

Hrst Action

{Caution: See 51.045 and 51.046.)

25.146 Method Ptrtwmmnem

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

^•147 Prmdpim

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

25.148 /t»*g»nts

(a) Solvents.—Acetone, benzene, and isopropanol are ail distd in glass (Burdick & Jackson Laboratories. Inc.; MCB Manufacturing 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 H Q soln 5 times with Vi its vol. of benzene by shaking vigorously 15 sec in separator. Discard betizene exts. Soln may be mixed in advance but must be extd immediately before use.

(c) Carrier gas.—GC quality Ar-CH. (95 + 5). (d) Sodium sulfate.—Heat overnight in 600* fumace. 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. (/) Stocic std soln.—\OO0 « Hg/mL. Weigh 0.1252 g CH,Hga (ICN-K&K Laboratories, Inc.. Plainview, NY 11803) imo 100 mL vol. flask. Dil. to vol. with benzene. (2) High intermediate std soln.—40 m Hg/mL. DU. 10.0 mL stock soln to 250.0 mL with benzene. (3) Low intermediate std soln.—2.0 m Hg/mL. Dil. 10.0 mL high intennediate std soln to 200.0 mL with benzene. (4) Worldng std jo/nj.—0.010-0.30 ng Hg/mL. Prep, monthly by dilg with benzene in vol. flasks as follows: Dil. 15 mL of 2.0 tig 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 |ig Hg/mL, resp. Dil. 20 mL of 0.10 iig Hg/ -iL std to 25.0 mL. 10.0 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 jig Hg/mL, resp.

(0 Mercuric chloride column treatment soln.—1000 ppm HgClj. Dissolve 0.1 g HgCI, in IOO mL benzene.

25.149 App*r»tus

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

(a) Centrifuge.—Model UV (International Equipment Co., Needham Heights, 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. K57000I, Kontes Glass Co.) and 10 mL graduated concentrator tube (No. IC570050, size 1025, Kontes Glass Co.).

(d) Modified Snyder distilling column.—Modify Snyder column (No. IC503000 size 121, Kontes Glass Co.) in eilher of 2 ways; (0 Shorten 3-section, 3-ball column to 2-section, 2-ball column by cutting off top at uppermost constriction, (it) Insulate 3-secuon, 3-ball column by wrapping glass wool around top section and holding it in place with Al foil. Glass wool and foil must surround only top section above top ball.

(c) Carborundum boiling chips.—20 mesh. HCI-washed. (f) Graduated cylinders.^^\asi A, 25 mL capacity, wiih ground-

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

(No. 13-678-6A, Fisher Scientific Co.. or equiv.). (h) Dropping pipets.—5 mL capacity (No. 13-7IOB, Fisher Sci

entific Co., or equiv.). (I) (jas chromatograph.—Hewlett-Packard Model 5710A or equiv.,

equipped with linear "Ni electron capture detector and 6 ft x 2 mm id silanized glass column packed with 5% DEGS-PS on 100-120 mesh Supelcoport (Supelco, Inc.). Pack column 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. CT 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 mLymin at room temp. Then heat 1 h at 100°. Next, heat coluran to 200° at programmed heating rate of 47min and hold at 200° ovemight. Do not connect column to detector during this conditioning process. Maintain 30 mLVmin carrier gas flow at all times during conditioning, treatment, and use. Operating conditions: column 155*; iryector 200°; detector, 300°; carrier gas flow 30 mU min; and recorder chart speed 0.5-1.0 cm/min. Under these conditions and with HgCli column treatment pnKedure described below, CH,HgCl peak will appear 2-3 min after sample injection.

25.150 Mercuric Chlorida Column Traatmant

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

(a) Following 200' column conditioning.—If column has just been conditioned ovemight at 20V, use this procedure. Adjust column temp, to 160° and connect detector. When baseline is steady, treat column by injecting 20 iiL HgCI] treatment soln 5 times at 5-10 min intervals. (Change in column performance may be monitored by injecting 5 |iL 0.010 iig Hg/mL std soln before and between HgOi treatment soln injections.) During treatment procedure, large broad peaks will elute. (CH,HgCI peak retention time will decrease and peak ht will increase.) Approximately \'/t-\Vt h after last HgCI, treatment soln injection, a final large peak will elute. (CH,HgCl peak ht and retention time will be stable.) This broad peak and CH,HgCI peak ht stability signal completion of treatment process. Adjust

•?, / l •i 6 ••]

AOAC OFFICIAL METHODS OF ANALYSIS (1984) SELENIUM 473

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 M.L HgClj treatment soln one time. Broad peaks will elute between 11 and 15 h after HgClj 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 155°.—If column has been used at 155* for ext analysis and column performance has degraded enough to require HgCI] treatment, increase column temp, to 160°, inject one 20 M.L aliquot of HgCIi treatment soln, and monitor baseline. Large, broad peaks will elute \-\Vi h after HgCI] 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 ot Mathyl Marcury Cliloride

Perform all operations, except weighing, in laboralory 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. Carefiilly 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 soln 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, and 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 1 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 HjO bath. Evap. so that 8 mL remains when cooled to room temp. Cool. Disconnect 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. Na,S04 must be added to 20 mL coned sample ext within 10 b of first acetone wash. Tightly stoppered exts may be held ovemight at this point. Analyze by GC.

25.152 ChrometoffrapAy

Verify that system is operating properiy by iiyecting 5 \iL vols of 0.01 \if Hg/mL working std soln into chromatograph. Difference between CH,HgC] peak hts for 2 injections should be «4%. Check detector linearity by chromatographing all 0.01-0.30 M Hg/mL working std solns.

Inject duplicate 5 |xL vols, (equiv. to 0.5 mg sample) of ext. Difference between CH,HgO peak hts for 2 injections should be «4%. Next, inject duplicate 5 lL vols, of std soln with CH,HgCl concn approx. equal to or slightly greater than ext CH,HgCl concn. Because column performance and peak ht slowly decrease with time, calc. each sample concn by comparison to std soln injected immediately after sample.

Calc. Me Hg content of homogenate in |i.g Hg/g (ppm Hg) by comparing av. CHjHgCl peak ht of duplicate sample injections with av. CHsHgCl peak ht of duplicate std injections.

ppm Hg = (RIR ) X (CIO x 20 where R = av. peak ht of duplicate sample injections; R' = av. peak ht of duplicate std injections; C = g sampie; C = concn of Hg in CHjHgCI std soln ( lg Hg/mL).

Ref.: JAOAC 66, 1121(1983).

CAS-7439-97-6 (mercury)

Nickal in Toe

Atomic Absorption Spcctrophotomatric Method

Final Action

25.153 5«e 25.031-25.035.

Selenium in Food

Fluorometrlc Method

Rnal Action

25.154 Apparattis

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

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

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

(d) Separators.—Glass, 250 and 125 mL. with Teflon stopcocks.

23.155 Raaganta

(Use anal, grade reagents and glass-distd H]0 thruout except as noted.)

(a) Nitric acid.—Distil from glass, discarding first and final 10%. (b) Dilute sulfuric acid.~5N. Dil. 140 mL HjSO. to 1 L with

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

to 1 L with H,0. (d) Disodium EDTA soln.—O.OiM. Dissolve 7.445 g

Na,H]EDTA.2H,0 and dil. to 1 L with H]0. (e) IJ-Diaminonaphthalene (DAN) soln.—I mg/mL. Pulverize

DAN (purest grade available; product from Aldrich Chemical Co. has been found satisfactory) in clean mortar to fine powder. Insert glass wool plug in stem of 250 mL separator and add 150 mL 5N HiSO.. Transfer 0.150 g DAN to separator and place on shaker 15 min to dissolve. Add 50 mL cyclohexane and shake 5 min. Let phases sep. 5 min, drain lower phase into another separator, and discard cyclohexane (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.

(f) Selenium std soln.—(1) Stock soln.—100 |ig/mL. Dissolve 0.1000 g black Se (purity »99.9%) in ca 5 mL HNO,, (a), and warm to dissolve. Dil. with H,0 and 20 mL 5N H,S04 to 1 L. (2) Working soln.—Dil. stock soln with Hfi and 5N H]SO< to give Se concns in O.IN HiSOt appropriate for level of Se expected in sample. Store all solns in all-glass containers. Solns are stable indefinitely.

23.156 Preparation ot Standard Curva and Fluoromotric Blank

Conduct appropriate vols of Se std solns («10 mL contg <s800 ng Se) and 10 mL H]0 each thru entire detn, including digestion, along with samples. Zero fluorometer against blank soln and read

n •' U -.:>

APPENDIX C

Section C-2

Analysis of Total Mercury in Biological Tissue Samples

3 4 Ci

APPENDIX C

Section C-2

Analysis of Total Mercury in Biological Tissue Samples

7 '• !''. •; i 'C'I

£?A 600/'l-31-055

United Statas Environmental Proteclion Agency

oEPA Research and Development

TntflHm ."atiiods For The Sampling and Analysis of Interim -^-^o^^^ Pollulants in Sediments

and rish Tissue

Prepared for Regional Guidance

Prepared by Phvsical and Chemical Methods Branch EnvlrSmeJtal .Monitoring and Sapport Laooratory Cincinnati, Ohio *5268

Analysis of Fish for Mercury

3 A O I 0 8 , ,|

I I I

1. Scope and ADO 1ication ^

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

Inorganic) 1n f1sh. A weighed portion of the sample is digested

I

I

1

with sulfuric and nitric acid at 5a°C followed by ovemight

oxidation with potassium permanganate at room traperature. Mercury

Is subsequently measured by the conventional cold vapor technique.

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

or below the normal instrument and recorder control.

2. Sample Preparation f

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 I

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

allowed to thaw before weighing.

3. Preparation of Calibration Curve

cone. H-SO^ and 1 ml of cone. HNO, to each bottle and place

In watar bath at 5a°C until the tissue 1s completely dissolved

(30 to 60 min.).

34

3.1 The calibration curve is prepared from values for portions of

spiked fish tissue treated In the manner used for the tissue

samples being analyzed. For preparation of the calibration

standards, choose a 5g portion of fish and blend in a Waring J

blender.

3.2 Transfer accurately weighed portions to each of six dry BOO

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

^ ' Q-, 6: O f

3.3 Cool and transfer 0-, 0.5- 1.0-, 2.0-, 5.0- and 10.0- ml aliquots

of the working raercury solution containing 0 to 1.0 ug of raercury

tp the BOO bottles. Cool to 4''c in an Ice bath and cautiously

add 15 ml of potassi ua 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 ral. 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 Methcd 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 ',4e1gh 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 ml of cone. HNO2 ^ "*^ bottle and place in a water bath

maintained at 58°C until the tissue is con^letely 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 Increments. Add an additional 10 ml

of more of permangante, as necessary to maintain oxidizing

35

•J 4 I - ij

conditions. Allow to stand overnight at room temperature (see

NOTE). Continue as described under 3.4.

PKJTE: 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 m1n. The sanple Is then cooled and 15 ml of

potasslin permanganate solution added cautiously. At this ooint,

the sample Is retumed to the water bath and digested for an

additional 90 m1n. at 30°C (9). If this method is followed, the

calibration standards must also be treated In this manner.

Continue as described under 3.4.

5. Calculation

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 raercury concentration In the sample by the formula:

ug Hg/gram - uq Hg in aliquot ug ng/grani ^rtTamTTquarTn gns

5.3 Report mercury concentrations as follows:

Below 0.1 ug/?B, < 0.1 ug; between 0.1 and 1 ug/gnJi 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

/, i'l f ! •' '"•' 1

'D S- L; 1 / I

7. Precision and Accuracy

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

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

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

these levels were 11.9%, 7.OX, and 3.6X, respectively. Recovery of

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

11235, 93X, and 86S, respectively.

37

3 4 EPA 600/4-81-055

Unrtad States Environmental Protection Agancy

^B^A Research and Development

Interfn Methods For The Sampling and Analysis of Priority Pollutants in Sediments

and Fish Tissue

Prepared for Regional Guidance

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

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APPENDIX D

CONTAINERS, PRESERVATION, AND HOLDING TIMES

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

AND PERMISSIBLE SAMPLE TYPES

Paraaeter Container

Concentrated Waate Saaples

Organic Coapounds

Hetals and Other

Inorganic Coapounds

KP Toxicity

Flash Point and/or

Heat Content

Fish Saaples

Organic Coapounds

Het als and Otlier Inorganic Coapounds

8-oz. wldeaouth glass

with Teflon liner


with Teflon IIner

8-oz. wldeaouth glass with Teflon liner


with Teflon liner

Wrap In alualnua foil

Place In plastic zip-lock bag

Liquid - Low to Hedlua Concentration Saaples

Alkalinity

Acidity

H;i r t l-l i i t l o g l i - a i

5 0 0 - a l o r l - l l 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 l i n e d c l o s u r e

500-aJ o r l - l l t e r p o l y - ' e t h y l e n e w i t h p<^>lyethy-Iene or p o l y e t h y l e n e I I n e d c l o s u r e

2SII-tnl g l a s s w i t h i; ' '*.^^ (- loHiire o r p L i s t i c cn\t-a l i l o of he Ing anl u r I .ivi-il

Preservative

None

None

None

None

Freeze

Freeze

Cool, 4'C

Cool, A'C

Cd.." /i°C

Mo III Ing

Tiae

ASAP

ASAP

ASAP - NS

ASAP - NS

ASAP

ASAP

\lt days

14 days

I) lir-

PenalsRihle Sampl (•

Type

G or C

Referent: tr

C. cki- C

C i>r C

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

AND PERMISSIBLE SAMPLE TYPES '

PermlsKihie Holding Sample

Paraaeter Container Preservative Tiae Type Referent:e

Liquid - Low to Hediua Concentration Saaples (Continued)

Static Bloassay l-gal. aaber glass Cool, ^'C A8 hrs. G or C D (not aolvent rinsed)

Blocheaical Oxygen l/2-gal. polyethylene' Cool, A'C A8 hrs. C or C C Demand (BOU) with polyethylene closure

Chloride 500-al or l-llter poly-' None 28 days G or C C ethylene with polyethylene or polyethylene lined closure

Chlorine Residual In-sltu, beaker or bucket None Analyze G C Immediately

Color 500-BI or l-llter poly-' Cool, 4*C A8 hrs. G or C C ethylene with polyethylene or polyethylene lined closure

Conductivity 500-ai or l-llter poly-' Cool, 4"C 28 days G or C C ethylene with polyethy- (tieteralne on lene or polyethylene site If pttsstble) '.; I Ined closure

Chrtkaliiffl, Hexavalent l-llter polyethylene with Cool, ^"C IU hrs. G (.' p o l y e t h y l e n e c l o s u r e

Cyan ide | - | l t e r o r 1 /2 -ga l Ion A s c o r h i c A c l d ^ i ^ I'i days <•' '-p o l y e t h y l e n e w i t h p o l y - Soilluro H y d r o x i d e , e t i i y l e i i e o r po l yet h y l CMH' pH > I2 l i n e d c i t i s i i r e Cot.l , A°C

>o

4-.--

APPENDIX D RECOMMENDED SAMPLE CONTAINERS, SAMPLE PRESERVATION, SAMPLE HOLDINP T T M P C


Container Paraaeter

Liquid - Low to Hedlua Concentration Saaplea (Continued)

Preservative

Dissolved Oxygen (Probe)

Dissolved Oxygen (Winkler)

EP Toxicity

Fluoride

llartlness

U S

Hetals

Metals, DIsntklved

In-sltu, beaker or bucket

300-al glasa. BOD bottle

l-gal. glass (aaber) with Teflon liner

l-liter polyethylene or'

1/2-gal. polyethylene with

polyethylene or polyethy

lene lined closure

500-al or |-llter poly

ethylene with polyethy

lene or polyethylene

lined closure

500-al or l-llter poly-' ethylene with polyethylene or polyethylene lined closure

l-llter polyethylene with polyethylene lined closure

l-liter ptilyethylene with polyethylene lined t: losure

None

Fix on site, store In dark

Cool. 4*C

None

50Z Nltric2

Acid. pH <2

Cool, 4"C

50X Nltrlc2

Acid, pH <2

Fl l t e r - o n - 8 l t e 2 SOI N i t r i c •

A t i d , pH <2

Holding

Tiae

Deteralne

On Site

Permissible

Sample

Type

8 hrs. (determine on site If possible)

ASAP - NS

28 days

6 aonths

48 hrs.

(t aonths

<> months

G

G or C

G or C

G or C

G or C

G or C

Reference

•'_"-i


AND PERMISSIBLE SAMPLE TYPES ' Permissible

Holding Sample Paraaeter Container Preservative Tiae Type Reference

Liquid - Low to Hedlua Concentration Saaples (Continued)

Nutrients^ l-llter polyethylene or 50X Sulfuric^ 28 days G or C C l/2-gal. polyethylene Acid, 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, 4'C

Organic Coapounds - C lilxtractable and Pesticide Scan

No Residual Chlorine l-gal. aaber glass or Cool, 4'C 47 days^ G or C C Present 2 1/2-gal. aaber glass

with Teflon liner

Residual Chlorine l-gal. aaber glass or Add 3 al lOZ 47 days^ G or C C Present 2 l/2-gat. aaber glass sodiua thiosulfate

with Teflon liner per gallon Cool, 4'C

O r g a n i c C o a p o u n d s -

P u r g e a b l e (VOA) Csi

No R e s i d u a l C h l o r i n e 2 4 0 - a l v i a l s w i t h 4 d r o p s c o n e , h y d r o - 14 d a y s G G -p:^.

P r e s e n t T e f l o n l i n e d s e p t u a c a p s c h l o r i c a d d .

Cool , 4°C

No R e s i d u a l C h l o r i n e 2 4 0 - a l v i a l s w i t h C o o l , 4 " C 7 d a y s G <" ' ^ - ' P r e s e n t T t f f l o n I i n e i l s e p t u m traps

H I ' N I . I I I . I I ( l i l i i i l i i f i /«l»-ml v i a l s w i t h K o o l c i o t e 6 IA d a y s C. <•" •""

I ' ' • . l l l l l i - M i i i l l l i l f i l S f | i l iiiB r , i | i s



Paraaeter Container Preservative

Liquid - Low to Hedlua Concentration Saaples (Continued)

Organic Coapounds -Specified and Pesticides (Non-Prlorlty Pollutants such as Herbicides)

l-gal. glass (aaber) or 2 1/2-gal. glass (aaber) with Teflon lined closure

Footnote 7

Holding Time

47 days'

PeriDl sslble

Sample

Type

C or C

Reference

Organic Halides -Total (TOX)

250-B1 aaber glass with Teflon lined septua closure

Cool, 4'C ASAP - NS

pll In-sltu, beaker or bucket

None Analyze Iaaediately

Phenols l-liter aaber glass with Teflon lined closure

50Z Sulfuric Acid, pH <2 Cool. 4°C

28 days

Phosphate-Ortho 500-al or l-llter polyethylene with polyethylene or polyethylene IIned closure

Fllter-on-site Cool, 4'C

48 hrs.

C'-J

Phosphorus. Total Dissolved

500-al or l-llter polyethylene with polyethylene or polyethylene lined closure

F l I t e r - o n - s i t e 50X S u l f t i r l c A c i d . pH <2

Gt)ol . 4 ' C

28 days

Solids. Settleable 1 / 2 - g a l . p o l y e t h y l e n e

w i t h p o l y i r l l i y l ene

r l o s u r e

Cool , 4°C 4H h r s . G o r C



P a r a m e t e r Contallner Preaeirwffltllwe

Lflquiti - Low t o MedfluD Coiniceinitrat ilon Saiopies (Contl lnued)

Cool- 4''C SolUda ( T o t a l end Suspended , e t c . )

S u l f a t e s

S u l f i d e s

Teape ra t t e re

Tu rbSd t ty

500-Eii o r I - E l t e r p o l y - ' e t h y l e n e uitDi p o l y e t h y l e n e or poLyetSiylene HQned c l o s u r e

500-Qa or l -EOter p o l y - ' e t h y l e n e wi th poOyc-'tJty-l ene o r p o l y e t h y l e n e llnetfi c l o s u r e

5 0 0 - D 1 o r l - i a t e r po ly -2 e t h y l e n e u i t h p o l y e t h y l ene or p o l y e t h y l e n e l i n e d c l o s u r e

I n - s i t u , beake r or bucket

500 -a l or l - E l t e r po ly-^ e t h y l e n e wi th p o l y e t h y l ene or ipo lye thy lene l i ned c l o s u r e

Coott, 4 'C

2 D I Zinc A c e t a t e ^ Cone. Sodiua roKilde t o pDS >9 Coo l , 4°C

IMone

C o o l , 4°C

S o i l . Sedftiaent o r S ludge S a a p l e s - Low t o Medfluc C o n c e n t r a t i o n

E. P . T o x i c i t y 8-f>z. widemouth g l a s s Coo l , 4 'C

H i ' X . i l a

8-f>z. wldeiBouth g l a s s wi th Teflon® 1Ined c l o s u r e

8-ti7.. wldomtitith ({lass wi th ier i t .n '* I Inetl t- I n su re

Cool , 4 ' c

H o l d i n g T i a e

7 days

28 days

7 days

Deteriaine On S i t e

48 h r s .

ASAP - NS

6 mtiii ths

PeiriDtssthlle SaiopDe

Type

G or C

G or C

G o r C

G o r C

G o r C

Reference

C-J.

4>.



Paraaeter Container Preservative Holding Tiae

Soil, Sediaent or Sludge Saaples - Low to Hedlua Concentrations (Continued)

Nutrients Including: 500-aI polyethylene with Nitrogen, Phos- polyethylene closure or phorus, Cheaical 8 oz. wldeaouth glass Oxygen Deaand with Teflon lined closure

Organics -Extractable

Organics -Purgeable (VOA)

Other Inorganic Coapounds -Including Cyanide

8-oz. wldeaouth glass with Teflon liner

4-oz. (120 nf.J i-tideititicvr.h. glass wich TeHc-n. l(n«t:

500-BI polyethylene with polyethylene closure or 8-oz. wldeaouth glass with Teflon I Ined closure

Cool, 4'C

Cool, 4'C

Cool, 4'C

Cool, 4'C

ASAP

ASAP

ASAP

ASAP

Permissible

Sample Type

G or C

G or C

G or C

G or C

Reference

Abbreviatlons: G - Grab C - Composite ASAP •• As Soon As Possible NS - Not Specified


Footnotes; AND PERMISSIBLE SAMPLE TYPES

1. Use Indicated container for single paraaeter requests, 1/2-gallon polyethylene citntalner for aultlple paraiaeter requests except those including BOD, or l-gal lon polyethylene container fitr 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 |>otasBl(ira Iodide-starch test paper; a blue color Indicates need for treatment. Add ascorbic a d d , a few crystals at a tiae, until a drop of saaple produces no color on the indicator paper. Then add an additional 0.6 g of ascorbic acid for each liter of saaple voluae.

4. Hay include nitrogen series (aaaonla, total Kjeldahl nitrogen, nltrate-nltrIte), total phosphorus, chemical oxygen deaand 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 4 oz. soil VOA container which has been pre-preserved with four drops of 10 pirrcent sodiua thiosulfate solution. Cently aix the saaple and transfer to a 40 al VOA vial that has been pnr-preserved with four drops concentrated HCl, cool to 4'C.

7. See Organic Coapounds - Extractable (page 4 of 8 ) . The Analytical Support Branch should be consult<?d for any special organic coapound analyses in order to check on special preservation requlreaents and or extr.-i sumplir voluae.

References;

A. US-EPA, Region IV, Environaental Services Division, "Analytical Support Branch, Operations and ()iiaMty Control Hanual," June I, 1985 or latest version.

B. EPA Hethod 1310, Extraction Procedures, "SW 846," US-EPA, Office of Solid Wastes, Washington, DC, 19H2.

C. 40 GFR Part 136, Federal Register, Vol. 49, No. 209, October 26, I9H4. r—>

U. US-F.PA, Region IV, Environmental Services Division, "Ecological S»ippt>rt Branch, Standard (IperatliiK Prticfdiirt's o '^ H.iniial ," latest versltin. [ • . . .

K. Ki'A lnti!rim Hethoil 450.1, "Total Organic Halltit- " IIS-KPA, OKI). KMSi., Pliyslcai .iiid Ciieroltal Mflln Hraixli. 'nciniiali. Oliio, November I9H0.

O-J

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