DRAFT SAMPLING AND ANALYSIS PLAN OCONOMOWOC … · Term Remedial Action (LTRA) activities at the OEP site in Oconomowoc, Wisconsin in accordance with the Statement of Work (SOW) dated

DRAFT SAMPLING AND ANALYSIS PLAN

OCONOMOWOC ELECTROPLATING Oconomowoc, Wisconsin

Long-Term Remedial Action

WA No. 236-RALR-05M8/Contract No. 68-W6-0025

June 2005

MKE\ III

Contents

A Quality Assurance Project Plan (QAPP) B Field Sampling Plan (FSP)

Quality Assurance Project Plan (QAPP)

DRAFT QUALITY ASSURANCE PROJECT PLAN




June 2005

MKE\ III





Prepared by: CH2M HILL Date: June 2005 Approved by: _____________________________________________ USEPA, Region 5, Work Assignment Manager William Ryan _____________________________________________ USEPA, Region 5, Quality Assurance Reviewer _____________________________________________ CH2M HILL Site Manager Bill Andrae _____________________________________________ CH2M HILL Quality Assurance Manager Gina Bayer Laboratory Director CT Laboratories

Laboratory Quality Assurance Manager CT Laboratories

MKE\050810001 V

Distribution List

Stephen Nathan, PO/USEPA, Region 5 (w/o enclosure)

Norvelle Merrill, CO/USEPA, Region 5 (w/o enclosure)

William Ryan, WAM/USEPA, Region 5

USEPA, Region 5, Quality Assurance Reviewer

Edward Lynch, WDNR

David Berwanger, Director/ CT Laboratories

Bill Andrae, SM/CH2M HILL, Milwaukee

Ike Johnson, PM/CH2M HILL, Milwaukee

Dan Plomb, DPM/CH2M HILL, Milwaukee

Regina Bayer, QAM/CH2M HILL, Milwaukee

Bob Tossel, QC RVW/CH2M HILL, Waterloo, Ontario, Canada

Joe Sandrin/CH2M HILL, Milwaukee (w/o enclosure)

Cherie Wilson, AA/CH2M HILL, Milwaukee

MKE\050810001 VII

Contents

Distribution List .................................................................................................................................v Acronyms and Abbreviations .........................................................................................................xi 1. Project Management ...................................................................................................................... 1

1.1 Introduction ......................................................................................................................... 1 1.2 Project Organization ........................................................................................................... 1

1.2.1 USEPA Region 5 Work Assignment Manager ................................................... 1 1.2.2 USEPA Region 5 Quality Assurance Reviewer ................................................. 2 1.2.3 WDNR Site Manager ............................................................................................. 2 1.2.4 CH2M HILL Program Manager........................................................................... 2 1.2.5 CH2M HILL QA Manager .................................................................................... 2 1.2.6 CH2M HILL Site Manager.................................................................................... 2 1.2.7 CH2M HILL Review Team Leader...................................................................... 4 1.2.8 CH2M HILL Project Chemist ............................................................................... 4

1.3 Problem Definition/Background Information................................................................ 4 1.3.1 Vapor Intrusion Evaluation .................................................................................. 5

1.4 Project Description and Schedule ..................................................................................... 6 1.4.1 Project Description ................................................................................................. 6 1.4.2 Project Schedule ..................................................................................................... 7

1.5 Data Quality Objectives and Criteria for Measurement Data....................................... 7 1.5.1 Step 1: State the Problem....................................................................................... 7 1.5.2 Step 2: Identify the Decision ................................................................................. 8 1.5.3 Step 3: Identify the Inputs to the Decision.......................................................... 8 1.5.4 Step 4: Define the Study Boundaries ................................................................... 9 1.5.5 Step 5: Develop a Decision Rule......................................................................... 10 1.5.6 Step 6: Specify Limits on Decision Errors ......................................................... 12 1.5.7 Step 7: Optimizing the Design............................................................................ 12 1.5.8 Measurement Performance Criteria .................................................................. 13

1.6 Instructions for Special Training Requirements/Certification................................... 13 1.7 Instructions for Documentation and Records ............................................................... 13

1.7.1 Field Sampling Documentation ......................................................................... 13 1.7.2 Data Reporting ..................................................................................................... 14 1.7.3 Electronic Analytical Record Format................................................................. 16 1.7.4 Project Record Maintenance and Storage ......................................................... 16

2. Data Generation and Acquisition ............................................................................................. 17 2.1 Sampling Process Design ................................................................................................. 17

2.1.1 Compliance Monitoring ...................................................................................... 17 2.1.2 Natural Attenuation Monitoring ....................................................................... 18 2.1.3 Water Level Measurements ................................................................................ 18 2.1.4 Field Parameters................................................................................................... 18 2.1.5 Sampling Method Requirements ....................................................................... 19

2.2 Sample Handling and Custody Requirements ............................................................. 19 2.2.1 Sample Handling and Preservation................................................................... 19 2.2.2 Sample Identification System ............................................................................. 20


VIII MKE\050810001

2.2.3 Sample Packaging.................................................................................................20 2.2.4 Sample Custody....................................................................................................21

2.3 Analytical Method Requirements ...................................................................................23 2.3.1 Analytical SOPs.....................................................................................................24

2.4 Quality Control Requirements.........................................................................................24 2.4.1 Quality Control Samples .....................................................................................24 2.4.2 Data Precision, Accuracy, and Completeness ..................................................25

2.5 Instrument/Equipment Testing, Inspection, and Maintenance Requirements........28 2.5.1 Field Instrument Maintenance............................................................................28 2.5.2 Laboratory Equipment/Instruments .................................................................28

2.6 Instrument Calibration and Frequency ..........................................................................29 2.6.1 Field Instruments..................................................................................................29 2.6.2 Laboratory Instruments .......................................................................................29

2.7 Inspection/Acceptance Requirements for Supplies and Consumables.....................29 2.8 Non-Direct Measurements ...............................................................................................30 2.9 Data Management Plan.....................................................................................................30

2.9.1 Team Organization and Responsibilities ..........................................................30 2.9.2 Sample Tracking ...................................................................................................31 2.9.3 Data Types .............................................................................................................31 2.9.4 Data Tracking and Management ........................................................................31 2.9.5 Computer Database..............................................................................................32 2.9.6 Documentation......................................................................................................33 2.9.7 Evidence File .........................................................................................................33 2.9.8 Presentation of Site Characterization Data .......................................................33 2.9.9 Evaluation of Natural Attenuation Monitoring Data......................................33

3. Assessment/Oversight..................................................................................................................35 3.1 Assessments and Response Actions................................................................................35

3.1.1 Field Audits ...........................................................................................................35 3.1.2 Laboratory Audits ................................................................................................36

3.2 Reports to Management....................................................................................................38 4. Data Validation and Usability....................................................................................................39

4.1 Data Review, Verification, and Validation.....................................................................39 4.2 Validation and Verification Methods .............................................................................39 4.3 Reconciliation with Data Quality Objectives .................................................................40

5. References.......................................................................................................................................41

CONTENTS

MKE\050810001 IX

Appendixes

A Analytical Standard Operating Procedures B Chain-of-Custody and Sample Tag

Tables

1-1 Project Action Limits and Reporting Limits for Natural Attenuation Parameters in Groundwater .................................................................................................................... 10

1-2 Project Action Limits for Volatile Organic Compounds in Groundwater ................... 11 2-1 Long-Term RemedialAction Sampling Summary ........................................................... 18 2-2 Sample Containers, Preservations, and Holding Times ................................................. 20 2-3 Long-Term Remedial Action Parameter List and Contract-Required Limits of

Quantification ....................................................................................................................... 24 Figures

1-1 Team Organization................................................................................................................. 3

MKE\050810001 XI

Acronyms and Abbreviations

BAT batch

CFR Code of Federal Regulations COC chain-of-custody

DMP Data Management Plan DMS Data Management System DO Dissolved oxygen DQO Data Quality Objective

EB equipment blank EDD Electronic data deliverable

FB Field blank FOP Field Operating Procedures FSP Field Sampling Plan FTL Field Team Leader

HPLC high performance liquid chromotography

ID Identification number

L liter LAN Local Area Network LIMS Laboratory Information Management System LTRA Long-Term Remedial Action

MCL maximum contaminant level μg/L micrograms per liter mg/L milligrams per liter ml milliliter MNA monitored natural attenuation MS/MSD Matrix spike/matrix spike duplicate

NAPL Nonaqueous phase liquid NIST National Institute of Standards and Technology

OEP Oconomowoc Electroplating ORP Oxidation-reduction potential

PAL Preventive Action Limit PARCC precision, accuracy, representativeness, completeness, comparability PE Performance evaluation PID Photoionization detector

QAM Quality Assurance Manager QAPP Quality Assurance Project Plan QA/QC Quality Assurance/Quality Control


XII MKE\050810001

RI/FS remedial investigation/feasibility study RL reporting limit ROD Record of Decision RPD Relative Percent Difference RTL Review Team Leader

SDG Sample Delivery Group SM Site Manager SMP sample SOP Standard Operating Procedure SOW Statement of Work

TB Trip blank TOC Total organic carbon TRSQC tests and results with quality control

USACE U.S. Army Corps of Engineers USEPA United States Environmental Protection Agency

VOC volatile organic compound

WAC Wisconsin Administrative Code WA Work assignment WAM Work Assignment Manager WDNR Wisconsin Department of Natural Resources

OCONOMOWOC ELECTROPLATING SITE DRAFT QUALITY ASSURANCE PROJECT PLAN REVISION: 2 DATE: JUNE 2005 PROJECT MANAGEMENT PAGE: 1 OF 59

MKE\050810001

SECTION 1

Project Management

1.1 Introduction The U.S. Environmental Protection Agency (USEPA) requires parties conducting environmental monitoring and measurement efforts mandated or supported by USEPA to participate in a centrally managed Quality Assurance Project Plan (QAPP). Parties generating data under this program must implement procedures so that the precision, accuracy, representativeness, completeness, and comparability (PARCC) of their data are known and documented. To meet this objective, a written QAPP must be prepared covering each project to be performed. All project participants, including subcontractors, must follow the procedures and protocols outlined in the QAPP.

This QAPP presents the organization, objectives, functional activities, and specific quality assurance (QA) and quality control (QC) activities for the Long-Term Remedial Action (LTRA) work being conducted at Oconomowoc Electroplating (OEP) site located in Ashippun, Wisconsin. Due to the close proximity of Ashippun to Oconomowoc, Wisconsin, the names of the township and the city are often interchanged. This document will refer to the site location as Oconomowoc, Wisconsin.

This section provides an overall approach for managing the project, including:

• Project organization, roles, and responsibilities • Problem definition and background information • Project description and schedule • Data quality objectives (DQOs) and criteria for measurement data • Instructions for special training requirements/certification • Instructions for documentation and records management

1.2 Project Organization At the direction of the USEPA Region 5, CH2M HILL is responsible for all phases of the Long-Term Remedial Action (LTRA) activities at the OEP site in Oconomowoc, Wisconsin in accordance with the Statement of Work (SOW) dated May 17, 2004 for Work Assignment No. 236-RALR-05M8, Contract No. 68-W6-0025. The various QA and management responsibilities of key project personnel are defined below and shown on Figure 1-1.

1.2.1 USEPA Region 5 Work Assignment Manager The USEPA work assignment manager (WAM) has overall responsibility for all phases of the LTRA. The WAM is also responsible for the review and approval of this QAPP. William Ryan is the WAM for the OEP site.


MKE\050810001

1.2.2 USEPA Region 5 Quality Assurance Reviewer The USEPA representative responsible for reviewing and approving this QAPP and the attached Special Analytical Services (SAS) forms. They are also responsible for overseeing the USEPA data validation effort of the SAS and Contract Laboratory Program Routine Analytical Services (RAS) data.

1.2.3 WDNR Site Manager Edward Lynch, the Wisconsin Department of Natural Resources (WDNR) Site Manager (SM) assigned to the OEP site, is participating in the LTRA activities.

1.2.4 CH2M HILL Program Manager Ike Johnson, the CH2M HILL’s Program Manager, has overall responsibility for meeting USEPA objectives and CH2M HILL quality standards, as well as technical QC and project oversight.

1.2.5 CH2M HILL QA Manager Gina Bayer, the Quality Assurance Manager (QAM), will remain independent of direct job involvement and day-to-day operations. The specific functions and duties of the QAM include:

• Directing the QA review of the various phases of the project, as necessary • Directing the review of QA plans and procedures • Providing QA technical assistance to project staff, as necessary

The QAM also has direct access to management staff to resolve QA disputes, as necessary.

1.2.6 CH2M HILL Site Manager Bill Andrae is the CH2M HILL Site Manager (SM) responsible for implementing the project. As such, he is authorized to commit the resources necessary to meet project objectives and requirements. His primary function is to achieve the technical, financial, and scheduling objectives of the project. He will report directly to the USEPA Region 5 WAM, and will be the major point of contact for matters concerning the project. The specific responsibilities of the SM include:

• Defining project objectives and developing a detailed Work Plan and schedule

• Establishing project policy and procedures to address the specific needs of the project as a whole, as well as the particular objectives of each task

• Acquiring and applying technical and corporate resources to meet budget and schedule constraints

• Orienting field leaders and support staff to the project’s special considerations

• Monitoring and directing other team members

• Developing and meeting ongoing project or task staffing requirements, including mechanisms for reviewing and evaluating each task product

CH2M HILL Remedial Action

Site Manager

Bill Andrae

CH2M HILLRAC V Program Manager

Ike Johnson

US EPA Region 5Quality Assurance Reviewer

To be determined

Senior Review Team

Kathi Ried/RTLGina BayerBob Tossell

Wisconsin Department of Natural Resources

Edward Lynch

EPA RemedialProject Manager

William Ryan

RAC V Contract Administrator

Matt Kluge

Analytical Testing/Quality Assurance

Heather Hodach

Subcontract Laboratory

CT Laboratories

Support StaffMiscellaneous Subcontracts/

Field Subcontracts

E062005008MKE E317734.DU.01 Org Chart 6-9-05tll

FIGURE 1-1Team Organization

Oconomowoc Electroplating Site Quality Assurance Project Plan


MKE\050810001

• Reviewing the work performed on each task to ensure quality, responsiveness, and timeliness

• Reviewing and analyzing overall task performance with regard to the planned schedule and budget

• Reviewing external reports (deliverables) before their submission to USEPA Region 5

• Representing the project team at meetings and public hearings

1.2.7 CH2M HILL Review Team Leader As the review team leader (RTL), Kathi Ried supports the SM in site management activities and coordinates CH2M HILL internal reviews. She will be involved in ongoing planning activities.

1.2.8 CH2M HILL Project Chemist Heather Hodach, the CH2M HILL project chemist, is responsible for tracking data and overseeing the data evaluation. The specific responsibilities of the project chemist include the following:

• Scheduling the analytical laboratories

• Coordinating activities with laboratories and data validators

• Overseeing data validation and the production of results tables

• Evaluating data usability

• Overseeing the tracking of samples and data from the time of field collection until results are entered into a database

1.3 Problem Definition/Background Information The 10-acre OEP site is composed of a former 4-acre electroplating facility located at 2572 Oak Street in Oconomowoc, Wisconsin, and 6 acres of wetlands located adjacent to and southwest of the former facility. OEP began operation in 1957. Electroplating processes performed at the facility used nickel, chrome, zinc, copper, brass, cadmium, and tin. Finishing processes included chromate conversion, coating, and anodizing. OEP ceased operations in 1990, and the facility was demolished and removed in May 1992.

The USEPA, in consultation with the WDNR, conducted a Remedial Investigation and Feasibility Study (RI/FS) at the site from April 1987 to September 1990. The RI determined that, as a result of hazardous waste disposal at the electroplating facility, various chemical contaminants leached into the groundwater, which flows toward Davy Creek. Associated soils have been contaminated with organic chemicals and metals. The quantities of chemicals found in the groundwater, soils, and landfill were found to present unacceptable potential risk levels to human and/or environmental receptors.

In 1990, the USEPA issued a Record of Decision (ROD) for the site, which required excavation and disposal of lagoon sludge and surrounding soils, excavation and disposal of


MKE\050810001

non-lagoon contaminated soils and debris (including an abandoned electroplating building), excavation and disposal of metals-contaminated sediments from the wetlands area adjacent to Davy Creek, and extraction and treatment of groundwater in compliance with State of Wisconsin groundwater quality standards.

In accordance with the ROD and the approved remedial design, USEPA constructed a treatment system to treat groundwater extracted from five wells at the site. The U.S. Army Corps of Engineers (USACE) has operated the groundwater treatment system on behalf of USEPA since 1996.

A subsequent study conducted by RMT Inc. of Madison, Wisconsin (on behalf of WDNR) concluded that, although pumping and treatment of groundwater has substantially lowered the concentration of contaminants, further treatment has been ineffective since the rate of treatment has leveled off. The model used for this study indicated that the only reason that this would occur would be the presence of nonaqueous phase liquid (NAPL) in the organic layers of site soils. The plateau of contaminant concentrations has rendered further treatment ineffective. As a result, the treatment plant was shut down in July 2004.

The history of OEP and its operations, previous investigations and remediation, and physical and chemical conceptual models are described in the Field Sampling Plan (FSP, CH2M HILL 2005).

1.3.1 Vapor Intrusion Evaluation Information from existing site characterization and investigation, remedial design, and remedial action efforts to date has indicated that nearby residences do not appear to be impacted by groundwater. However, uncertainty existed regarding vapor intrusion into residential dwellings close to the site. This uncertainty was a concern to USEPA and WDNR.

At the request of USEPA and WDNR, a vapor intrusion evaluation for buildings was conducted by CH2M HILL using the evaluation process recommended in USEPA’s Draft Guidance For Evaluating The Vapor Intrusion To Indoor Air Pathway From Groundwater And Soils (November, 2002). The evaluation is used to determine if an exposure pathway is complete or incomplete. Only readily available data has been used in this evaluation.

The guidance document calls for proceeding in a careful stepwise fashion and recommends the specific sequential approach. There are three tiers of assessment that involve increasing levels of complexity and specificity.

• Tier 1—Primary screening is designed to be used with general knowledge of a site and the chemicals known or reasonably suspected to be present in the subsurface; it does not call for specific media concentration measurements for each constituent of concern.

• Tier 2—Secondary screening is designed to be used with some limited site-specific information about the contamination source and subsurface conditions (e.g., measured or reasonably estimated concentrations of target chemicals in groundwater or soil gas, and depth of contamination and soil type).

• Tier 3—Site-specific pathway assessment involves collecting more detailed site specific information and conducting confirmatory subslab and/or indoor air sampling. The evaluation process presents a logical and linear progression designed to screen out sites


MKE\050810001

ordinarily not needing further consideration and focuses attention on those sites that generally need further consideration of the vapor intrusion pathway or action.

The guidance document suggests starting at Tier 1. However, the evaluation does not need to begin with Tier 1 and may proceed directly to Tier 2 or 3 if appropriate.

1.3.1.1 Tier 1 Evaluation

The Remedial Investigation/Feasibility Study completed in 1990 documented existing conditions prior to remedial activities and the remedies for each operable unit.

Remedial activities were completed in 1994 to remove source areas and in 1996 the groundwater treatment system began operation. For 8 years, the groundwater extraction system operated at the site. This extraction system substantially lowered the concentration of metals and chlorinated volatile organic compounds (VOCs) in groundwater.

The extraction system was shut down in July 2004 because groundwater concentrations from the extraction wells were no longer decreasing with continued operation or were decreasing at a very small rate. However, site related chemicals still remain in the groundwater near residential dwellings, but at much lower concentrations.

Thus, historic soil and groundwater data indicate the presence of site-related chemicals of concern in the subsurface and secondary screening is recommended.

1.3.1.2 Tier 2 Evaluation

During the RI, a soil gas survey was performed, including offsite locations near residential dwellings, and no organic vapors were detected at any offsite locations. Since that time, source areas have been removed, VOC concentrations in groundwater have been significantly reduced, and VOCs within the unsaturated zone have likely volatilized; thus, vapor intrusion into the residential dwellings is highly unlikely. Therefore, based on historic data and current conditions at the site, the exposure pathway is considered incomplete and no further vapor intrusion investigation is warranted.

1.4 Project Description and Schedule

1.4.1 Project Description As discussed in this QAPP, groundwater and surface water sampling will be performed based on the overall objective to gather data to evaluate impacts to potential receptors (compliance monitoring) and to evaluate natural attenuation as a stand alone remedy (natural attenuation monitoring). Samples will be collected from private water wells and groundwater monitoring wells. In addition, surface water samples will be collected from the wetland and Davy Creek located to the south of the site.

Monitored natural attenuation (MNA) refers to the reliance on natural attenuation processes to achieve remediation objectives by reducing the mass, toxicity, mobility, volume, or concentration of contaminants within a time frame that is reasonable (USEPA 1998, USEPA 1999, USEPA 2000, USEPA 2004, WDNR 2004). Natural attenuation processes acting on contaminants can involve a number of interactive processes including dilution, adsorption,


MKE\050810001

advection and dispersion, volatilization, geochemical dynamics and chemical or biological transformation (microbial attenuation). Any of these processes can be significant and will likely affect the nature and distribution of the contaminants in the subsurface environment.

The magnitude of each process will be governed by the prevailing site conditions and the nature of the compound under study. The Office of Solid Waste and Emergency Response (OSWER) Directive 9200.4-17 (1999) identifies three lines of evidence that can be used to demonstrate the occurrence of the natural attenuation of chlorinated aliphatic hydrocarbons, including the following:

• Documented loss of contaminants at the field scale

• Documented presence and distribution of geochemical and biochemical indicators of natural attenuation

• Direct microbiological evidence

At this site, MNA will be evaluated using the first two lines of evidence. These two lines of evidence are often sufficient to determine if MNA is viable at the site, or if enhancements can be made (usually by adding an electron donor) to accelerate cleanup at the site.

1.4.2 Project Schedule CH2M HILL will conduct sampling events through June 30, 2006. Compliance samples will be collected semiannually in the second and fourth quarters of the year and natural attenuation samples will be collected quarterly through June 30, 2006. This will include measurement of water levels, measurement of field parameters, and collection of groundwater and surface water samples, as appropriate. Section 2 of this document describes the sampling schedule and analyses in detail.

1.5 Data Quality Objectives and Criteria for Measurement Data DQOs are qualitative and quantitative statements that specify the quality of data required to support decisions made during or after site-related activities. Project-specific DQOs are developed using the seven-step process presented below.

1.5.1 Step 1: State the Problem For 8 years, a groundwater extraction system operated at the OEP site. This extraction system substantially lowered the concentration of metals and chlorinated (VOCs in groundwater. RMT Inc., of Madison, Wisconsin (on behalf of WDNR) conducted a study to evaluate the potential for further reductions of chlorinated VOCs with continued operation of the groundwater extraction system. The study concluded further subsurface concentration reductions may not be probable using the extraction system. As a result, the extraction system was shut down in July 2004.

For the remaining concentrations of chlorinated VOCs in groundwater, natural attenuation processes are being monitored and evaluated at the site and at downgradient locations. The LTRA consists of monitored natural attenuation (MNA) and compliance with federal


MKE\050810001

groundwater and surface water quality standards for downgradient private water supply wells and Davy Creek, respectively.

The primary decision maker for this project is the USEPA WAM, who is responsible for all phases of the LTRA activities at the OEP site. The USEPA WAM may consult with the WDNR Site Manager prior to making decisions and finalizing plans.

1.5.2 Step 2: Identify the Decision

1.5.2.1 Compliance Monitoring

• Confirm that groundwater contaminants do not extend to drinking water receptors (private water wells) and surface water receptors (Davy Creek).

1.5.2.2 Monitored Natural Attenuation

• Confirm the contaminant plume is not expanding. • Confirm that natural attenuation processes are occurring in groundwater.

1.5.3 Step 3: Identify the Inputs to the Decision


• Groundwater monitoring well, private water well, and surface water samples will be collected and analyzed for chlorinated VOCs to verify that contaminants have not impacted drinking water wells and surface water.

• Groundwater and surface water levels will be collected during sampling events to assess groundwater and contaminant flow directions.

• An offsite laboratory subcontracted by CH2M HILL will analyze the groundwater compliance samples for chlorinated VOCs using the appropriate analytical methods to reach the project specific analytical requirements.

• Compliance groundwater monitoring wells and private water wells will be sampled and analyzed for chlorinated VOCs on a semiannual basis.

• Surface water monitoring for chlorinated VOCs in Davy Creek and the wetland area at three locations: upstream in Davy Creek, downgradient from the site in Davy Creek, and downgradient from the site in wetland area will be conducted on a semiannual basis.


• Groundwater monitoring well samples will be collected and analyzed for chlorinated VOCs, natural attenuation parameters, and field parameters to assess plume size and concentration and to assess natural attenuation of chlorinated VOCs.

• Natural attenuation monitoring wells will be sampled on a quarterly basis for 2 years, with an optional year of monitoring to be conducted at the discretion of the WAM, and analyzed for hydrogeologic and geochemical parameters and chlorinated VOCs to assess natural attenuation conditions and to evaluate natural attenuation as a standalone


MKE\050810001

remedy for this site. The natural attenuation sampling schedule will be reviewed and adjusted after the first 2-year period.

• Groundwater and surface water levels will be collected during sampling events to assess groundwater and contaminant flow directions.

• An offsite laboratory subcontracted by CH2M HILL will analyze the natural attenuation samples using the appropriate analytical methods to reach the project-specific analytical requirements.

• Available historical organic contaminant data will be used in evaluating trends in natural attenuation conditions at the site over time.

1.5.4 Step 4: Define the Study Boundaries The 10-acre study area is composed of the former 4-acre OEP facility site located at 2572 Oak Street in Oconomowoc, Wisconsin and 6 acres of adjacent wetlands located to the southwest of the former facility. Based on data collected during the groundwater treatment system operation in Spring 2004 (RMT Inc. 2004), the organic contaminants of concern for the LTRA are located in unconsolidated aquifer groundwater at the former electroplating site and in the downgradient adjacent wetland area.

Several water supply wells installed in bedrock and associated with private residences are located adjacent to the site. Previous monitoring has shown no detection of site contaminants in the wells (RMT Inc. 2004).

Groundwater elevations at site monitoring wells within the unconsolidated unit (shallow and deep) appear to vary seasonally. Based on the available groundwater elevation data set (elevations only recorded during non-pumping condition in July 2003 and October 2004), and known regional water table behavior, groundwater elevations are expected to be at their maximum in the early spring due to increased precipitation events and at their minimum in late summer/early fall due to decreased precipitation. A comparison between groundwater elevations collected in July 2003 and October 2004 show a range in fluctuation of approximately 0.1 to 2 feet in unconsolidated wells. Surface water elevations are expected to follow this seasonal fluctuation pattern, due to the interconnection of surface water and groundwater.

It is unknown whether all of the groundwater in the unconsolidated unit discharges to Davy Creek or whether part of it flows beneath the creek. A sentinel well nest, to be installed south of Davy Creek, will evaluate the flow between Davy Creek and the unconsolidated groundwater (see FSP, Figure 1). The sentinel wells will be installed further to the south from the site than any existing monitoring wells and on the opposite side of Davy Creek. These wells, once installed, with the existing site monitoring wells and staff gauges will allow for greater understanding of surface water/groundwater interaction. The proposed sentinel well nest location was chosen to be in an apparent downgradient location for both the shallow and deep unconsolidated aquifers. Additionally, the location was chosen based on accessibility using standard drilling techniques.


MKE\050810001

1.5.5 Step 5: Develop a Decision Rule


• For compliance monitoring, Maximum Concentration Limits (MCLs) apply for drinking water samples. Wisconsin Administrative Code (WAC) NR 105, applies for surface water samples.

• If MCL exceedances are observed at a private well, then the private well will be resampled to verify the exceedance. If the resampling results also exceed the MCLs, the private well may be placed on a point of service treatment or other service to provide drinking water below the MCL.

• If exceedances of NR 105 (surface water) criteria are documented for several consecutive quarters of monitoring, then modifications to the monitoring program or remediation approach for the site will be considered.


The WDNR Preventive Action Limits (PALs) are the cleanup criteria for the groundwater at the OEP site (WAC NR 140). The PALs are compared to achievable laboratory reporting limits (RLs) and project quantitation limits in Tables 1-1 and 1-2 for the parameters of interest.

Groundwater data will be evaluated to determine if natural attenuation processes are occurring and to evaluate if the plume is expanding. If the plume has documented expansion over several sampling rounds or if natural attenuation processes do not appear to be occurring, then modifications to the monitoring program or remediation approach will be implemented. Following several quarterly rounds of natural attenuation groundwater sampling, sufficient data would be available to calculate attenuation rates, if necessary.

TABLE 1-1 Project Action Limits and Reporting Limits for Natural Attenuation Parameters in Groundwater Oconomowoc Electroplating Site, Oconomowoc, Wisconsin

Compound Enforcement

Standard Preventive Action Limit

Project Quantitation

Limitsb

Achievable Laboratory

RLs Alkalinity -- Background plus 100 mg/L 5 mg/L 5 Chloride 250 mg/La 125 mg/La 1.0 mg/L 0.8 Sulfate 250 mg/L 125 mg/L 10 mg/L 0.3 Sulfide -- -- 1.0 mg/L 1 Nitrate -- -- 1.0 mg/L 0.04 Total Manganese 50 µg/La 25 µg/La 6 µg/L 1.2 Dissolved Manganese 50 µg/La 25 µg/La 6 µg/L 1.2 Total Iron 300 µg/La 150 µg/La 30 µg/L 24.5 Dissolved Iron 300 µg/La 150 µg/La 30 µg/L 24.5 Methane -- -- 10 µg/L 0.5 Ethane -- -- 10 µg/L 0.5 Ethene -- -- 10 µg/L 0.5 Ammonia (surface water sample only)

-- -- 1.0 mg/L 0.03


MKE\050810001

TABLE 1-1 Project Action Limits and Reporting Limits for Natural Attenuation Parameters in Groundwater Oconomowoc Electroplating Site, Oconomowoc, Wisconsin

Ortho-phosphateb (surface water sample only)

-- -- 1.0 mg/L 0.11

Total Organic Carbon -- Background plus 1 mg/L 1.0 mg/L 0.8 a Criteria is for public welfare concerns (taste or odor aesthetics). b PQLs are determined from common achievable laboratory RLs to be sufficiently lower than the PALs if possible -- = No criteria mg/L = milligrams per liter µg/L = micrograms per liter TABLE 1-2 Project Action Limits for Volatile Organic Compounds in Groundwater Oconomowoc Electroplating, Oconomowoc, Wisconsin

Compound Enforcement

Standard (µg/L) Preventive Action

Limit (µg/L)

Project Quantitation Limits

(µg/L) a

Achievable Laboratory RLs

(µg/L) Acetone 1000 200 2.0 1.5 Benzene 5 0.5 0.2 0.05 Bromodichloromethane 0.6 0.06 0.2 0.04 Bromoform 4.4 0.44 0.2 0.07 Bromomethane 10 1 0.2 0.06 2-butanone (MEK) 460 90 2.0 0.4 Carbon Disulfide 1000 200 0.4 0.1 Carbon Tetrachloride 5 0.5 0.2 0.05 Chlorobenzene -- -- 0.2 0.05 Chloroethane 400 80 0.2 0.06 Chloroform 6 0.6 0.2 0.07 Chloromethane 3 0.3 0.2 0.05 Dibromochloromethane 60 6 0.2 0.09 1,1-dichloroethane 850 85 0.2 0.031 1,2-dichloroethane 5 0.5 0.2 0.04 1,2-dichloroethene 7 0.7 0.2 0.06 cis-1,2-dichloroethene 70 7 0.2 0.06 trans-1,2-dichloroethene 100 20 0.2 0.04 1,2-dichloropropane 5 0.5 0.2 0.06 cis-1,3-dichloropropene 0.2 0.02 0.016 0.016 trans-1,3-dichloropropene 0.2 0.02 0.015 0.015 Ethylbenzene 700 140 0.05 0.05 2-hexanone -- -- 2.0 0.5 4-methyl-2-pentanone -- -- 2.0 0.6 Methylene Chloride 5 0.5 0.2 0.11 Styrene 100 10 0.2 0.04 1,1,2,2-tetrachloroethane 0.2 0.02 0.018 0.018


MKE\050810001

TABLE 1-2 Project Action Limits for Volatile Organic Compounds in Groundwater Oconomowoc Electroplating, Oconomowoc, Wisconsin

Tetrachloroethene 5 0.5 0.2 0.05 Toluene 1000 200 1.0 0.08 1,1,1-trichloroethane 200 40 1.0 0.07 1,1,2-trichloroethane 5 0.5 0.2 0.09 Trichloroethene 5 0.5 0.2 0.03 Vinyl Chloride 0.2 0.02 0.018 0.018 Xylenes (total) 10000 1000 0.2 0.012 a PQLs are determined from common achievable laboratory RLs to be sufficiently lower than the PALs if possible -- = No criteria

1.5.6 Step 6: Specify Limits on Decision Errors The probability of sampling and measurement errors at any site under investigation necessitates developing sampling guidelines and collecting QC samples. Field errors are minimized by having each member of the field team follow the same standard field operating procedures (FOPs) for sampling. Sampling techniques are discussed in detail in the FSP for the site. QC samples are used to verify the data’s accuracy and precision. When a QC sample is outside of the established control limits, the data will be qualified and field corrective action will be implemented when applicable (e.g., when field duplicates are outside of the established control limits).

Field-collected data, such as groundwater pH, temperature, conductance, dissolved oxygen (DO), and redox, will not be subject to data validation procedures.

Decisions made on data that accurately reflects site conditions allows for remedial action evaluation and modification to achieve a reduction in risks to human health and the environment. Consequences of incorrect data decisions might include further downgradient migration of contaminants and potential increased risk to human health and the environment. The likelihood for incorrect decisions is minimized through controlling sampling and measurement errors through adherence to procedures as specified in this QAPP and the Field Sampling Plan.

1.5.7 Step 7: Optimizing the Design

1.5.7.1 Compliance Monitoring Semiannual compliance groundwater samples will be collected initially from 11 residential water wells, 20 groundwater monitoring wells, and 3 surface water locations primarily located downgradient to monitor the edge of the chlorinated VOC detections. Subsequent compliance sampling events will include a group of 8 residential wells composed of residential wells primarily located near the corner of Eva Street and Elm Street. The proposed sample locations will be in the shallow unconsolidated zone, deep unconsolidated zone and the upper bedrock unit. The compliance sampling frequency will be reevaluated and modified, if necessary, each year.


MKE\050810001


Natural attenuation groundwater samples will be collected on a quarterly basis for a 2-year period, with an optional year of monitoring to be conducted at the discretion of the WAM, from 14 existing deep and shallow groundwater monitoring wells. The wells are located both up and down-gradient from the site and will be used to monitor natural attenuation groundwater conditions at the site. The natural attenuation sampling frequency will be reevaluated and modified, if necessary, after the initial 2-year period.

For efficiency and data comparability, it is recommended that compliance and natural attenuation sampling events be coordinated. Water levels will be measured at all accessible monitoring wells, drive-point piezometers, and staff gauges during each sampling event.

1.5.8 Measurement Performance Criteria The measurement performance criteria will be checked on several levels using:

• Built-in QC standards • Senior review • Management controls

The measurement data must abide by specific QC standards. Data that do not meet these standards are qualified accordingly. The analytical data and the QC results will be checked by the bench chemist, the Laboratory’s QAM, and CH2M HILL’s project chemist.

CH2M HILL staff members with relevant technical experience will review all documents that pertain to the project’s quality standards. The field team leader (FTL) will supervise activities to assess whether FOPs are being followed during field sampling activities. Section 3 describes specific QC checks and corrective action measures.

1.6 Instructions for Special Training Requirements/Certification As noted in Subsection 1.2, Project Organization, project team members with the necessary experience and technical skills were chosen to perform required project tasks.

The subcontractor chosen to perform laboratory analyses will meet the project-specific requirements and USEPA and WDNR specifications. Project team members performing fieldwork, including subcontractors, will be required to show proof of meeting 29 Code of Federal Regulations (CFR) 1910.120.

1.7 Instructions for Documentation and Records

1.7.1 Field Sampling Documentation Field sampling activities will be recorded in field logbooks. Field logbook entries will be described with as much detail as possible so that persons going to the site may reconstruct a particular situation without reliance on memory. Modifications to field sampling protocols must be documented in the field logbook. The FTL is responsible for ensuring that modifications to sampling protocols are also documented.


MKE\050810001

The field logbooks to be used will be bound field survey books or notebooks. Logbooks will be assigned to the field crew, but stored in a secure location when not in use. Project-specific document numbers will identify each logbook, the title page of which will contain:

• The name of the person to whom the logbook is assigned • The logbook number • The project name • The project start date • The project end date

At the beginning of each entry, the date, start time, weather, names of all sampling team members present, and the signature of the person making the entry will be documented. Measurements and samples collected will be recorded with a detailed description of the location of the station. The number of all photographs taken will also be noted. Equipment used to make measurements will be identified, along with the date of calibration.

All entries will be made in ink and no erasures will be allowed. If an incorrect entry is made, the information will be crossed out with a single strike mark and initialed. Blank pages will be noted as being intentionally blank.

Samples will be collected following the sampling procedures documented in the Field Operating Procedures (FOPs) located in the FSP. Sample collection equipment will be identified, along with the time of sampling, sample description, parameters being analyzed, and number of containers used. Unique sample identification numbers (IDs) will be assigned to each sample as described in the FSP. Field duplicate samples, which will receive a unique sample ID, will be noted in the field logbook.

Field personnel will provide comprehensive documentation of all aspects of field sampling, field analysis, and sample chain-of-custody (COC). This documentation constitutes a record that allows for the reconstruction of all field events to aid in the data review and interpretation process. All documents, records, and information relating to the performance of the field work will be retained in the project file.

1.7.2 Data Reporting For the purposes of this investigation, two data reporting levels have been defined:

Level 1—Field Data and Health and Safety Reporting. This level of minimal or “results only” reporting is used for the field data and health and safety monitoring, as extensive supporting documentation is not generated or required.

Level 2—Analytical Reporting. Level IV data packages are required for compliance monitoring and natural attenuation data.

1.7.2.1 Field Data Reporting

Information collected in the field through visual observation, manual measurement, and/or field instrumentation will be recorded in field notebooks and then entered into an electronic data log. The FTL or project chemist will review the data for adherence to this QAPP and consistency. Any concerns identified as a result of this review will be discussed with the QAM, corrected if possible, and incorporated into the data evaluation process.


MKE\050810001

Field data calculations, transfers, and interpretations will be conducted by the field crew and reviewed for accuracy by the FTL or project chemist. The appropriate task manager will review field documentation, data reduction, and accuracy of data entries into the data log. The data logs and documents will be checked for:

• General completeness • Readability • Use of appropriate procedures • Whether modifications to sampling procedures are clearly stated • Appropriate instrument calibration and maintenance records • Reasonability of data collected • Correctness of sample locations • Correctness of reporting units, calculations, and interpretations

Where appropriate, field data forms and calculations will be processed and included as appendixes to the reports generated. Original field logs, documents, and data reductions will be kept in the project file.

1.7.2.2 Laboratory Data Reporting

Calculations for analyses are based on regression analyses of calibration curves. Regression analysis is used to fit a curve through calibration standard data. Sample concentrations are calculated using the resulting regression equations.

Whenever possible, analytical data will be transferred directly from the instrument to a computerized data system. Raw data will be stored electronically and a hard copy file will be maintained. Laboratory data entry will be sufficient to document the information used to arrive at reported values.

Electronic data storage will be used when possible. All electronic data shall be maintained in a manner that prevents inadvertent loss, corruption, and inappropriate alteration. Electronic data shall be accessible and retrievable for a period of 10 years after project completion.

Raw data will be examined by the laboratory to assess compliance with the QC guidelines stated in the appropriate analytical standard operating procedures (SOPs) in Appendix A. Surrogate, matrix spike, and QC check sample recoveries will be checked. In addition, samples and laboratory blanks will be checked for possible contamination or interferences. Chromatograms (where applicable) and concentrations will be checked to ensure that sample results are within the calibration range; if necessary, dilutions will be performed as defined by the initial calibration range.

Any deviations from stated guidelines must be addressed through corrective action. Deviations caused by factors outside of the laboratory’s control, such as matrix interference, will be noted with an explanation in the report narrative. Calculations will be checked and reports will be reviewed for errors, oversights, or omissions.

Data will then be submitted to the laboratory QAM for review and approval. The Laboratory QAM will review the package, ensure that any necessary corrections are made, and forward it to the laboratory project manager for review. A copy of the data package will be filed in the project file. Mailed data packages, along with applicable electronic data


MKE\050810001

deliverables (EDDs), will be sealed in an appropriate shipping container with a custody seal and logged on a document mailing log.

1.7.3 Electronic Analytical Record Format CH2M HILL requests that three ASCII text files be generated as the EDDs for each batch/sample delivery group (SDG): one for sample (SMP) data, one for tests and results with quality control (TRSQC) data, and one for test batch (BAT) data. The specifications for these files are given to the laboratory in the laboratory contract or SOW.

1.7.4 Project Record Maintenance and Storage Project records will be stored and maintained in accordance with CH2M HILL’s Data Management Plan (DMP) discussed in Subsection 2.9 of this QAPP. Each project team member is responsible for filing all project information or providing it to the project assistant familiar with the project filing system. Individual team members may maintain separate files or notebooks for individual tasks, but must provide such materials to the project file room upon completion of each task.

The general project file categories are as follows:

• Correspondence • Non-laboratory project invoices and approvals by vendor • Original unbound reports • Non-laboratory requests for proposals (solicitations), bids, contracts, and SOWs • Field data • Data evaluation and calculations • Site reports from others • Bound report copies of Category C • Photographs • Insurance documentation • Laboratory analytical data and associated documents/memos • Regulatory submittals, licensing, and permitting applications • Site and reference material • Health and safety plans • Figures and drawings

A project-specific index of file contents must be kept with the project files at all times.


MKE\050810001

SECTION 2

Data Generation and Acquisition

This section describes the procedures for acquiring, collecting, handling, measuring, and managing data in support of this sampling activity. It addresses the following data generation and acquisition aspects:

• Sampling process design

• Sample handling and custody requirements

• Sampling method requirements

• Laboratory analytical method requirements

• Laboratory QC requirements

• Field and laboratory instrument calibration and frequency

• Inspection and acceptance requirements for supplies and consumables

• Data acquisition requirements

• Data management

• Field and laboratory instrument and equipment testing, inspection, and maintenance requirements

2.1 Sampling Process Design The sampling locations and frequencies of collection chosen best fulfill the project objectives stated in Step 2 of the DQO process. There are two intended purposes to groundwater sampling for the project. The first purpose is to gather groundwater data at residential wells, monitoring wells located in the downgradient portions of the chlorinated VOC plume, and surface water samples to evaluate impacts to potential receptors and compliance with state and federal groundwater and surface water standards (i.e., compliance monitoring). Secondly, groundwater data will be collected throughout the chlorinated VOC plume to assess natural attenuation as a sole remedy for the site (i.e., natural attenuation monitoring).

2.1.1 Compliance Monitoring Compliance groundwater monitoring will be performed at 11 water supply wells, 20 groundwater monitoring wells, and 3 staff gauges (for collection of surface water samples) on a semi-annual basis (Table 2-1). Groundwater sampling of the shallow unconsolidated zone, deep unconsolidated zone, and the upper bedrock unit will be performed. The sample locations are primarily located in downgradient locations to monitor the edge of the area of


MKE\050810001

chlorinated VOC detections. VOC analysis will be performed at compliance sampling points (FSP, Table 2). Sampling will be performed in accordance with the methods identified in the FSP.

Water supply wells are generally within 250 feet of the site (defined as area bounded by Oak, Eva, and Elm Streets and the Town of Ashippun property).

2.1.2 Natural Attenuation Monitoring Supplementing the compliance sampling is quarterly natural attenuation sampling which is being evaluated as a standalone remedy for the site. Natural attenuation monitoring will be performed at 14 groundwater monitoring wells and 3 surface water locations on a quarterly basis to evaluate seasonal variability (Table 2-1). Groundwater sampling of the shallow and deep unconsolidated zone will be performed. The sample locations are within apparent source areas and areas upgradient and downgradient from these sources. Natural attenuation parameters (nitrate, total and dissolved manganese, total and dissolved iron, sulfate, sulfide, methane, ethane, ethane, chloride, alkalinity, and total organic carbon), VOC, and field parameters (water level, temperature, pH, specific conductance, dissolved oxygen [DO], and oxidation reduction potential [ORP]) will be sampled. Sampling will be performed in accordance with the methods identified in the FSP.

TABLE 2-1 Long-Term Remedial Action Sampling Summary Oconomowoc Electroplating Site, Oconomowoc, Wisconsin

QC Samples

Sampling Event Type Samples Dup EB TB MS MSD FB

Total Number of Samples2

Compliance Monitoring 11 private wells1, 20 monitoring wells, 3 surface water samples

3 2 8 2 2 1 50

Natural Attenuation Monitoring 14 monitoring wells, 3 surface water samples 1 1 4 1 1 1 26

Note: 1Initially 11 private wells will be sampled. Subsequent sample events will include 8 private wells. A rotating sampling schedule for the private wells will be established. 2 Total number is estimated and is subject to change based on field conditions. EB = equipment blank TB = trip blank FB = field blank

2.1.3 Water Level Measurements Water levels will be taken at accessible groundwater monitoring wells, drive point piezometers, and staff gauges during each sample event.

2.1.4 Field Parameters DO, pH, ORP, temperature, and specific conductance measurements will be taken at each natural attenuation monitoring point using a flow-through cell or a down-hole instrument.


MKE\050810001

2.1.5 Sampling Method Requirements The following SOPs are contained in the FSP for field sampling method and decontamination procedures:

• Low-flow groundwater sampling • Groundwater and surface water level measurement • Field logbook • Equipment calibration ( air monitoring, pH, conductivity, temperature, DO, ORP) • Field filtering samples • Field sampling equipment decontamination • Sample handling, packaging, and shipping • Documentation/chain of custody procedures • Surface water sampling • Private residential well groundwater sampling • Hollow-stem auger drilling and soil sampling logging • Monitoring well installation and development

Before sampling at a station, reusable (i.e., non-dedicated) sampling equipment will be rinsed with Alconox, rinsed with distilled water, then rinsed with methanol, again rinsed with distilled water, and air-dried. Large sampling equipment will be washed with a high-pressure water wash using a brush, as necessary, to remove any particles. Equipment blanks (EBs) will be collected by passing high performance liquid chromotagraphy (HPLC)-grade laboratory water over decontaminated sampling equipment. The EBs will then be analyzed for the same parameters as the field samples to assess the effectiveness of the decontamination procedures. Details can found in the FOPs in the FSP.

2.2 Sample Handling and Custody Requirements

2.2.1 Sample Handling and Preservation Table 2-2 summarizes the sample preservation and holding requirements.

Corrective actions will be taken as soon as a problem is identified. Such actions may include discontinuing the use of a specific bottle lot; contacting the bottle suppliers for retesting the representative bottle from a suspect lot; resampling suspect samples; validating the data, taking into account that the contaminants could be introduced by the laboratory (e.g., common laboratory solvents, sample handling artifacts) as a bottle QC problem; and determining whether the bottles and data are usable.


MKE\050810001

TABLE 2-2 Sample Containers, Preservations, and Holding Times Oconomowoc Electroplating Site, Oconomowoc, Wisconsin

Parameter Container Preservation/Storage Maximum Holding

Time

VOCs Three 40-mL glass vials HCl to pH <2, 4°C 14 days to analysis

Metals ( Diss. Mn &Fe)a One 500-mL poly HN03 to pH <2, 4°C 180 days

Metals (Total Fe & Mn) One 500-mL poly HN03 to pH <2, 4°C 180 days

Alkalinityb One 1-L poly 4°C 14 days

Chloride, Sulfateb One 1-L poly 4°C 28 days

Sulfide One 1-L amber glass NaOH to pH>9, Zn acetate, 4°C

7 days

Methane, Ethane, Ethene Three 40-mL glass vials 4°C 14 days

Total Organic Carbon One 250-mL poly HCl to pH < 2, 4°C 28 days

Ammonia (surface water sample only)

One 250-mL poly H2SO4 to pH < 2, 4°C 28 days

Ortho-phosphateb (surface water sample only)

One 1-L poly 4°C 48 hours

Nitrateb One 1-L poly 4°C 48 hours

Notes: a Dissolved Iron and Manganese will be field filtered and collected in a separate container than the total metals. bAlkalinity, chloride, sulfate ortho-phosphate and nitrate will all be collected in one 1-L poly bottle. mL = milliliter L = liter

2.2.2 Sample Identification System CH2M HILL has devised a sample numbering system that will be used to identify each sample, including duplicates and blanks. Detailed sample-numbering information is located in Section 4.1.1, Sample Identification, of the FSP.

2.2.3 Sample Packaging Sample handling, packaging and shipping procedures are described in Sample Handling, Packaging, and Shipping FOP, of the FSP.

Sample coolers will be shipped to arrive at the laboratory the morning after sampling (priority overnight) or will be sent by a courier to arrive the same day. The laboratory will be notified of the sample shipment and the estimated date of arrival of the samples being delivered.

2.2.3.1 Shipping Airbills If samples are shipped, airbills will be retained to provide a record for sample shipment to the laboratory. Completed airbills will accompany shipped samples to the laboratory and be


MKE\050810001

forwarded along with data packages. The airbill number will be documented on the COC form accompanying the samples to the laboratory for sample-tracking purposes. Airbills will be kept as part of the data packages in the project files.

2.2.4 Sample Custody Accurate records and control of sample and data custody are necessary to provide relevant and defensible data. COC is addressed during field sample collection, data analyses in the laboratory, and through proper handling of project files. Persons will be considered to have custody of samples when samples are in their physical possession, in their view after being in their possession, or in their physical possession and secured to prevent tampering. In addition, when samples are secured in a restricted area accessible only to authorized personnel, they will be deemed to be in the custody of such authorized personnel.

COC forms will provide the record of responsibility for sample collection, transport, and submittal to the laboratory. Field personnel designated as responsible for sample custody will fill out COC forms at each sampling site, at a group of sampling sites, or at the end of each day of sampling. In the event that samples are relinquished by the designated sampling person to other sampling or field personnel, COC forms will be signed and dated by the appropriate personnel to document the custody transfer. Original COC forms will accompany samples to the laboratory, and copies will be forwarded to the project files.

2.2.4.1 Field Custody Procedures COC forms will be required for all samples. The sampling crew in the field will initiate COC forms. COC forms will contain the sample’s unique ID, sample date and time, sample description, sample type, preservation (if any), and analyses required. Original COC forms, signed by the sampling crew, will accompany the samples to the laboratory (see example forms in Appendix B). A copy of relinquished COC forms will be retained with the field documentation. COC forms will remain with the samples at all times. Samples and signed COC forms will remain in the sampling crew’s possession until samples are delivered to the express carrier (e.g., Federal Express), hand delivered to the laboratory, or placed in secure storage.

2.2.4.2 Laboratory Custody Procedures

Laboratory custody procedures will be in place to ensure the integrity of sample and laboratory data handling. Laboratory custody procedures are defined in the laboratory’s COC SOP in Appendix A.

2.2.4.3 Laboratory Sample Receipt

Upon sample receipt, the laboratory sample custodian will verify package seals, open the packages, check temperature blanks (and record temperatures), verify sample integrity, and inspect contents against COC forms. The laboratory project manager will be contacted to resolve any discrepancies between sample containers and COC forms. Once the shipment and COC form are in agreement, the sample custodian will initiate an internal COC form as well as supply the laboratory task manager with a sample acknowledgement letter. When applicable, sample preservation will be checked and pH documented. If the sample


MKE\050810001

temperatures are outside the required range, the laboratory will contact the SM or the contractor, who will determine the proper course of action.

Samples will be logged into the Laboratory Information Management System (LIMS), which assigns a unique laboratory number to each sample. LIMS will be used by all laboratory personnel handling samples, to ensure all sample information is captured. Analyses required, will be specified by codes assigned to samples at log-in. Labels containing the laboratory sample number are generated and placed on sample bottles.

2.2.4.4 Laboratory Sample Storage

After the laboratory labels the samples, they will be moved to locked refrigerators where they will be maintained at 4 degrees Celcius(°C). Access to refrigerators will be limited to members of the sample management department.

When samples are required, an appropriate member of the sample management department will locate the samples in the locked refrigerator, sign and date the internal sample tracking form and provide the sample(s) to the analyst. When the analyst is finished with samples, unused portions will be returned to an appropriate member of the sample management department for replacement in a secure refrigerator. The analyst will sign and date internal COC forms. In the event that entire samples are depleted during analysis, a notation of “sample depleted” or “entire sample used” will be made on the internal COC forms.

Sample extracts will be stored in designated secure, refrigerated storage areas. Samples and sample extracts will be maintained in secure storage until disposal. No samples or extracts will be disposed of without prior written approval from an appropriate member of the project team. The sample custodian will note sample disposal date in the sample ledger. The laboratory will dispose of samples in accordance with applicable regulations.

2.2.4.5 Laboratory Logbooks

Workbooks, bench sheets, instrument logbooks, and instrument printouts will be used to trace the history of samples through the analytical process and document important aspects of the work, including associated QC. As such, all logbooks, bench sheets, instrument logs, and instrument printouts will be part of the laboratory’s permanent record. In addition, relevant information will be entered into the LIMS at the time information is generated.

Each page or entry will be dated and initialed by the analyst at the time of entry. Entry errors will be crossed out in indelible ink with a single stroke, corrected without obliterating or writing directly over the erroneous entry, and initialed and dated by the individual making the correction. Unused pages of logbooks will be completed by lining out unused portions that are then initialed.

The analyst will record information regarding the sample, the analytical procedures performed, and the results on laboratory forms or personal notebook pages, and enter this information in LIMS. These notes will be dated and will identify the analyst, instruments used, and instrument conditions.

Sufficient raw data records must be retained to permit reconstruction of initial instrument calibrations (e.g., calibration date, test method, instrument, analysis date, each analyte


MKE\050810001

name, concentrations and responses, calibration curves, response factors, or unique equations or coefficients used to reduce instrument responses into concentrations).

The laboratory group leaders will periodically review laboratory notebooks for accuracy, completeness, and compliance with this QAPP. The laboratory group leader will verify all entries and calculations. If all entries on the pages are correct, the laboratory group leader will initial and date the pages. Corrective action will be taken for incorrect entries before the laboratory group leader signs.

2.2.4.6 Laboratory Project File

Documentation will be placed in a single, secured project file, maintained by the Laboratory Project Manager. This file will consist of these components, all filed chronologically:

• Agreements • Correspondence • Memos • Notes and Data

Reports (including QA reports) will be filed with correspondence. Analytical laboratory documentation and field data will be filed with notes and data. Filed materials may only be removed by authorized personnel on a temporary basis. The name of the person removing the file will be recorded. Laboratories will retain project files and data packages for a minimum of 7 years unless otherwise agreed.

2.2.4.7 Computer Tape and Hard Copy Storage

All electronic files will be maintained on CD-ROM (preferred media), magnetic tape, or diskette for 10 years; hard copy data packages (including chromatograms) will be maintained in files for 7 years. The computer tape and hard copy storage should include notation of instrument run files and calibration.

2.3 Analytical Method Requirements Once the samples have been properly collected and documented, they will be submitted to the selected Wisconsin-certified (per WAC NR 149) laboratory for analysis. The analytical laboratory(s) will be chosen both on required certification and the ability to perform the analyses with a high level of analytical quality. Samples will be analyzed in accordance with USEPA methods and USEPA SW-846 methods.

Table 2-3 lists the required methodologies and quantification limits for the analyses to be performed during the LTRA.


MKE\050810001

TABLE 2-3 Long-Term Remedial Action Parameter List and Contract-Required Limits of Quantification Oconomowoc Electroplating Site, Oconomowoc, Wisconsin

Parameter Analytical Method Project Quantitation Limits

Alkalinity EPA 310.2 5 mg/L

Chloride EPA 300.0 1.0 mg/L

Sulfate EPA 300.0 10 mg/L

Sulfide EPA 376.1 1.0 mg/L

Nitrate EPA 353.2 1.0 mg/L

Total manganese SW-846 6010/6020 6 µg/L

Dissolved manganese SW-846 6010/6020 6 µg/L

Total Iron SW-846 6010/6020 30 µg/L

Dissolved iron SW-846 6010/6020 30 µg/L

Methane, ethane, ethene RSK 175 10 µg/L

Ammonia 350.1 TBD

Ortho-phosphate 300.0 or 365.1 TBD

Total Organic Carbon SW-846 9060 1.0 mg/L

VOCs SW-846 8260 Per Table 1-2

2.3.1 Analytical SOPs The laboratory uses analytical SOPs to ensure that the samples submitted are accurately and analyzed precisely. The analytical SOPs reflect the requirements of the stated methods while including internal QC criteria. If not otherwise stated within this QAPP, the QC criteria used during the analyses are those stated within the analytical SOPs.

2.4 Quality Control Requirements The contracted analytical laboratory shall have a QC program to assess the reliability and validity of the analyses being performed. The purpose and creation of QC samples is discussed and summarized below. Table 2-1 outlines the anticipated field QC samples to be taken.

2.4.1 Quality Control Samples Field QC samples will be collected to determine the accuracy and precision of the analytical results. The QC sample frequencies are stated below and summarized in Table 2-1. All sampling activities will be conducted in accordance with the Health and Safety Plan and all sample-handling procedures will be in accordance with this QAPP. Table 2-3 summarizes sample containers, holding times, and preservation requirements.


MKE\050810001

EBs will be collected to monitor cleanliness of sampling equipment and the effectiveness of decontamination procedures. Contamination from the sampling equipment can bias the analytical results high. EBs will be prepared by filling sample containers with laboratory-grade analyte-free water that has been passed through a decontaminated or unused disposable sampling device (see FSP, Appendix A for the FOP on equipment decontamination). The required QC limits for EB concentrations are to be less than the method’s RL. Composite EBs will be sampled at a frequency of one for every 20 field samples from every non-dedicated piece of sampling equipment. The results from the EBs will be assessed for bias resulting from contamination. If bias is present, the usability of the associated analytical results will be further assessed and qualified, as appropriate. EBs will only be analyzed in the event that non-dedicated sampling equipment will be used.

Matrix spikes and matrix spike duplicates (MS/MSDs) will be used to assess the effects of sample matrix interference on the precision and accuracy of analyte recovery. MS/MSD pairs will be analyzed at a frequency of one pair for every 20 samples. QA/QC precision and accuracy criteria shall be those stated in the attached analytical SOPs.

Field duplicates are collected in the field from a single aliquot of sample to determine the precision and accuracy of the field team’s sampling procedures. Field duplicates will be collected and analyzed at a frequency of one duplicate for every 10 samples. The precision criteria for the duplicate samples will be + 20 percent for aqueous samples.

Volatile trip blanks (TBs) are used to detect VOC contamination during bottle shipment to the sampling site and subsequent sample handling and shipping. The laboratory will provide TB samples along with the bottle shipment. TBs will consist of a certified clean sample vial filled with contaminant-free laboratory water. The vials will contain no head space and be preserved with hydrogen chloride (HCl) to a pH less than 2. At a minimum, one volatile TB sample will be sent in each cooler containing VOCs.

The laboratory accuracy and precision control limits are those specified in the analytical SOPs found in Appendix A. The laboratory must follow the QC requirements located in Table 2-4 if they are more stringent than the analytical SOPs.

TABLE 2-4 Laboratory Quality Control Requirements Oconomowoc Electroplating Site, Oconomowoc, Wisconsin

Compound Percent Recovery Relative Percent Difference

LCS/LCSD 60-130% 30%

MS/MSD 60-130% 30%

2.4.2 Data Precision, Accuracy, and Completeness Field QA/QC samples and laboratory internal QA/QC samples are collected and analyzed to assess the data’s usability. Analytical SOPs, state acceptance criteria for precision, and accuracy requirements for these QC samples. The QA/QC criteria for the internal laboratory QC samples that are not referenced in the appropriate analytical SOPs shall be those stated


MKE\050810001

in the referenced methods. Completeness is the percentage of usable data obtained during the sampling event and its acceptance criteria is project-specific.

2.4.2.1 Precision

The precision of laboratory analysis will be assessed by comparing the analytical results between MS/MSDs. The precision of the field sampling procedures will be assessed by reviewing field duplicate sample results. The relative percent difference (RPD) will be calculated for the duplicate samples using the equation

%RPD = {(S - D)/[(S + D)/2]} × 100

where: S = First sample value (original value)

D = Second sample value (duplicate value)

The precision criteria for duplicate samples will be + 20 percent for aqueous samples. Sample results shall be qualified “J” as estimated in quantity when this QC limit is exceeded. The acceptable MS/MSD precision criteria are stated in Table 2-4 if they are more stringent than the analytical SOPs.

2.4.2.2 Accuracy

Accuracy of laboratory results will be assessed for compliance with the established QC criteria using the analytical results of method blanks, reagent/ preparation blanks, and MS/MSD samples. Laboratory results accuracy will be assessed for compliance with the established QC criteria described in the analytical SOPs. The percent recovery (%R) of laboratory control samples will be calculated using the equation

%R = (A/B) × 100

Where: A = The analyte concentration determined experimentally from the laboratory control sample

B = The known amount of concentration in the sample

The accuracy criteria for the QA/QC samples are those stated in Table 2-4 if they are more stringent than the analytical SOPs.

2.4.2.3 Completeness

The data completeness of laboratory analyses results will be assessed for compliance with the amount of data required for decision making. Complete data is data that is not rejected. Data qualified with qualifiers such as a “J” or a “UJ” are still deemed acceptable and can still be used to make project decisions. The completeness of the analytical data is calculated using the following equation:

% Completeness = [(Valid data obtained)/(Total data planned)] × 100

The percent completeness goal for this sampling event is 90 percent.


MKE\050810001

2.4.2.4 Representativeness

Representativeness is the degree that sampling data accurately and precisely represent site conditions, and is dependent on sampling and analytical variability and the variability of environmental media at the site. Representativeness is a qualitative “measure” of data quality.

The goal of achieving representative data in the field starts with a properly designed and executed sampling program that carefully considers the project’s overall DQOs. Proper location controls and sample handling are critical to obtaining representative samples.

The goal of achieving representative data in the laboratory is measured by assessing accuracy and precision. A laboratory will provide representative data when all of the analytical systems are in control. Therefore, representativeness is a redundant DQO for laboratory systems if proper analytical procedures are followed and holding times are met.

In addition, laboratories must demonstrate that the staff is qualified to perform the analyses, certified, and proficient in the analytical methods being employed.

2.4.2.5 Comparability

Comparability is the degree of confidence that one data set can be compared to another. Comparability is a qualitative “measure” of data quality.

The goal of achieving comparable data in the field starts with a properly designed and executed sampling program that carefully considers the project’s overall DQOs. Proper location controls and sample handling are critical to obtaining comparable samples.

The goal of achieving comparable data in the laboratory is measured by assessing accuracy and precision. A laboratory will provide comparable data when all of the analytical systems are in control. Therefore, comparability is a redundant DQO for laboratory systems if proper analytical procedures are followed and holding times are met.

2.4.2.6 Sensitivity

Sensitivity is defined as the ability of the method or instrument to detect the contaminant of concern and other target compounds at the level of interest. Appropriate sampling and analytical methods will be selected (see Tables 1-1 and 1-2) that have QC acceptance limits that support the achievement of established performance criteria. Assessment of analytical sensitivity will require thorough data validation. Sensitivity of field parameters during the collection of water samples will be monitored until stabilized as indicated in Table 2-5.

TABLE 2-5 Stabilization Criteria with References for Water Quality Indicator Parameters*

Parameter Stabilization Criteria

pH ± 0.1

Specific Electrical Conductance (SEC) ± 3%

Oxidation-Reduction Potential (ORP) ± 10 millivolts


MKE\050810001

TABLE 2-5 Stabilization Criteria with References for Water Quality Indicator Parameters*


Turbidity ± 10% (when turbidity is greater than 10 nephelometric turbidity units)

Dissolved Oxygen (DO) ± 0.3 milligrams per liter

*USEPA, 2002.

2.5 Instrument/Equipment Testing, Inspection, and Maintenance Requirements

2.5.1 Field Instrument Maintenance

2.5.1.1 Equipment Monitoring The field equipment will be calibrated daily, checked for indications of poor performance, and the results documented. Any discrepancies will be immediately reported to the appropriate personnel for resolution.

The field team will maintain a sufficient supply of spare parts to minimize downtime. Whenever possible, backup instrumentation will be on hand.

The field equipment will be maintained as stated in the equipment’s specific operating manuals. The field equipment to be used in taking field measurements includes:

• Organic vapor photoionization detector (PID) • DO, temperature, pH, conductivity, and ORP meters

2.5.2 Laboratory Equipment/Instruments Only qualified personnel will service instruments and equipment. Repairs, adjustments, and calibrations will be documented in the appropriate logbook or data sheet.

2.5.2.1 Instrument Maintenance

Preventive maintenance of laboratory equipment will follow guidelines recommended by the manufacturer. A malfunctioning instrument will be repaired by in-house staff or through a service call to the manufacturer.

The laboratory will maintain a sufficient supply of spare parts for its instruments to minimize downtime. Whenever possible, backup instrumentation will be on hand.

Whenever practical, analytical equipment should be maintained under a service contract. Such contracts allow for preventative system maintenance and repair on an “as-needed” basis. The laboratory should have sufficiently trained staff to allow for the day-to-day maintenance of equipment. All laboratory instruments will be maintained in accordance


MKE\050810001

with manufacturer’s specifications and within the requirements of the laboratory Quality Assurance Manual.

All maintenance activities are required to be documented in the logbooks to provide a history of maintenance records.

2.5.2.2 Equipment Monitoring

Operation of balances, ovens, refrigerators, and water purification systems will be checked daily and documented. Any discrepancies will be immediately reported to the appropriate laboratory personnel for resolution.

Specific laboratory preventative maintenance procedures are found in the laboratory’s internal laboratory Quality Assurance Manual.

2.6 Instrument Calibration and Frequency

2.6.1 Field Instruments Calibration of field instruments, as specified by the FOPs (see FSP, Appendix A), will be performed at the intervals specified by the manufacturer or more frequently as conditions dictate. In the event that an internally calibrated field instrument fails to meet calibration/checkout procedures, the vendor will replace it and return it to the manufacturer for service.

2.6.2 Laboratory Instruments Calibration procedures for the laboratory equipment will be as specified in the analytical SOPs. The designated laboratory personnel performing QC activities will maintain and file records of calibration, repairs, or replacement. These records will be filed where the work is performed and subject to a QA audit.

All standards used in equipment will be traceable, directly or indirectly, to the National Institute of Standards and Technology (NIST). All standards received will be logged into standard receipt logs maintained by the individual analytical groups. Each group maintains a standards log that tracks the preparation of standards used for calibration and QC purposes.

2.7 Inspection/Acceptance Requirements for Supplies and Consumables

It is expected that several contractors will provide various services under multiple project tasks. The required services must meet the task scope, specified levels of quality, and the submittal schedule. Project contractors or vendors should have contractual arrangements with their material suppliers.


MKE\050810001

2.8 Non-Direct Measurements This subsection describes the identity of the types of data needed for project implementation and decision making not obtained from direct measurements.

The project objectives are first identified, to assess what types of information are needed to implement a project plan to meet the proposed objectives summarized in Section 1. Typically, the data needed to achieve the project objectives include site maps, sampling location selection and sample identifiers, laboratory method selection and detection limit verification, analytical parameter lists and critical values, field measurement lists, and a project schedule. This information is included in this QAPP.

The sampling design and rationale of the LTRA sampling activities were based upon previously collected data. Site maps and other site characterization data were used in the selection of monitoring well locations.

2.9 Data Management Plan This DMP outlines the procedures for storing, handling, accessing, and securing data collected during this sampling event. Data gathered during this sampling event will be consolidated and compiled into a project database system that can be used to evaluate site conditions and data trends. This DMP will serve as a guide for all database users. The DMP is subject to future revision to allow the database management system to be modified as it is developed and maintained. This plan describes the following:

• The responsibilities of the project team for data management • The Data Management System (DMS) to be established for the project • The development of the base maps onto which the data will be plotted • The types of data that will be entered into the DMS and the process of data entry

2.9.1 Team Organization and Responsibilities The following are the team members and their responsibilities for the data management process:

Site Manager—Responsible for establishing the sample tracking system.

Project Chemist—Responsible for providing weekly the COC forms and other sampling information to the SM for use in sample tracking. Oversees proper use of the Forms II Lite EPA system and accuracy of the information entered. Reviews laboratory data for accuracy and quality and compares electronic outputs for accuracy to laboratory hard copies. Conducts tracking of samples, forwards tracking information and received data to the Database Manager, and identifies the data inputs (e.g., sample numbers) to use in generating tables and plots.

Database Manager—Responsible for setting up DMS in consultation with the Project Chemist at the beginning of the data evaluation task. Also oversees the data management process including data conversion/manual entry into DMS, QC of the entered data, and


MKE\050810001

preparation of the required tables and plots of the data. Coordinate with person responsible for review of the entered data for QC purposes. Forwards all deliverables to the SM.

2.9.2 Sample Tracking The Project Chemist is responsible for tracking samples to ensure that the analytical results for all samples sent for analysis are received. Copies of the COC’s from the field team are used to enter in sample IDs, collect date, and analyses. Upon receipt of a sample receipt notice from the laboratory, the date received by the laboratory and a date the hardcopy is due will be entered. Likewise, upon receipt of the hardcopy and EDD, the date they were received will also be entered. The EDDs will be uploaded when received from the laboratory, and will be tracked in the sample tracking table. Validation qualifiers will be added to the database and results qualified accordingly.

2.9.3 Data Types Activities performed at the site will involve accessing a number of different types of data collected or retained for various uses. The following provides a general description of the overall contents of the project database, as based upon the available data and the data to be collected.

2.9.3.1 Historical Data Sources of historical data for the site include information collected by the USEPA, WDNR, and RMT Inc. to characterize site conditions. This information includes both chemical and physical data for the site collected from previous OEP site activities.

2.9.3.2 Site Characterization Data

The QAPP, of which this DMP is a part, identifies additional data to be collected for further site characterization. Natural attenuation parameters along with VOCs will be collected during the Enhanced Attenuation Study Plan include the following:

• Groundwater level measurements • Groundwater field parameter measurements • Monitoring analyte concentrations

These data will be added to the project database as they become available. The data will include new data collected in the field and laboratory and reviewed by CH2M HILL. The data source will be noted in the database. Procedures for incorporating the data into the database are presented in subsequent sections of this DMP.

2.9.4 Data Tracking and Management Every data set received from analytical laboratories will be tracked individually as discussed in Section 2.9.2 of this QAPP.

2.9.4.1 Hard Copy

Measurements made during field data collection activities will be recorded in field logbooks. Field data will be reduced and summarized, tabulated, and stored along with the field logbooks.


MKE\050810001

All raw analytical laboratory data are stored as the original hard copy. Hard copy information includes COC forms, analytical bench sheets, instrument printouts and chromatograms, certificates of analyses, and QA/QC report summaries. Validation reports will be stored with the hard copy reports.

2.9.4.2 Data Input Procedures

Sampling information, analytical results, applicable QA/QC data, data validation qualifiers, and other field-related information will be entered into the project database for storage and retrieval during data evaluation and report development. The analytical data will be loaded into the database using EDD files received from the analytical laboratory. Validation qualifiers will be entered manually into the database. Printing validated data reports from the database and manually comparing them to the validated summary analytical forms received from the USEPA validators will confirm correct data entry. Other available field-related data collected, such as water levels, newly installed well information, etc., will be manually entered onto standard EDD templates for loading into the database and for QC after loading.

Historical data, either in hard copy or electronic form, will be manually entered onto or formatted to standard EDD templates for database loading. The entry of other field-related data, as well as historical site data, will be confirmed by comparing the hard copy printouts from the database against the hard copies used to perform the data entry. All data entry confirmation procedures and results will be documented.

2.9.5 Computer Database The technical data, field observations, laboratory analytical results and analytical data validation will be managed using EQuIS®, a third-party database system by Earthsoft, Inc. that is currently used by portions of USEPA Region 5 to store and analyze project data submissions. The core EQuIS® applications are the Chemistry and Geology modules, each of which is associated with its own underlying Microsoft Access database. CH2M HILL currently owns licenses for the Geology and Chemistry modules. The EQuIS® database system is based on a relational model, in which independent tables, each containing a certain type or entity of data, can be linked through selected fields that are common to two or more tables. This database design allows for the inclusion of historical data, and allows users to effectively conduct trend analysis and generate a variety of data reports to aid in data interpretation.

The database must be protected from unauthorized access, tampering, accidental deletions or additions, and data or program loss that can result from power outages or hardware failure. The following procedures will be adopted to ensure this protection:

• The master database will be stored on a network file server local to the installation of the EQuIS® DMS. Members of the data management team involved in loading, modifying, or querying the database will be given access through EQuIS® user accounts and passwords, as well as the appropriate network server permissions.

• Copies of the master database will be stored on the local area network (LAN) file server for access by project staff through reporting tools developed to minimize possible


MKE\050810001

database corruption by users. Whenever the master database is updated or modified, it will be recopied to the LAN to ensure that the current copy is available to users.

• Daily backups of the master database and its copies will be made to ensure that the data will not be lost due to problems with the network.

2.9.6 Documentation Documentation of data management activities is critical because it provides:

• A hard copy record of project data management activities • Reference information critical for database users • Evidence that the activities have been properly planned, executed, and verified • Continuity of data management operations when personnel changes occur

This DMP will serve as the initial general documentation of the project data management efforts. Additional documentation will also be maintained to document specific issues, such as database structure definitions, database inventories, database maintenance, user requests, database issues and problems, and client contact.

2.9.7 Evidence File The final evidence file will be the central repository for all documents that constitute evidence relevant to sampling and analysis activities. CH2M HILL is the custodian of the evidence file and maintains the contents of the evidence files for the project, including all relevant records, reports, logs, field notebooks, pictures, contractor reports, and data reviews in a secured area with limited access.

CH2M HILL will keep all records until project completion and closeout. As necessary, records may be transferred to an offsite records storage facility. The records storage facility must provide secure, controlled-access records storage. Records of raw analytical laboratory data, QA data, and reports will be kept by the subcontract laboratory for at least 7 years.

2.9.8 Presentation of Site Characterization Data Depending on the data user needs, data presentation may consist of any of the following formats:

• Tabulated results of data summaries or raw data • Figures showing concentration isopleths or location-specific concentrations • Tables providing statistical evaluation or calculation results • Presentation tools, such as ARCINFO, Surfer8 or similar analysis/ presentation aids

In addition to laboratory data, other physical data will be collected during field efforts, including (but not limited to) water level measurements. This information will be stored in the project database. Other types of data elements may be added as the field investigation needs and activities evolve.

2.9.9 Evaluation of Natural Attenuation Monitoring Data Data evaluation methods as presented by Pope, et. al. (2004) will be used for natural attenuation monitoring data and include:


MKE\050810001

• Determination of temporal and spatial trends in contaminant concentrations or mass

• Comparisons of observed contaminant concentrations with previous predictions or established milestones

• Comparisons of contaminant concentrations in areas outside of previous plume boundaries with specified action levels

The results of the data evaluation will be documented in a summary report on an annual basis in accordance with Pope, et. al. (2004) and WDNR (2003). Representative spatial and trend plots will be included in the report. The list of wells to be sampled and the parameters analyzed at each well will be reevaluated each year based on previous data collected. Following collection of sufficient data (several monitoring rounds), recommendations for MNA or possibly enhanced attenuation can be made.


MKE\050810001

SECTION 3

Assessment/Oversight

3.1 Assessments and Response Actions Field and laboratory assessments will be performed to assess technical and procedural compliance with this QAPP. Performance and system audits are key to ensuring this compliance. The purposes of the audits are to:

• Confirm that appropriate documents are properly completed and kept current and orderly

• Ensure measurement systems are accurate

• Identify nonconformance or deficiencies and to initiate necessary corrective actions

• Verify that field and laboratory QA procedures called for in this QAPP are properly followed and executed

The SM and the laboratory QAM are responsible for ensuring conformance with analytical SOPs and FOPs (FSP, Appendix A). Activities selected for audit will be evaluated against specified requirements, and the audit will include an evaluation of the method, procedures, and instructions. Documents and records will be examined as necessary to evaluate whether the QA program is effective and properly implemented. Reports and recommendations must be prepared on all audits and submitted to the QAM for retention in the project files.

3.1.1 Field Audits Planning, scheduling, and conducting QA audits and surveillance are required to verify that site activities are being performed efficiently in conformance with approved plans, standards, federal and state regulatory requirements, sound scientific practices, and contractual requirements. Planned and scheduled audits may be performed to verify compliance with aspects of the QA program and to evaluate the effectiveness of the QA program. Audits include the following:

• Objective examination of work areas, activities, and processes • Review of documents and records • Interviews with project personnel • Review of plans and standards

The FTL will regularly conduct internal review of the sampling program during the investigation and pay particular attention to the sampling program with respect to representativeness, comparability, and completeness of the specific measurement parameters involved.

The FTL or a designee will review field documentation (COC forms, field daily sheets, and logbooks) as it is generated for accuracy, completeness, and compliance with QAPP


MKE\050810001

requirements. The FTL will also periodically audit field sampling procedures for compliance with QAPP procedures. The auditor will check that:

• Sampling protocols are followed • Samples are placed in proper containers • Samples are stored and transported properly • Field documentation is completed

The USEPA or WDNR hold the right to perform field audits during sampling activities.

3.1.1.1 Field Corrective Action

Any project team member may initiate a field corrective action process, which action process consists of identifying a problem, acting to eliminate it, monitoring the effectiveness of the corrective action, verifying that the problem has been eliminated, and documenting the corrective action.

Corrective actions include correcting COC forms, problems associated with sample collection, packaging, shipping, field record keeping, or additional training in sampling and analysis. Additional approaches may include re-sampling or evaluating and amending sampling procedures. The FTL will summarize the problem, establish possible causes, and designate the person responsible for a corrective action. The FTL will verify that the initial action has been taken and appears effective, as well as follow up to verify that the problem has been resolved.

Technical staff and project personnel will be responsible for reporting suspected technical or QA nonconformances or suspected deficiencies by reporting the situation to the FTL. The FTL will be responsible for assessing suspected problems in consultation with the QAM and the SM, and make a decision based on the situation’s potential to impact data quality. If it is determined that the situation warrants a reportable nonconformance requiring corrective action, the FTL will initiate a nonconformance report.

The FTL will be responsible for ensuring that corrective actions for nonconformances are initiated by:

• Evaluating all reported nonconformances

• Controlling additional work on nonconforming items

• Determining disposition or action to be taken

• Maintaining a log of nonconformances

• Reviewing nonconformance reports and corrective actions taken

• Ensuring nonconformance reports are included in the final documentation in the project files

3.1.2 Laboratory Audits The laboratory QAM may conduct internal system audits, which are qualitative evaluations of all components of the laboratory QC measurement system. The audit serves to determine


MKE\050810001

if all measurement systems are used appropriately. The system audits are conducted to evaluate the following:

• Sample handling procedures • Calibration procedures • Analytical procedures • QC results • Safety procedures • Record keeping procedures • Timeliness of analysis and reporting.

In addition, laboratories are subject to external audits, which focus on assessing general laboratory practices and conformance to this QAPP. Laboratory audits may be performed prior to the start of analyses and at any time during the course of the project as deemed necessary.

The laboratory QAM will review internal laboratory performance. The laboratory QAM will evaluate laboratory precision and accuracy by comparing results of duplicate samples, QC samples, spikes, and blanks. The laboratory QAM or other client services individual will check the analytical prior to distribution when a beyond-control-limit situation is encountered

External laboratory performance reviews may also be conducted based on evaluation of the results of check samples analyzed as part of the USEPA and/or state certification requirements. In addition, performance audits may be conducted by sending “double blind” performance evaluation (PE) samples (those that are not discernable from routine field samples) to the analytical laboratory. USEPA Region 5 or the WDNR may conduct external audits.

3.1.2.1 Laboratory Corrective Action

Corrective actions may be required for two classes of problems: analytical/ equipment problems and noncompliance problems. Analytical/ equipment problems may occur during sampling, sample handling, sample preparation, laboratory instrumental analysis, or data review.

A corrective action program will be determined and implemented when a noncompliance problem is identified. The person identifying the problem will be responsible for notifying the proper project member. If the problem is analytical in nature, information on these problems will be communicated to the laboratory QAM and the QAM, who will in turn direct information to proper project members. Implementation of corrective action will be confirmed through similar channels.

Implementation of all corrective actions will be documented. No staff member will initiate corrective action without prior communication of the action needing correction and the proposed corrective action through the proper channels. If corrective actions are insufficient, the SM or the QAM may issue a stop work order.


MKE\050810001

Corrective actions are required whenever an actual or potential out-of-control event is noted. The specific investigative action taken will depend on the analysis and the event in question. Laboratory personnel are alerted that corrective action may be necessary if:

• QC data are outside the warning or acceptable windows for precision and accuracy

• Blanks contain target analytes above acceptable levels

• Undesirable trends are detected in spike recoveries or RPD between duplicates

• Unusual changes in detection limits occur

• Inquiries concerning data quality are received

• Deficiencies are detected by the laboratory QAM during internal or external audits or from results of PE samples

Corrective action procedures are often handled at the bench level by the analyst, who reviews preparation and/or extraction procedures for possible errors, checks instrument calibrations, spike and calibration mixes, and instrument sensitivity. If problems persist, or cannot be identified, matters are referred to the laboratory supervisor, laboratory project manager, or laboratory QAM for further investigation. Once resolved, full documentation of the corrective action procedures is filed with the Laboratory QA Manager after approval by CH2M HILL. Corrective action may include:

• Re-sampling and analyzing

• Evaluating and amending sampling procedures

• Evaluating and amending analytical procedures

• Accepting data and acknowledging the level of uncertainty

• Re-analyzing the samples, if sample or extract volume is adequate and holding time criteria permit

If re-sampling is deemed necessary due to laboratory problems, the SM must identify the appropriate course of action to be taken, including potential cost recovery from the laboratory for the additional sampling effort.

3.2 Reports to Management In addition to the audit reports that may be submitted to the SM in accordance with this QAPP, a monthly progress report is prepared by the SM, addressing all QA issues and corrective actions proposed or already taken to be submitted to the USEPA WAM and the WDNR. In addition, after the sample results have been received from the laboratory, and they have been evaluated, reduced, and tabulated, a data evaluation report will be submitted to USEPA and WDNR that documents the field investigation.


MKE\050810001

SECTION 4

Data Validation and Usability

4.1 Data Review, Verification, and Validation Data validation is the process by which data generated in support of a project are reviewed against the data QA/QC requirements. The data are evaluated for precision and accuracy against the analytical protocol requirements. Nonconformance or deficiencies that could affect the precision or accuracy of the reported result are identified and noted. The effect on the result is then considered when assessing whether the result is sufficient to achieve DQOs.

Deficiencies discovered as a result of data validation, as well as corrective actions implemented in response, will be documented and submitted in the form of a written report with supporting documentation supplied as check sheets. USEPA Functional Guidelines will be used as guidance on data validation procedures. QC requirements specified in the Analytical SOPs shall take precedence over the Functional Guidelines requirements when listed.

4.2 Validation and Verification Methods The data validation process is conducted to assess the effect of the overall sampling and analysis process on the usability of the data. There are two areas of review: laboratory performance evaluation and the effect of matrix and sampling interference. The laboratory performance evaluation is a check for compliance with the method requirements and a straightforward examination. The laboratory either did or did not analyze the samples within the QC limits of the analytical method and according to protocol requirements. The assessment of potential matrix and sampling affects consists of a QC evaluation of the analytical results; the results of testing blank, duplicate, and matrix spike samples; and then assessing how, if at all, this could affect the usability of the data.

All analytical data will be supported by a data package. The data package will contain the supporting QC data for the associated field samples (see Section 1.7 of this QAPP for the data package content requirements). Before the laboratory will release each data package, the laboratory QAM (or the analytical section supervisor) must carefully review the sample and laboratory performance QC data to verify sample identity, the completeness and accuracy of the sample and QC data, and compliance with method specifications.

USEPA will perform data validation for laboratory-generated data for Compliance Monitoring samples. CH2M HILL will perform data validation for laboratory-generated data for Natural Attenuation Monitoring samples in a manner consistent with USEPA’s Contract Laboratory Program National Functional Guidelines for Organic and Inorganic Data Review. Sample results will then be assigned a degree of usability based upon overall data quality.

The CH2M HILL project team will evaluate the data validation results. This evaluation will assess how the data, as qualified by the data validation, can be used on the project.


MKE\050810001

The data, after validation, will also be verified to assess if the correct samples were analyzed and the correct parameters were reported. The data is also verified to assess if the EDDs and the hard copy data deliverables are consistent with one another to assure an accurate database. Also, the data will be looked at in such a way as to see if the results make sense in comparison to what is anticipated. If the data is consistent with anticipated results, no corrective action will be deemed necessary. However, if the data obtained from the laboratory is not consistent with the anticipated results, a more in-depth evaluation of the results may be necessary to interpret the deviation.

4.3 Reconciliation with Data Quality Objectives The final activity of the data validation process is to assess whether or not the data fulfilled the planned objectives for the project. The final results, as adjusted for the findings of any data validation/ data evaluation, will be checked against the DQOs. The data acquired from the additional site investigation should fulfill the following project objective to evaluate groundwater data to determine whether materials should be added to the subsurface to enhance degradation of organic contaminants existing in groundwater at and downgradient from the site.

The data collected from the LTRA will be evaluated to assess if the above project objectives have been met. The above question will be answered assuming all scheduled samples and data readings documented in this QAPP are obtainable, and all of the data is deemed usable after sufficient validation and evaluation. If this question is not answered, future data collection will be required and implemented accordingly. If the data, after validation and evaluation, are sufficient to achieve project objectives, the QAM and SM will release the data and work may proceed.


MKE\050810001

SECTION 5

References

Ebasco Services, Inc. 1990. Final Remedial Investigation Report at Oconomowoc Electroplating Company Site, Ashippun, Wisconsin. March 23, 1990.

Pope, D.F., S.D. Acree, H. Levine, S. Mangion, J. van Ee, K. Hurt, and B. Wilson. 2004. Performance Monitoring of MNA Remedies for VOCs in Ground Water. EPA/600/R-04/027.

RMT. 2004. Hydrogeologic Investigation and Groundwater Extraction System Evaluation, Former Oconomowoc Electroplating Company, Inc., Ashippun, Wisconsin.

CH2M HILL. 2005. Field Sampling Plan, Oconomowoc Electroplating, Oconomowoc, Wisconsin.USEPA. 2001. USEPA Contract Laboratory Program National Functional Guidelines for Low Concentration Organic Data Review. EPA-540-R-00-006.

USEPA. 1998. Technical Protocol for Evaluating Natural Attenuation of Chlorinated Solvents in Ground Water. EPA/600/R-98/128.

USEPA. 1999. Use of Monitored Natural Attenuation at Superfund, RCRA Corrective Action, and Underground Storage Tank Sites. Office of Solid Waste and Emergency Response (OSWER) Directive 9200.4-17.

USEPA. 1999. USEPA Contract Laboratory Program National Functional Guidelines for Organic Data Review. EPA-540/R-99-008 (PB99-963506).

USEPA. 2000. Region 5 Framework for Monitored Natural Attenuation Decisions for Groundwater. September 19, 2000.

USEPA. 2004. USEPA Contract Laboratory Program National Functional Guidelines for Inorganic Data Review. OSWER 9240.1-45. EPA 540-R-04-004.

USEPA. 2004. Performance Monitoring of MNA Remedies for VOCs in Ground Water. EPA/600/R-04/027. April 2004.

WDNR. 2003. Understanding Chlorinated Hydrocarbon Behavior in Groundwater: Investigation, Assessment and Limitations of Monitored Natural Attenuation. RR-699. April 2003.

Appendix A Analytical Standard Operating Procedures

Standard Operating Procedures

CC-10 Alkalinity, Automated Colorimitrec

CC-IC ION Chromotography

CC-18 Ammonia, Automated

6105B Trace Metals

CC-TOC Total Organic Carbon in Water

CC-32 Sulfide, Titrimetric Method

5200 Dissolved Methane, Ethene, Ethane, Acetylene, Carbon Dioxide in Water

SS-4 Restrictive Sample Handling and Documentation

5280B Analysis of VOCs by GC/MS

FO-8 Laboratory Waste Disposal

CT Laboratories SOP No; CC-10 Rev. 7Inorganics Laboratory Section Page 1 of 12 08/23/04

CT Laboratories

Title: Alkalinity, Automated Colorimetric

SOP Number: CC-10

Prepared by: ___________________________________Date

Technical Review by: ___________________________________Date

Reviewed by: ___________________________________Quality Assurance Date

Ab ___________________________________Laboratory Director Date

SOP Manual Control Number:____________________


1.0 SCOPE AND APPLICATION1.1 This method is used to determine the alkalinity in potable waters, surface

waters, domestic wastes and industrial wastes.1.2 The working (linear) range for this method is 10 to 625 mg/L. Samples

which measure >625 mg/L are analyzed by the titrimetric method.

2.0 METHOD SUMMARY2.1 Methyl orange is used as a color reagent for this method because its pH

range is the same as the pH of the equivalence point for a total alkalinitytitration. The methyl orange indicator is in a dilute pH 3.1 buffer which isjust below its color change pH. When an alkaline sample is injected, thepoorly buffered methyl orange changes color in proportion to the changein pH of the weak buffer, and thus in proportion to the alkalinity of thesample.

3.0 DEFINITIONS3.1 Reagent Water: Deionized water.3.2 Initial Calibration Verification (ICV): A midrange check standard

analyzed after the calibration has been completed.3.3 Initial Calibration Blank (ICB): Reagent water fortified with the same

matrix as the calibration standards (in this case simply reagent water),analyzed immediately after the ICV.

3.4 Lab Control Sample (LCS): A known concentration obtained from asecond source. The LCS is analyzed exactly like a sample.

3.5 Continuing Calibration Verification (CCV): A check standard analyzedafter every ten samples and at the end of the analytical run.

3.6 Continuing Calibration Blank (CCB): Reagent water fortified with thesame matrix as the calibration standards, analyzed immediately after eachCCV.

3.7 Duplicate Analysis: Two aliquots of a given sample are analyzed. Therelative percent difference (RPD) is then determined from the two resultsand compared to the lab control limits for that particular matrix.

4.0 HEALTH AND SAFETY4.1 Gloves and protective clothing should be worn to protect against

unnecessary exposure to possibly hazardous chemicals and contaminantsin samples. All activities performed while following this procedureshould utilize appropriate laboratory safety systems (see CTL Health andSafety Manual).

5.0 CAUTIONS5.1 This method cannot be used for SWDA samples.

6.0 INTERFERENCES 6.1 Turbidity and color will interfere with this method. Turbidity can be

removed by filtration.


7.0 PERSONNEL QUALIFICATIONS7.1 All personnel need to demonstrate capability by completing a valid IDC,

initial demonstration of capability, study prior to performing analysis onactual samples.

8.0 APPARATUS AND MATERIALS8.1 Balance: analytical, capable of accurately weighing to the nearest 0.0001g8.2 Glassware: Class A volumetric flasks and pipettes8.3 Lachat QuickChem 8000 containing a:

8.3.1 ASX-500 autosampler.8.3.2 Lachat Dual Resolution Dilutor-Autodilutor.8.3.3 Multichannel proportioning pump8.3.4 Injection module with a 69.0 cm sample loop.8.3.5 Reaction manifold (Alkalinity 10-303-31-1-A)8.3.6 Colorimetric detector with interference filter wavelength of 550

nm8.3.7 Data system (Omnion software system)8.3.8 PVC pump tubes- PVC tubes must be used for this method

8.4 Reagents. Use CO2 –free deionized water to prepare all solutions.8.4.1 Hydrochloric Acid (HC1) 0.1M.: In a 1 L volumetric flask

containing about 800 mL of DI water add 8.3 ml of concentratedhydrochloric acid. Dilute to the mark with DI and invert to mix.Store on reagent shelf in wet chem lab.

8.4.2 KHP Buffer (pH 3.1): In a 1 L container, dissolve 5.0 g ofpotassium acid phthalate [potassium hydrogen phthalate,potassium biphthalate, KHP, 2-(HO2C) C6H4COOK] in 900ml ofCO2-free DI water. Add 85.0 ml of 0.1 M hydrochloric acid(8.4.1), then add acid (no more than 5.0 mL) to bring the pH to 3.1± 0.05. If greater than 5.0 mL of 0.1 M HCL is necessary, startover in the preparation of this reagent. If this fails usestandardized 0.1 M HCl. Pour into a glass storage bottle. Store ina glass bottle on reagent shelf in wet chem lab. Reagent expiresafter one week.

8.4.3 Methyl Orange Reagent: In a 1 L volumetric flask, dissolve0.1313g of methyl orange in about 700 ml of DI water. Dilute tothe mark and invert to mix. Alternately, dilute Methyl Orangesolution by placing 10mL of solution into a 100mL volumetricflask and diluting to volume with CO2-Free deionized water. Storein glass on reagent shelf in wet chem lab

8.4.4 Stock Standard 2500 mg CaCO3/l as Na2CO3.: In a 1 L volumetricflask, dissolve 2.650 g of anhydrous sodium carbonate (Na2CO3)that has been dried at 103-105oC for four hours in about 900 mlcarbon dioxide-free water. Dilute to the mark and invert to mix.Prepare fresh monthly and protect it from the atmosphere, as it willabsorb carbon dioxide. Store on reagent shelf in wet chem lab.


8.4.5 Working Standards: Using the stock standard 2500 mg/L (8.4.4),pipet into 200 mL volumetric flasks the following amounts:Standard mLs of Stock (8.4.4)625 mg/L 50500 mg/L 40375 mg/L 30250mg/L 20125mg/L 1075mg/L 625mg/L 20mg/L 0

Dilute all standards to mark with DI water and mix well. Store onreagent shelf in wet chem lab. Standards expire monthly.

8.4.6 Laboratory Control Standard Stock 2500mg/L : In a 500mLvolumetric flask, dissolve 1.325g of anhydrous sodium carbonate(Na2CO3) that has been dried at 103-105oC for four hours in about900 ml carbon dioxide-free water. Dilute to the mark and invert tomix. Prepare fresh monthly and protect it from the atmosphere, asit will absorb carbon dioxide. Store on shelf in wet chem lab. Thisstandard is also used as the ICV/CCV for this analysis.

8.4.7 Laboratory Control Standard 375mg/L (LCS): Into a 200mLvolumetric flask, add 30mL of LCS Stock (8.4.6) and dilute tovolume with CO2 free DI water. Prepare fresh daily.

9.0 INSTRUMENT OR METHOD CALIBRATIONSee Sample preparation and analysis section 11.0.

10.0 SAMPLE COLLECTION, HANDLING AND PRESERVATION10.1 A minimum of 125 mL of sample may be collected.10.2 Cool to 4o C. Hold time is 14 days.10.3 Plastic or glass containers are acceptable.

11.0 SAMPLE PREPARATION AND ANALYSIS11.1 Open the Omnion software by double-clicking on the Omnion icon.11.2 Open the alkalinity.omn file under C:\Lachat\Data\Alkalinity. If this file

is not available, see the QuikChem FIA+ User Manual for file set up andAppendix A for the timing for the method.

11.3 Right click on the ICB line in the Run Worksheet window and chooseAppend Many.

11.4 Enter the number of lines you need to add then click OK.11.5 Enter the samples in the order you wish to run into the Run Worksheet

window.11.6 Right click on the tenth sample and choose insert many. Type in two and

ok.11.7 Into the two rows you inserted, enter sample names of CCV and CCB.


11.8 Into the Cup No column, enter the vial location of the CCV and the CCB.In the Run Properties window, enter the known concentration and theupper and lower acceptable concentration limits for the each. If you wanta message to appear if the QC fails, you can enter a message in the FailMessage area. If you would like the instrument to perform an action whenthe QC fails, Choose the appropriate Fail Action. Change sample type toCheck Standard.

11.9 Highlight the CCV and CCB rows.11.10 Right click on the highlighted rows and choose Define DQM11.11 Click radio button next to After every N samples. Type 10 after the Enter

# and place a check mark in Close End of Run. This will insert the CCVand CCB after every 10 samples and at the end of the run.

11.12 Inspect modules for proper connections. See Appendix A for manifolddiagram

11.13 Turn on power to all modules. Place reagent lines into proper containers.Apply tension on pump tube cassettes.

11.14 Pump system until a stable baseline is attained.11.15 Place calibration standards and blank in sample tray in descending order

of concentration followed by check standards and unknowns. Theconcentrations of the unknowns (samples) as well as the check standardsand other QC will be evaluated in relation to the absorbences of thecalibration standards. The Lachat program prints out the raw data inmg/L.

11.16 After the calibration has been established, it must be verified by theanalysis of a LCS/ICV. If measurements exceed + 10 % of the establishedLCS/ICV concentration, the analysis should be terminated and theinstrument recalibrated. The new calibration must be verified beforecontinuing analysis. An LCS/CCV is also analyzed at the frequency of 1per 10 samples and at the end of the run. All LCS/CCV must be followedby a CCB.

11.17 Following the LCS/ICV, an ICB must be analyzed. If the ICB isunacceptable, recalibrate and/or make new standards until acceptable.

11.18 Samples must be checked for color and turbidity. If a sample is turbid, itmay be filtered prior to analysis. Samples with color must be titrated todetermine alkalinity. See SOP CC-11 for further instruction on alkalinityby titration.

11.19 Samples with results greater than 625 mg/L must be analyzed by titration.See SOP CC-11 for further instruction on alkalinity by titration.

11.20 At end of run, place all transmission lines in water, and flush system.11.21 Pump lines dry.11.22 Turn off pump, all modules, and release tension levers on pump tube

cassettes.11.23 Clean area thoroughly.11.24 Data will automatically export to C:\ directory on the Lachat computer.

Rename the file that has been automatically generated (the generated file


will have the date and time of the export in the file name) with the LIMSrun number.

11.25 Move the renamed file to I:\LaChat8000. Data will be automaticallyimported into LIMS.

11.26 Review data that has been imported and submit for review.

12.0 TROUBLESHOOTING AND MAINTENANCE12.1 Refer to Lachat QuikChem User Manual for troubleshooting and

maintenance instructions.

13.0 DATA ACQUISITION, CALCULATION AND REDUCTION13.1 RPD = (ORIG – DUP) x 100 (ORIG + DUP)/2

where ORIG = Original sample concentrationDUP = duplicate sampleconcentration

13.2 Accuracy- check standards% Recovery = measured concentration X 100

true concentration

14.0 COMPUTER HARDWARE AND SOFTWARE14.1 Computer with StarLIMS14.2 Lachat Omnion 3.0 software

15.0 DATA MANAGEMENT AND RECORD MANAGEMENT15.1 After data has been captured by LIMS, it is reviewed by the analyst for

accuracy and completeness. See checklist for data review guidance.15.2 Once analyst has reviewed and approved the data, it is given to a peer or

supervisor for review.15.3 After the second reviewer approves the data, the reviewer sends the data to

“validated” status in LIMS.15.4 The original data is filed by test in the file cabinet and periodically the

contents of the file cabinet are archived.

16.0 QUALITY CONTROL16.1 The analyst must show an initial demonstration of capability (IDC) to

generated acceptable data, by successfully analyzing four replicates of astandard and one unknown sample.

16.2 ICV (initial calibration verification): This mid range second-source checkstandard is analyzed after calibration. Control limits are +/- 10% of thetrue concentration. If the recovery is outside of this range, terminate therun and correct the problem before proceeding.

16.3 ICB (initial calibration blank): Analyzed immediately after the ICV. Theconcentration of the ICB must be below the method LOD. If the ICB isunacceptable, any samples processed that have a concentration of < 20


times the blank detection and greater than the MDL must be reanalyzed orqualified with a ‘B’ flag.

16.4 LCS/CCV (lab control sample/continuing calibration verification):Analyze an LCS/CCV standard obtained from a second source for every10 samples. Control limits are +/- 10% of the established concentration.An out of control LCS may indicate that the calibration standard stocksolution may be inaccurate. If the recovery exceeds this, terminate theanalysis and correct the problem before proceeding

16.5 CCB (continuing calibration blank): Analyzed immediately after theLCS/CCV. The concentration of the CCB must be below the methodLOD. If the CCB is unacceptable, any samples processed that have aconcentration of < 20 times the blank detection and greater than the MDLmust be reanalyzed or qualified with a ‘B’ flag.

16.6 Contract Specific Sample Analysis: For certain samples, limits arespecified by the QAPP (Quality Assurance Project Plan) associated with agiven project. For these samples follow the limits specified in the QAPPfor that project.

16.7 A duplicate analysis must be performed for every 20 samples of eachmatrix type. Two aliquots of a given sample are analyzed. The relativepercent difference (RPD) is then determined from the two results andcompared to the lab control limits for that particular matrix. If RPDexceeds in-house limits and the results of the sample are greater than theLOQ, the results must be ‘Y’ flagged.

17.0 REFERENCES17.1 Methods for Chemical Analysis of Water and Wastes. 1983

EPA-600/4-79-020, Method 310.2.17.2 Lachat QuikChem FIA+ Automated Ion Analyzer User Manual, Third

Edition, Issued: 03/0317.3 Lachat Omnion 3.0 Tutorial Manual, Part Number 02134, Revision C

Revision Date: May 0317.4 Lachat QuikChem 8000 Automated Ion Analyzer Training Manual for

Omnion 3.0, Part Number 02135, 18 Jun 2002 release17.5 Lachat QuikChem Method 10-303-31-1-A, Determination of Alkalinity

(Methyl Orange) in Surface and Wastewaters By Flow Injection Analysis,Revision Date 23 January 2001


18.0 SUMMARY OF QUALITY CONTROL REQUIREMENTS

Procedure Frequency ofProcedure

Acceptance Criteria Corrective Action ifUnacceptable

Seven-point initial calibration plusblank (ICAL) Initially and as needed r > 0.995 for regression line Repeat until acceptable

Initial calibration verification (ICV) After each ICAL, priorto sample analysis %R: 90-110% for all analytes

Remake and reanalyze ICVstandard once, if still

unacceptable repeat ICAL

Initial calibration blank (ICB) After each ICV, priorto sample analysis < MDL

Remake and reanalyze ICBonce, if still unacceptable

investigate and correct problemor ‘B’ qualify all results <20

times the ICB and greater thanthe MDL.

Laboratory control sample(LCS)/Continuing calibration

verification (CCV)

Daily after every 10samples, and at end of

run%R: 90-110%

Remake and reanalyzeLCS/CCV once, if still

unacceptable investigate andcorrect problem. Reanalyze all

samples after last acceptableLCS/CCV.

Continuing calibration blank (CCB) After each LCS/CCV <MDL

If the CCB is unacceptable, anysamples processed that have

detection < 20 times the blankdetection and are greater than

the MDL must be reanalyzed or‘B’ qualified.

Capability demonstration sample(IDC)

Four (4) preparedsamples and oneunknown sample

analyzed one time priorto any sample analyses

In-house determined criteria forLCS recovery and precision

Retrain and repeat untilacceptable

Sample duplicate (DUP) One per 20 samples ofthe same matrix

In-house derived limits Default:RPD < 20% if analytes > LOQ

Investigate problem and, ifnecessary, qualify results.

.

CT Laboratories SOP No; CC-10 Rev. 7Inorganics Laboratory Section Page 9 of 12 08/23/04Data Validation Checklist

LIMS #: Method: Alkalinity Automated EPA310.2

Analysis Date Analyst / Data Interpreter Independent Reviewer Date of Review Approved

Yes … No

Instructions: Complete one checklist per analytical run. Enter the appropriate response for each question. Each “No” response requires an explanation in the Commentssection, and may require the initiation of a Nonconformance Report.

Requirement: Acceptance AnalystReview

IndependentReview

Comments:

Criteria Yes No Yes No (indicate reference to an attachment if necessary)

1. Were the samples analyzed within hold time? 14 days

2. Was the calibration performed using the required number of standards? Seven plus a blank

3. Is the standard prep log number noted on the analytical report? ---

3. Was the correlation coefficient acceptable? >= 0.995

4. Were the ICV and ICB run immediately after the calibration curve? ---

5. Was the ICV recovery acceptable? 90 – 110 %

6. Was the ICB result acceptable? < LOD

7. Were the LCS/ CCV’s and the CCB’s analyzed at the required frequency? 1per 10 samples

8. Were the LCS/CCV recoveries acceptable? 90 – 110 %

9. Were the CCB results acceptable? < LOD

10. Was the LCS/CCV used before the indicated expiration date? ---

11. Were all over-range or colored samples analyzed by titration? ---

12. Were duplicate samples run at the required frequency? 1 per 20 of the samematrix

13. Was the RPD of the duplicates acceptable? Within in house QClimits

14. Are all samples on the job lists accounted for? ---


Appendix A

Alkalinity Manifold Diagram

Timing for Method

Pump Speed: 35Cycle Period: 55 sAnalyte Data:Concentration Units: mg CaCO3/LPeak Base Width: 29.5 s% Width Tolerance: 50Threshold: 60,000Inject to Peak Start: 30.5 sChemistry: Inverse


Calibration Rep Handling: AverageCalibration Fit Type: 3rd Order PolynomialWeighting Method: NoneForce through zero: noSampler Timing:Min. Probe in Wash Period: 5 sProbe in Sample Period: 30 sValve Timing:Load Time: 0 sLoad Period: 15 sInject Period: 40 sTime to Valve: 25 s

CT Laboratories SOP No: CC-IC Rev. 2Inorganics Laboratory Section Page 1 of 19 10/11/04

CT Laboratories.

Title: Ion Chromatography

SOP Number: CC-IC

Prepared by: ___________________________________Date






1.0 SCOPE AND APPLICATION1.1 This method covers the sequential determination of the anions chloride, fluoride,

nitrite, nitrate, ortho-phosphate, and sulfate in all water samples as well as soil andsludge samples that have been extracted according to the procedure in this SOP.

2.0 METHOD SUMMARY2.1 A small volume of a water or extracted sample is injected into an ion

chromatograph to flush and fill a 25 or 50uL constant volume sample loop. Thesample is then injected into a stream of carbonate-bicarbonate eluent.

2.2 The sample is pumped through three different ion exchange columns and into aconductivity detector. The first two columns, a guard column and a separatorcolumn, are packed with low-capacity, strongly basic anion exchanger. Ions areseparated into discrete bands based on their affinity for the exchange sites of theresin. The last column is a self-regenerating suppressor column that reduces thebackground conductivity of the eluent to a low or negligible level and converts theanions in the sample to their corresponding acids. The separated anions, in theiracid form, are measured using an electrical-conductivity cell. Anions are identifiedbased on their retention times compared to known standards. Quantitation isaccomplished by measuring the peak area and comparing it to a calibration curvegenerated from known standards.

3.0 DEFINITIONS3.1 Calibration Blank (CB)—A volume of reagent water fortified with the same matrix

as the calibration standards. It is analyzed immediately following the calibrationstandards (Initial Calibration Blank-ICB), at a frequency of 1 per 10 samples during arun (Continuing Calibration Blank-CCB), and at the end of a run to check for driftsin calibration, or possible analyte carry-over. Control criteria consist of the absolutevalue being less than or equal to the MDL for a given analyte. If this range isexceeded, a new calibration will be necessary or data flagged appropriately.

3.2 Calibration standard (CAL)—A solution prepared from the stock standardsolutions. The CAL solutions are used to calibrate the instrument. Acceptance ofthe calibration requires a correlation coefficient of 0.995 or better. No samples willbe analyzed without acceptable calibration.

3.3 Laboratory Control Standard (LCS)-- A mid-range standard prepared from a sourcedifferent from that used for calibration standards. The LCS is analyzed exactly like asample and its purpose is to determine whether the methodology is in control. Theretention times of the analytes in the LCS must be within 10% of the retention timeof the those analytes in the calibration curve.

3.4 Matrix duplicate (DUP)—Two separate aliquots of a sample are analyzed at a rateof one per 10 samples of a given matrix per day for 9056 and 300.0. ACOEduplicates should be analyzed at a rate of one per project per run or as specified by


the client. To be considered acceptable RPD between the sample and the sampleduplicate must meet in house acceptance criteria.

3.5 Matrix spike (MS)—An aliquot of a sample to which known quantities of theanalytes of interest are added. The MS is analyzed exactly like the samples and itspurpose is to determine whether the sample matrix contributes bias to the analyticalresults. An MS is prepared for every 20 samples of a given matrix per day for 9056or CLP, for every 10 samples of a given matrix per day for 300.0, and at the samerate as the matrix duplicates for ACOE work. Failure to meet criteria may be due tomatrix interference within the sample. To be considered acceptable, MS must meetin house % recovery criteria.

3.6 Matrix spike duplicate (MSD)—An additional aliquot of sample treated exactly asthe MS. The MSD is run along with the DUP and MS for ACOE work. To beconsidered acceptable it must meet the same RPD criteria as the DUP and %recovery criteria as the MS.

3.7 Method blank (MB)—An aliquot of reagent water that is treated exactly as asample including exposure to all glassware, equipment, solvents, and reagents thatare used with other samples. The MB is used to determine if method analytes orother interferences are present in the lab environment, the reagents or the apparatus.A minimum of one MB is prepared per batch of 20, and is analyzed at the beginningof an analytical batch. Blank recovery should be less than the MDL.

3.8 Linear calibration range (LR)—the concentration range over which the instrumentresponse is linear. Samples with results greater than the highest calibration standardshould be diluted to a concentration that falls within the calibration curve range andreanalyzed.

3.9 Method detection limit (MDL)—The minimum concentration of an analyte that canbe identified, measured and reported with 99% confidence that the analyteconcentration is greater than zero.

3.10 Calibration Verification Standard-Initial (ICV) & Continuing (CCV) - A midpointcalibration standard which is analyzed at the beginning of the run (ICV), at afrequency of 1 per 10 samples during a run (CCV), and at the end of a run to verifycalibration throughout the run. The ICV must be from a second source different thanthat of the calibration standards, while the CCV may be from the same source as thecalibration standards.

3.11 Contract Required Detection Limit (CRDL) Standard--Detection level standard at alevel near the reporting limit, or at a level specified by client contract. Whenrequired, it is to be analyzed following the ICB, and prior to the last CCV standard inthe run.

4.0 HEALTH AND SAFETY4.1 The toxicity or carcinogenicity of each reagent used in this method has not been fully

established. Each chemical should be regarded as a potential health hazard andexposure should be as low as reasonable achievable.


4.2 Gloves and protective clothing should be worn to protect against unnecessaryexposure to hazardous chemicals and contaminants in samples. All activitiesperformed while following this procedure should utilize appropriate laboratory safetysystems.

5.0 CAUTIONS5.1 Nitrate, Nitrite and o-Phosphate have 48 hour holding times. Nitrate and nitrite can

be analyzed together when they are preserved with sulfuric acid. The combinedNitrate/Nitrite test has a 14 day holding time when preseverd with acid but cannot beused to speciate between Nitrate and Nitrite. Chloride, Sulfate and Fluoride have a 28day holding time when stored at 40C.

5.2 Standards should be stored at 4o C.

6.0 INTERFERENCES6.1 Any species with a retention time similar to that of the desired ion will interfere.

Large quantities of ions eluting close to the ion of interest will also result in aninterference. Separation can be improved by adjusting the eluent concentrationand/or flow rate. Sample dilution and/or the use of the method of standard additionscan also be used. Two common species, formate and acetate, elute betweenfluoride and chloride.

6.2 Because bromide and nitrate elute very close together, they are potentialinterferences for each other. It is advisable not to have Br- /N03

- ratios higher than1:10 or 10:1 if both anions are to be quantified.

6.3 Method interferences may be caused by contaminants in the reagent water,reagents, glassware, and other sample processing apparatus that lead to discreteartifacts or elevated baseline in ion chromatograms. Insure that all glassware isrinsed with Milli-Q water prior to use and use only Milli-Q water for makingstandards and reagents.

6.4 Samples that contain particles larger than 0.45 µm and reagent solutions thatcontain particles larger than 0.20 µm require filtration to prevent damage toinstrument columns and flow systems.

6.5 Large amounts of an anion can interfere with the peak resolution of an adjacentanion. Sample dilution can be used to solve most interference problems associatedwith retention times.

6.6 The water dip or negative peak that elutes near, and can interfere with, the fluoridepeak. This is taken care of by using the void volume function of the software forthe fluoride peak.

6.7 Any anion that is not retained by the column or only slightly retained will elute inthe area of fluoride and interfere. Known coelution is caused by carbonate andother small organic anions. At concentrations of fluoride above 1.5 mg/L, thisinterference may not be significant.


6.8 The acetate anion elutes early during the chromatographic run. The retention timesof the anions also seem to differ when large amounts of acetate are present.Therefore, this method is not recommended for leachates of solid samples whenacetic acid is used for pH adjustment.

7.0 PERSONNEL QUALIFICATIONSPersonnel operating the IC should have background knowledge of the scientific principlesused during this application. All operators should perform an initial demonstration ofcapability (IDC) prior to analyzing any samples. It is preferable for the operator to have atleast two semesters of college chemistry.

8.0 APPARATUS AND MATERIALS8.1 Dionex DX-120 Ion chromatograph

8.1.1 Guard column, Dionex AG14A-7uM, placed before the separator column toprotect the separator column from being fouled by particulates or certainorganic constituents (4 x 50 mm, Dionex P/N 056897 or equivalent)

8.1.2 Separator column, Dionex AS14A-7uM,a column packed with low-capacitypellicular anion exchange resin that is etheylvinylbenzene crossed withdivinylbenzene (4 x 250 mm, Dionex P/N 056904 or equivalent)

8.1.3 Self-regenerating suppressor, Dionex SRS-Ultra, a column that is capable ofconverting the eluent and separated anions to their respective acid forms(Dionex P/N 53946 or equivalent)

8.1.4 Detector, a low-volume, flow-through, temperature-compensated, electricalconductivity cell (approximately 1.25 µL volume, Dionex DS4 orequivalent) equipped with a meter capable of reading from 0 to1,000µseconds/cm on a linear scale.

8.1.5 Pump, capable of delivering a constant flow of 0.5 to 4 mL/min throughoutthe test.

8.1.6 Autosampler, Dionex AS40 with autosampler trays (Dionex P/N 046032 orequivalent), tubes and filter tops (Dionex P/N 038141 or equivalent).

8.1.7 Eluent reservoirs, suitable containers for storing eluent under pressure.8.1.8 Computer with PeakNet 5.1 software and a printer, to integrate the area

under the chromatogram. Software controls the DX-120 as well asprocessing and calculating data for the DX-120. Printer generates a papercopy of the data for archival purposes.

8.1.9 Bed support assembly- (Dionex P/N 042955 044689 or equivalent)8.2 Analytical balance, capable of weighing to the nearest 0.0001 g.8.3 Pipets, Class A volumetric flasks, beakers: assorted sizes8.4 Autopipettors of various volumes (Oxford Macro and Eppendorf micro)8.5 Syringes8.6 Glass Fiber Syringe Pre-Filters8.7 0.45um Syringe filters with pre-filter


8.8 Reagents8.8.1 Reagent water--Milli-Q water8.8.2 Eluent Concentrate—Into a 2L volumetric flask add 84.0g dried sodium

bicarbonate and 371.0g dried sodium carbonate and bring to volume withMilli-Q water.

8.8.3 Eluent—Use 20mL eluent concentrate (8.8.2) and bring to 10 liters withMilli-Q water in carboy. Helium purge to remove bubbles prior to use.Filter if necessary. Store on counter in IC lab.

8.8.4 Nitrate Nitrogen-200mg/L- Into a 1L volumetric flask, add 1.444g ofPotassium Nitrate and 2.0mL of chloroform. Bring to volume with Milli-Qwater. Store in standards refrigerator in wet chem lab.

8.8.5 Nitrite Nitrogen-200mg/L- Into a 1L volumetric flask, add 1.214g ofPotassium Nitrite and 2.0mL of chloroform. Bring to volume with Milli-Qwater. Store in standards refrigerator in wet chem lab.

8.8.6 LCS/ICV/CCV Concentrate #1—Into a 1L volumetric flask add 40mL100mg/L Flouride, 20mL 1000mg/L Chloride, 26.55mL 226mg/L Nitrogenin the form of Nitrate (alternately use 6.0mL 1000mg/L N as NO3 or 30mL200mg/L N as NO3(8.8.4)), 4mL 1000 mg/L ortho-phosphate and 20mL1000mg/L Sulfate. Bring to volume with Milli-Q water. Store in therefrigerator in the wet chemistry laboratory. TV = 4mg/L F, 20mg/L Cl,6mg/L N as NO3, 4mg/L O-Phos and 20mg/L SO4. Expires after one yearor sooner if stock solutions expire first.

8.8.7 LCS/ICV/CCV Concentrate #2—Into a 1L volumetric flask add 6mL1000mg/L Nitrogen in the form of Nitrite (alternately use 30mL 200mg/L Nas NO2 (8.8.5)) and fill to volume with Milli-Q water. Store in therefrigerator in the wet chemistry laboratory. TV = 6mg/L N as NO2.Expires after one month.

8.8.8 LCS/ICV/CCV- Into a 100mL beaker add 30mL LCS Concentrate #1(8.8.6) and 30mL LCS Concentrate #2 (8.8.7). Mix well. Use immediately.True value for solution is Fluoride and Phosphorus 2mg/L, Chloride andSulfate 10mg/L and Nitrate and Nitrite Nitrogen 3 mg/L. NOTE: ACOErequires that the LCS/ICV/CCV be exactly one-half the value of the highcalibration standard. Adjust concentrations accordingly.

8.8.9 100mg/L Chloride--add 10mL of 1000 mg/L Chloride to a final volume of100mL with Milli-Q water.

8.8.10 100mg/L Nitrite Nitrogen—add 10mL of 1000 mg/L Nitrite Nitrogen (alternately use 50mL of 200mg/L Nitrite Nitrogen) to a final volume of100mL with Milli-Q water.

8.8.11 100mg/L Nitrate Nitrogen—add 10mL of 1000 mg/L Nitrate Nitrogen(alternately use 50mL of 200mg/L Nitrate Nitrogen or 44.25mL of 226mg/LNitrate Nitrogen) to a final volume of 100mL with Milli-Q water.


8.8.12 100 mg/L Phosphorus--add 10mL of 1000 mg/L Phosporus to a finalvolume of 100mL with Milli-Q water.

8.8.13 Calibration standards- Into 8-100mL volumetric flasks pipet the followingand fill to volume with Milli-Q water.

Level 1 2 3 4 5 6 7 8 Vol of 100mg/L F 0 0.02 0.10 0.5 1.0 2.0 5.0 7.0mL

Vol of 100mg/L Cl 0 0.04 0.50 1.0 5.0 10.0 20.0 30.0mLVol of 100mg/L NO2 0 0.02 0.10 0.5 1.0 2.0 5.0 7.0mLVol of 100mg/L NO3 0 0.02 0.10 0.5 1.0 2.0 5.0 7.0mLVol of 100mg/L P 0 0.02 0.10 0.5 1.0 2.0 5.0 7.0mLVol of 1000mg/L SO4 0 0.025 0.05 0.1 0.5 1.0 2.0 5.0mL

Prepare fresh daily. Calibration Standards must be made from differentsources than the LCS.

8.8.14 Calibration check concentrate #1—Prepared as the LCS/ICV/CCVConcentrate #1 (8.8.6) with standards from the same source as thecalibration. Store in the wet chemistry refrigerator.

8.8.15 Calibration check concentrate #2—Prepared as the LCS/ICV/CCVConcentrate #2 (8.8.7) with the same standard used to make the calibration.Store in the wet chemistry refrigerator.

8.8.16 Calibration Check—Into a portion cup combine 5.0mL of CalibrationCheck Concentrate #1 (8.8.15) and 5.0mL of Calibration ConcentrateConcentrate #2 (8.8.16). Mix well. Prepare fresh daily.

8.8.17 Spiking solution #1- Into a 200mL volumetric flask pipet 64mL 100mg/L F,51.2mL 1000mg/L Cl, 12.8mL 1000mg/L N as NO3 (alternately 60.64mL200mg/L N as NO3 or 56.64mL 226mg/l N as NO3), 6.4mL 1000mg/L Pand 51.2mL 1000mg/L SO4. Bring to volume with Milli-Q water. Truevalue is 256mg/L Cl and SO4, 64mg/L N as NO3 and 32mg/L F and P.Add 0.1mL to 3.0mL of sample for a true value of 8mg/L Cl and SO4,2mg/L N as NO3 and 1mg/L F and P. Store solution in wet chemrefrigerator. Expires after one year.

8.8.18 Spiking solution #2- Into a 200mL volumetric flask pipet 12.8mL1000mg/L N as NO2 (alternately 60.64mL 200mg/L N as NO2). Bring tovolume with Milli-Q water. True value is 64mg/L N as NO2 . Add 0.1mLto 3.0mL of sample for a true value of 2mg/L N as NO2. Store solution inwet chem refrigerator. Expires after one month.

8.8.19 Sodium Chloride (NaCl)- 1M- Dissolve 58.5g of NaCL in DI water in a 1Liter volumetric flask and dilute to volume with DI water. Adjust the pH to2.0 using HCl. Stored in plastic bottle on top of IC.

8.8.20 pH 2.0 200 mM NaCl in 80% acetonitrile- Into a 500mL volumetric flask,combine 100mL of 1M NaCl solution (8.8.12) and 400mL of Acetonitrile(stored in extraction lab). This solution needs to be made fresh for eachuse.


8.8.21 10X Eluent--Into a 500mL volumetric flask, add 10.0mL of EluentConcentrate (8.8.2) and dilute to volume with Milli-Q water.

8.8.22 Oxalic Acid solution- 0.1 M8.8.23 200mN sulfuric acid- Into a 1 liter volumetric flask, add 5.6 mLs of

concentrated sulfuric acid and dilute to volume with DI water.

9.0 INSTRUMENT CALIBRATION9.1 Start DX-120 and allow to equilibrate. See section 11.0 for further instructions on

start up and method development.9.2 In the PeakNet software, go to the Method Editor. Open a new file. See Section

11.3 for further instructions on method set-up.9.2.1 Click on the Calibration Parameters icon.

9.2.1.1 Choose the General page. Choose the method of standardization tobe external, the number of replicates is 1 the linear weighting isequal and the calibration standard volume is 1. Check the ReplaceRetention Time and Update Response/replace under the UpdateData.

9.2.1.2 Choose the Defaults page. The sample volume, sample weight anddilution factor should all default to 1. The unknown response factorshould default to 0 and the response for unknowns should default toarea.

9.2.2 Click on the Component table icon.9.2.2.1 On the Identification page:

9.2.2.1.1 The components for the anions group will elute in thefollowing order: Fluoride, Chloride, Nitrite, Nitrate, ortho-Phosphate and Sulfate.

9.2.2.1.2 The retention times will be set based on the elution time of theanalytes in a known standard. See method set up in Section11.0 for further instructions.

9.2.2.1.3 For the Tolerance, choose 0.5 minutes.9.2.2.1.4 For the Reference Component, choose none.

9.2.2.2 On the calibration Standards page:9.2.2.2.1 The concentrations for each level in mg/L are:

Level 1 2 3 4 5 6 7 8F 0 0.02 0.1 0.5 1 2 5 7Cl 0 0.04 0.5 1 5 10 20 30NO2 0 0.02 0.1 0.5 1 2 5 7NO3 0 0.02 0.1 0.5 1 2 5 7o-Phos 0 0.02 0.1 0.5 1 2 5 7SO4 0 0.25 0.5 1 5 10 20 509.2.2.3 On the Calibration page:

9.2.2.3.1 For the curve fit type, choose linear.9.2.2.3.2 For the Origin, choose ignore


9.2.2.3.3 For Calibrate by, choose Area.9.2.3 Save the method under C:\Instrument Archive\Method\Sytstem x\W####, where x

is the system number and #### is the calibration standard number for thecalibration curve.

9.3 Go to the Schedule Editor.9.3.1 Under sample name, enter Level number. Repeat this for all eight levels.9.3.2 Under the Sample type, choose calibration standard9.3.3 Under Level, choose the appropriate level number for each level9.3.4 Under the method name, choose the method just created (C:\instrument

archive\method\system x\W####)9.3.5 Under data file copy and paste the entries from the sample name column.9.3.6 Save schedule under c:\instrument archive\schedule\system *\W####

9.4 Go to the Run Menu.9.4.1 Go to file and choose load schedule.

9.4.1.1 Choose the schedule that you saved under c:\instrumentarchive\schedule\system *\W####

9.4.2 On the Sample page:9.4.2.1 Under Data File, choose Browse.9.4.2.2 Create a new directory under c:\instrument archive\data\system *. Name

the new directory by the calibration standard number. Click OK9.4.2.3 Under Data Collection, confirm that the defaults of DX-120 and the

method run time appear.9.4.3 On the Modes page:

9.4.3.1 Choose upon receiving signal at module.9.5 On the AS-40 Autosampler:

9.5.1 Load the calibration standards in order.9.5.2 Press the Run button to begin running.

10.0 SAMPLE COLLECTION, HANDLING AND PRESERVATION

10.1 For Nitrate, Nitrite and o-Phosphate, refrigerate water and soil samples at 40C untilanalyzed. Hold time for samples is 48 hours.

10.2 For Chloride, Sulfate, and Fluoride, refrigerate water and soil samples at 40C untilanalyzed. Hold time for samples is 28 days.

10.3 For Nitrate + Nitrite, preserve samples to a pH <2 with sulfuric acid. Refrigerate samplesat 40C until analyzed. Hold time for samples is 14 days.

11.0 SAMPLE PREPARATION AND ANALYSIS

11.1 Sample Preparation11.1.1 For water samples, filter, if necessary, with a 0.45um syringe filter 3-5mL of an

appropriately preserved sample into an autosampler vial and cap with a filter cap.11.1.2 For soil samples, place 5g +0.01g of sample in a specimen cup and add 50mL of

Milli-Q water. Place on shaker table for 30 minutes then filter 3-5 mL of samplethrough a 0.45um syringe filter into an autosampler vial and cap with a filter cap.

11.2 Instrument equilibration


11.2.1 Turn on DX-120.11.2.2 Ensure that Helium tank has an adequate supply of Helium for the run.11.2.3 Fill the eluent containers on the top of the instrument with degassed eluent.11.2.4 Turn on the Helium supply for the DX-120.11.2.5 Press the Local/Remote button on the front of the DX-120. Make sure that the

instrument screen on the front of the DX-120 says Local.11.2.6 Press the Eluent pressure button. A green light should indicate that it is on.11.2.7 Open the front cover of the instrument and locate the small screw, in the middle of

the panel, that controls the purge for the pump.11.2.8 Loosen the screw by turning 2 or 3 times11.2.9 Press the pump button on the front of the instrument. A green light should indicate

that it is on.11.2.10 Allow the pump to prime for approximately one minute. If air is not purged from

the system, increase the flow rate by pulling the knob adjacent to the pump andturning it clockwise. Turn the knob until the air is purged or until the flow rate isapproximately 2.0mL/min. Allow the pump the prime for approximately oneminute.

11.2.11 Close the pump screw11.2.12 Press the SRS button on the front of the instrument. A green light should indicate

that it is on. If the flow rate was increased to prime the pump return it to itsoriginal setting by turning the knob counterclockwise.

11.2.13 Allow instrument to stabilize for 20-30 minutes prior to analysis.11.3 Method creation in PeakNet software

11.3.1 Turn on computer11.3.2 Open the PeakNet software by double clicking on the icon11.3.3 Open the Method editor by left clicking on the Method icon.11.3.4 Click on the new file icon (blank sheet) in the toolbar to open a new method file.11.3.5 Highlight DX-120 under modules and then click add. Press Exit.11.3.6 After the dialog box opens

11.3.6.1 Set the data collection time to 15 minutes.11.3.6.2 Set the rate to 5.00 Hz11.3.6.3 Set the Detector Unit to uS11.3.6.4 Set the Plot Scales to 30.0 uS for the maximum and –3uS for the

minimum.11.3.6.5 Click on the timed events icon (stopwatch).

11.3.6.5.1 For time INIT, place a check mark next to TTL1. All othersshould be unchecked. Click enter.

11.3.6.5.2 For time 0.0, place a check mark next to offset. All othersshould be unchecked. Click enter.

11.3.6.5.3 For time 0.01, place a check mark next to begin. All othersshould be unchecked. Click enter.

11.3.6.5.4 Click exit.11.3.6.6 Click on the integration icon (peak).

11.3.6.6.1 Set the Peak detection algorithm to standard11.3.6.6.2 Set the peak width to 10.00 seconds.11.3.6.6.3 Set the peak threshold to 0.01


11.3.6.6.4 Set the area reject to 10011.3.6.6.5 Set the reference area reject to 10011.3.6.6.6 Click OK

11.3.6.7 Click on the smoothing parameters icon.11.3.6.7.1 Set the filter type to none.

11.3.6.8 Click on the data events icon (baseline)11.3.6.8.1 Move the time line to the time that corresponds to the elution

time of Fluoride (usually around 3 minutes).11.3.6.8.2 Highlight the event option, void volume treatment for this

peak.11.3.6.8.3 Click add event11.3.6.8.4 Click exit

11.3.6.9 For the calibration and component table icons, refer to section 9.0 todetermine the correct settings.

11.3.6.10 Save the method as C:\INSTRUMENT ARCHIVE\METHOD\SYSTEMx\ W####where x = the system number the method is for and the#### is for the W number of the standard prep.

11.3.6.11 Close the method editor.11.3.6.12 NOTE: a calibration must be run for the method before it can be

used to analyze samples. See Section 9.0 for further details.11.4 Creating a schedule

11.4.1 Open the schedule editor by clicking on the icon.11.4.2 A new file should appear. If not, click on the new file icon in the toolbar.11.4.3 Under the sample column

11.4.3.1 Type in the CTI sample ID for the sample to be analyzed. For DUP, MSand MSD samples, place the letters DUP, MS or MSD in front of the CTIsample ID.

11.4.3.2 The first line in the schedule editor should be the CAL CHECK.11.4.3.3 The second line in the schedule editor should be ICV.11.4.3.4 The third line in the schedule editor should be ICB.11.4.3.5 After every ten samples and at the end of the run, a CCV, which is also

used as an LCS, and CCB, which is also used as a MB, should be run.11.4.4 Under the Method column, all lines should haveC:\ INSTRUMENT

ARCHIVE\Method\System x\ W####.met, where W#### is the calibrationstandard number and x is the system number you are using.

11.4.5 Under the data file column, enter the same thing as the sample field. It is easier tocopy and paste the sample column for this rather than hand entering all theinformation again.

11.4.6 Under the comments column, enter any dilution factors that you might have.11.4.7 Save the schedule as c:\ INSTRUMENT ARCHIVE\Sequences\System X\******

where x is the system number you are using and ****** is the LIMS run number.11.4.8 Exit the schedule editor.

11.5 The run program in PeakNet11.5.1 Click on the Run icon (center of screen)11.5.2 Click on the window for the system you want to use.11.5.3 Click on file. Choose Load Schedule.


Select the schedule for that corresponds to the LIMS run number you want to run.11.5.4 Click Open11.5.5 Under data on the load schedule page

11.5.5.1 Click on browse11.5.5.2 Double click on the folder under C:\instrument archive\data\system x11.5.5.3 In the new directory box type in the LIMS run number that you want to

run.11.5.5.4 Click Create to create the file folder11.5.5.5 Click OK to get back to the load schedule page

11.5.6 Under modes on the load schedule page11.5.6.1 Click on the “upon receiving signal at module” button.

11.5.7 Click OK at the bottom of the Load Schedule page. The computer will be waitingfor the autosampler to signal that a sample has been injected.

11.6 Load the autosampler with the samples in the order indicated in the schedule editor.11.7 Press the Run/Hold button on the Autosampler. A green light will indicated that the

autosampler is running.11.8 To turn off the DX-120

11.8.1 Close the run in PeakNet11.8.2 Close PeakNet software11.8.3 On the DX-120:

11.8.3.1 Press the SRS button. The green light next to SRS should shut off.11.8.3.2 Press the pump button. The green light next to pump should shut off.11.8.3.3 Press the eluent pressure button. The green light next to the eluent

pressure should shut off.11.9 If system will remain off for an extended period of time

11.9.1 Press the button on the front of the DX-120 to turn off the power to it.11.9.2 Turn off the power to the autosampler using the button on the left rear.

12.0 DATA CAPTURE12.1 Select Batch in the PeakNet Main Menu.12.2 Under File click open

12.2.1 Open C:\PeakNet\Schedule\DC.bch12.3 Under Processing select Input

12.3.1 Click Select12.3.1.1 Select the schedule you want to data capture. C:\Insturment Archive\

Schedule\System x\***** where ***** is the LIMS run number.12.3.1.2 Click Open

12.3.2 Process Injection should default to 1 through the last line of your schedule. If thereare more than 100 lines in the schedule capture it in parts. For example whencapturing a schedule that has 129 lines change the 129 to 100. Capture theschedule then repeat the process changing the 1 to 101 and leaving the 129.

12.3.3 Select All under included Detectors12.3.4 Choose from schedule for process method

12.4 Under Output unselect all options.12.5 Select Export


12.5.1 Change the file name to I:\DX120\***** +.csv where ***** is the LIMS runnumber followed by +, an arbitrary letter. If capturing more than once to the samerun, changing this letter prevents the files from being overwritten.

12.5.2 Select summary as the report type.12.5.3 Choose Peak as the summary option.

12.6 Click OK12.7 Click the Start Button12.8 Exit the batch program. Do not save the changes.

13.0 TROUBLESHOOTING AND MAINTENANCE13.1 See Dionex PeakNet Software User’s Guide, Dionex DX-120 Operator’s manual,

Dionex Installation Instructions, Troubleshooting Guide for the IonPac AS14,Column Care Guide for IonPac AS14 and ASRS-Ultra Installation Instructions andTroubleshooting Guide for troubleshooting instructions not covered in this section.

13.2 The column bed support assemblies should be replaced when they become clogged.A clog usually causes an increase in the pressure of the system. NOTE Replace theoutlet bed support ONLY if high pressure persists after replacement of the inletfitting.13.2.1 Disconnect the column from the system.13.2.2 Carefully unscrew the inlet (top) column fitting. Use two open-end

wrenches.13.2.3 Remove the bed support. Turn the end fitting over and tap it against a

benchtop or other hard, flat surface to remove the bed support and sealassembly. If the bed support must be pried out of the end fitting, use a sharppointed object such as a pair of tweezers, but be careful that you DO NOTSCRATCH THE WALLS OF THE END FITTING. Discard the old bedsupport assembly.

13.2.4 Place a new bed support assembly into the end fitting. Make sure that theend of the column tube is clean and free of any particulate matter so that itwill properly seal against the bed support assembly. Use the end of thecolumn to carefully start the bed support assembly into the end fitting. Ifthe column tube end is not clean when inserted into the end fitting,particulate matter may obstruct a proper seal between the end of the columntube and the bed support assembly. If this is the case, additional tighteningmay not seal the column but instead damage the column tube or the endfitting.

13.2.5 Screw the end fitting back onto the column. Tighten it fingertight, then anadditional 1/4 turn (25 in x lb). Tighten further only if leaks are observed.

13.2.6 Reconnect the column to the system and resume operation.13.3 The column will need to be cleaned when the retention time window shift more

than 10%, calibrations are no longer linear or the column becomes contaminatedfrom a sample.13.3.1 Prepare a 500 mL solution of pH 2.0 200 mM NaCl in 80% acetonitrile


13.3.2 Disconnect the ASRS-Ultra from the IonPac AS14 Analytical Column.Reverse the order of the guard and analytical column in the eluent flowpath. Double check that the eluent flows in the direction designated on eachof the column labels.CAUTION When cleaning an analytical column and aguard column in series, ensure that the guard column is placed after theanalytical column in the eluent flow path. Contaminants that haveaccumulated on the guard column can be eluted onto the analytical columnand irreversibly damage it. If in doubt, clean each column separately.

13.3.3 Set the pump flow rate to 1.0 mL/min13.3.4 Rinse the column for 15 minutes with deionized water before pumping the

NaCl/Acetonitrile cleanup solution over the column.13.3.5 Pump the NaCl/Acetonitrile cleanup solution through the column for 60

minutes.13.3.6 Rinse the column for 15 minutes with deionized water before pumping the

Oxalic acid cleanup solution over the column.13.3.7 Pump the Oxalic Acid cleanup solution through the column for 60 minutes.13.3.8 Rinse the column for 15 minutes with deionized water before pumping the

10X eluent cleanup solution over the column.13.3.9 Pump the 10X eluent cleanup solution through the column for 60 minutes.13.3.10 Rinse the column for 15 minutes with deionized water before pumping

eluent over the column.13.3.11 Equilibrate the column(s) with eluent before resuming normal operation for

at least 30 minutes.13.3.12 Reconnect the ASRS-Ultra to the AS14 Analytical Column and place the

guard column in line between the injection valve and the analytical column.13.4 Small analyte peak area is caused by running eluent through the ASRS while the

power is off to the ASRS. To regenerate the ASRS:13.4.1 Disconnect the eluent line from the analytical column attached to the

ELUENT IN port of the ASRS-ULTRA at the analytical column end of theline. Direct this line to a separate waste beaker.

13.4.2 Disconnect the eluent line from the ELUENT OUT port of the ASRS-ULTRA.

13.4.3 Using a plastic syringe push approximately 3 mL of 200 mN sulfuric acidthrough the ELUENT OUT port and approximately 5 mL of 200 mNsulfuric acid through the REGEN IN port.

13.4.4 Reconnect the eluent line from the ELUENT IN port of the ASRS-ULTRAto the analytical column and the eluent line from the ELUENT OUT portof the ASRS-ULTRA to the conductivity detector cell.

13.4.5 Turn on the power and then begin pumping eluent.

14.0 DATA ACQUISITION, CALCULATIONS AND DATA REDUCTION13.1 LIMS will calculate the following according to these equations:


13.1.1 Liquid Concentration (mg/L) = A x Cwhere A = instrument reading for sample (mg/L)

C= dilution factor

13.1.2 Solid Concentrations (mg/kg) = A x B x C , D x E

where A = instrument reading for sample (mg/L)B = total volume of extraction (L)C= dilution factorD = amount of sample used in extraction (Kg)E = percent solids/100 (if reporting on a Dry Weight Basis)

13.1.3 Spike Recovery (%)= (Spiked sample value – Sample value) x 100 (Spike amount)

13.1.4 %RSD = |(Sample – DUP)| x 100 , (Sample + DUP)/2

where DUP = Duplicate concentration

15.0 COMPUTER HARDWARE AND SOFTWARE15.1 Computer with LIMS15.2 Printer15.3 PeakNet 5.0 Software

16.0 DATA MANAGEMENT AND RECORD MANAGEMENT16.1 After data has been captured by LIMS, it is reviewed by the analyst for accuracy and

completeness. See checklist for data review guidance.16.2 Once analyst has reviewed and approved the data, it is given to a peer or supervisor for

review.16.3 After the second reviewer approves the data, the reviewer sends the data to “validated”

status in LIMS.16.4 The original data is filed by test in the file cabinet and periodically the contents of the file

cabinet are archived.

17.0 QUALITY CONTROL AND QUALITY ASSURANCE17.1 After every 10 injections, analyze a CCV, a midrange calibration standard. If the

instrument retention time has changed by more than 10% or recovery is outside of 90-110%, remake solution and analyze the fresh solution. If it still does not fall within theabove criteria, recalibrate.

17.2 Analyze one in every ten samples in duplicate for 300.0 or every twenty samples induplicate for 9056A. Take the duplicate sample through the entire sample preparation andanalytical process.

17.3 A matrix spiked sample should be run for each analytical batch or twenty samples for9056A or 10 samples for 300.0, whatever is more frequent, to determine matrix effects.

17.4 Prior to analyzing samples, each analyst must perform an IDC, initial demonstration ofcapability. The IDC consists of running a standard solution in quadruplicate and getting arecovery and RPD within method limits.


17.5 Method Detection Limit (MDL)—MDLs must be established for all analytes, using reagentwater fortified at a concentration of 3-5 times the estimated instrument detection limit. Todetermine MDL values, take seven or eight replicate aliquots of the fortified reagent waterand process through the entire analytical method. Calculate the MDL using thespreadsheet in H:\MDLs\classical\MDL water blank workbook.xls for waters ofh:\MDLs\classical\MDL soil blank workbook.xls for soils. MDLs should be determinedannually or whenever there is a significant change in background or instrument response.

17.6 Calibration check standard—A mid-point calibration standard run as a sample. If theinstrument retention time has changed by more than 10% or recovery is outside of 90-110%, remake solution and analyze the fresh solution. If it still does not fall within theabove criteria, recalibrate. A calibration check standard should be run once a day.

17.7 Calibration Blank (CB)—A volume of reagent water fortified with the same matrixas the calibration standards. It is analyzed immediately following the calibrationstandards (Initial Calibration Blank-ICB), at a frequency of 1 per 10 samples during arun (Continuing Calibration Blank-CCB), and at the end of a run to check for driftsin calibration, or possible analyte carry-over. Control criteria consist of the absolutevalue being less than or equal to the MDL for a given analyte. If this range isexceeded, a new calibration will be necessary or data flagged appropriately.

Standard Quality Control Requirements and Corrective Action Guidelines

QCType Frequency Conc. Level Acceptance Criteria Corrective Action

ICAL As needed R > 0.995 Recalibrate Instrument

ICV 1 per calibrationMidpoint of

cal curve 90-110% Reanalyze or recalibrate

ICB 1 per calibration <MDL

Correct problem andreanalyze or qualify datathat is not > 20 times the

ICB or <MDL

CCV1 after every 10th

sampleMidpoint of

cal curve 90-110%Correct problem and

reanalyze.


CCBImmediately

following eachCCV

<MDL

Correct problem andreanalyze or qualify datathat is not > 20 times the

ICB or <MDL

LCS1 per batch of 20

samplesMidpoint of

cal curve90-110%

Correct problem andreanalyze.

DUP10% (1 for every 10samples) per matrix In house limits. Default is 20%

Identify source ofproblem. Qualify data orreanalyze depending on

source of problem.

MS-MSD5% (1 in 20) of

samplesper batch per matrix

In-house limits. Default limitsare 80-120%

Identify source ofproblem. Qualify data orreanalyze depending on

source of problem.


Data Validation Checklist

LIMS #: Method: Anions by Ion Chromatography 300.0/9056


Yes … No

Instructions: Complete one checklist per analytical run. Enter the appropriate response for each question. Each “No” response requires an explanation in the Comments section,and may require the initiation of a Nonconformance Report.


IndependentReview

Comments:


1. Were the samples analyzed within hold time?

28 days for Cl, F,SO4;14 days for

preserved NO2+NO3;48 hours for O.Phos,and unpreserved NO2

and NO3

2. Was the calibration performed using the required number of standards? Three plus a blank



5. Was Calibration Check standard run prior to analysis of samples? ---

6. Was the Calibration Check standard recovery acceptable? 90 – 110 %

7. Were the ICV and ICB run immediately after the calibration check standard? ---



11. Were the CCV’s and the CCB’s analyzed at the required frequency? 1per 10 samples

12. Were the CCV recoveries acceptable? 90 – 110 %


14. Was a LCS run at the required frequency? 1 per 20 samples

15. Was the LCS recovery acceptable? 90-110 %


16. Was the LCS used before the indicated expiration date? ---

17. Were the MS and MSD prepared at the required frequency? 1per 20 field samples

18. Were the MS and MSD recoveries acceptable? Within in house QClimits


IndependentReview Comments:


19. Was the RPD between the MS and MSD acceptable? Within in house QClimits

20. Were all chromatograms checked to ensure accurate peak identification? ---


CT Laboratories SOP No: CC-18 Rev.3Inorganics Laboratory Section Page 1 of 13 1/27/03

CT LaboratoriesBaraboo Laboratory Divison

Title: Ammonia, Automated

SOP Number: CC-18

Prepared by: ___________________________________Date






1.0 SCOPE AND APPLICATION1.1 This method is used to determine ammonia in potable water, surface

water, domestic wastes and industrial wastes.1.2 The range for this method is 0.1 to 10.0 mg N/l as NH3.

2.0 METHOD SUMMARY2.1 Alkaline phenol and hypochlorite react with ammonia to form indophenol

blue that is proportional to the ammonia concentration. The blue colorformed is intensified with sodium nitroprusside.

3.0 DEFINITIONS3.1 Reagent Water: Deionized water.3.2 Initial Calibration Verification (ICV): A midrange check standard

analyzed immediately after the calibration has been completed.3.3 Initial Calibration Blank (ICB): An aliquot of reagent water analyzed

immediately after the ICV.3.4 Lab Control Sample (LCS): A standard obtained from a second source3.5 Continuing Calibration Verification (CCV): A check standard analyzed

after every ten samples and at the end of the analytical run.3.6 Continuing Calibration Blank (CCB): An aliquot of reagent water

analyzed fortified with the same matrix as the calibration standardsanalyzed immediately after the CCV.

3.7 Method Blank (MB): Reagent water taken through the same process as thesamples.

3.8 Matrix spike-matrix spike duplicate (MS-MSD): To two of three aliquotsof a given sample a known amount of spike solution is added. Matrixspikes and matrix spike duplicates are taken through all steps ofpreparation and analysis, exactly like a sample. The amount of spikerecovered helps to assess the effect of the sample matrix on the analysis.The precision of the method is also determined, by calculating the relativepercent difference (RPD) of the two spiked aliquots. An MS-MSD shouldbe prepared for every 20 samples in each matrix.


unnecessary exposure to possibly hazardous chemicals and contaminantsin samples. All activities performed while following this procedureshould utilize appropriate laboratory safety systems (see CTI Health andSafety Manual).

5.0 CAUTIONS5.1 When starting reagents, always add the nitroprusside reagent last.

Nitroprusside can form a precipitate if the other reagents are not beingpumped through the lines at the same time.

6.0 INTERFERENCES


6.1 Calcium and magnesium ions may precipitate if present in sufficientconcentration. Tartrate or EDTA is added to the sample in-line in order toprevent this problem.

6.2 Color, turbidity and certain organic species may interfere. Turbidity isremoved by manual filtration. Sample color may be corrected for byrunning the samples through the manifold with all reagents pumpingexcept hypochlorite which is replaced by DI water. The resultingabsorbance readings are then subtracted from those obtained for samplesdetermined with color formation in addition to sample color. This can bedone with the Quik Calc software.

7.0 PERSONNEL QUALIFICATIONS7.1 Analysts should be familiar with safety requirements for the lab.7.2 Analysts should have a working knowledge of the Lachat AE system.7.3 Analysts should have a valid IDC on file.

8.0 APPARATUS AND MATERIALS8.1 Lachat QuikChemAE automated flow injection ion analyzer, which

includes:8.1.1 Automated sampler8.1.2 Peristaltic pump8.1.3 Injection module with a 50cm, 0.81 mm I.D. sample loop.8.1.4 Colorimeter8.1.5 Flow cell, 10mm, 80 uL8.1.6 Interference filter, 630 nm8.1.7 Reaction module 10-107-06-1-A8.1.8 QuikCalc II software system.8.1.9 Heating bath with temperature controller and a circulating cell.

8.2 ReagentsUse DI water for all solutions.8.2.1 Sodium Phenolate: By volume: In a 1 L volumetric flask, dissolve

88 mL of 88% liquefied phenol or 83 g of crystalline phenol(C6H5OH) in approximately 600 mL water. While stirring, slowlyadd 32 g sodium hydroxide (NaOH). Cool, dilute to the mark, andinvert three times.

CAUTION : Wear gloves. Phenol causes sever burns and is rapidlyabsorbed into the body through the skin.8.2.2 Sodium Hypochloride: Dilute 100 mL of household bleach

containing 5.25 % NaOCl) to 200 in a volumetric flask with DIwater.

8.2.3 Buffer: In a 1 L volumetric flask, dissolve 50.0 disodiumethylenediamine tetraacetate (Na2EDTA) and 5.5 g of sodiumhydroxide (NaOH) in about 900 mL of water. Dilute to the markand invert three times.

8.2.4 Sodium Nitroprusside: Dissolve 3.50 g of sodium nitroprusside,also know as sodium nitroferricyanide, in 1 L of water.


8.2.5 Stock Standard, 1000 mg N/L as NH3 : Dissolve 3.819 g ofammonium chloride (pre-dried for 2 hours at 110°C) in 800 mL ofDI water. Dilute to the mark in a 1000 ml volumetric flask invertthree times. 1.0 mL = 1.0mg NH3-N. Store in either plastic ofglass in the refrigerator for up to six months.

8.2.6 Laboratory Control Sample (LCS) Stock: Dissolve 3.819 g NH4Cl(pre-dried for 2 hours at 110°C), from a second source in distilledwater and bring up to volume in a 1 liter volumetric flask. 1.0 mL= 1.0mg NH3-N. Store in either plastic of glass in the refrigeratorfor up to six months. Alternatively, a nutrient standard may bepurchased.

8.2.7 Working Stock Standard, 200.0 mg N/L as NH3 : In a 100mLvolumetric flask add 20.0 ml of the stock standard (8.2.5) with avolumetric pipet and dilute to the mark with DI water, invert threetimes.

8.2.8 Working Standards: Dilute in 200 ml volumetric flasks,respectively, 10.0mL, 5.0mL, 1.0mL, 0.5mL and 0.1mL of theworking stock standard (8.2.7) and fill to mark with DI water. Thismakes standards with concentrations of 10.00, 5.00, 1.00, 0.50 and0.10 mg N/L as NH3, respectively.

8.2.9 Laboratory Control Sample (LCS): In a 200mL volumetric flaskpipet 1.0mL LCS Stock (8.2.6) and fill to mark with DI water.TV=5.0mg/L.

9.0 INSTRUMENT OR METHOD CALIBRATIONSee section 12.0

10.0 SAMPLE COLLECTION, HANDLING AND PRESERVATION10.1 A minimum of 125 mL of sample may be collected in either plastic or

glass containers.10.2 Samples should be cooled to 4°C and preserved to pH <2 with H2SO4 until

analysis.10.3 Samples must be analyzed within 28 days of sampling.

11.0 METHOD CREATION11.1 From the Main Menu tab over to Methods and select Method Definition.11.2 Under File Select new.11.3 Enter the Method name as Ammonia.11.4 Enter the full name as Ammonia and the date.11.5 Tab over to channels. Enter.

11.5.1 Type ammonia and hit enter.11.5.2 Select ammonia. A new screen will appear.11.5.3 Information

11.5.3.1 Name of Channel –Ammonia11.5.3.2 Quik Chem Method Number—10-107-06-1-A11.5.3.3 Detector Selection


Are both a and b detectors active? NConcentration to switch to b—0.00mg/L

11.5.4 Standards11.5.4.1 Units—mg/L11.5.4.2 Format--#######.##11.5.4.3 Concenration

Starting Standard—ANumber of Standards—6Escape to a new screen

A—10.0B—5.0C—1.0E—0.5F—0.1

11.5.5 Evaluation11.5.5.1 Boundries—type “x” after standards A and F11.5.5.2 Strategies—Normal11.5.5.3 Pass Fail—Normal 0.99500 Max Std Dev 10%

11.5.6 Presentation11.5.6.1 Data Window

Heading—AmmoniaLeft Border—10.0%Right Border—90.0%Bottom Border—10.0%Top Border—90.0%Top Scale Response—1.25Bottom Scale Response—0.00

11.5.6.2 Chart ModeBottom Border—10.0%Top Border—10.0%

11.5.7 Timing11.5.7.1 Periods

Cycle Period—50.00sInjet to Start Period—23.00s

11.5.7.2 Mode—Manual Timing? N11.5.8 Escape to the Method Definition Menu

11.6 Tab to Standards11.6.1 Definition

11.6.1.1 Units—choose Ammonia, enter mg/L. Escape.11.6.1.2 Format—Enter #######.##. Escape.11.6.1.3 Concentration—A-F are 10.0, 5.0, 1.0, 0.5, and 0.1

mg/L respectively. Escape.11.6.2 Calibration

11.6.2.1 Protocol—A B C D E F11.6.2.2 Actions—N

11.7 Tab over to Timing


11.7.1 Fluid System Timing11.7.1.1 Cycle Period—50.00s11.7.1.2 Probe Sample Period—30.00s11.7.1.3 Period of inactivity to go to standby—180.00s11.7.1.4 Period of pump at normal speed—15.00s

11.8 Tab over to Options11.8.1 Runtime Display Options

11.8.1.1 Record Peaks? Y11.8.1.2 Display Individual Chords? N11.8.1.3 Master printer to echo runtime report? N

11.8.2 Hardware MappingChan Alpha Beta Valves1 1 5 12 2 6 23 3 7 34 4 8 45 9 12 56 10 13 67 11 14 7Reference 1 . . 15Reference 2 . . 16

11.9 Tab to File and Save.11.10 For further instruction refer to the Lachet operations manual.

12.0 SAMPLE PREPARATION AND ANALYSIS12.1 Inspect modules for proper connections.12.2 Insert the 630nm wavelength filter.12.3 Turn on and set heating bath at 60oC. It should take approximately 15

minutes to reach desired temperature.12.4 Turn on power to all modules.12.5 Load method

12.5.1 In the main menu chose Methods12.5.2 Select Analysis Selection and Download.12.5.3 Scroll through the options and choose Ammonia or desired

method.12.6 Create a sample schedule.

12.6.1 In the main menu chose Sample. A new page will be displayed.12.6.2 Under File select Read Template (Method); choose nh3_qc. This

template has the check standards entered in the correct spots.12.6.3 Tab over to Edit.

12.6.3.1 Under Identification, type in the sample numbers inthe order that they will be loaded. For Matrix Spike andMatrix Spike Duplicate samples type either MSW orMSDW for water samples or MSS or MSDS for solidsamples. For the prep QC enter its standard abbreviation.


For example LCSW or MBS. Press Escape to return to theEdit menu.

12.6.3.2 Under Dilution enter any applicable dilution factors.Press escape to return to the Edit menu.

12.6.3.3 Under Operator Comments enter the LIMS runnumber as the operator. Under comments type the standardprep, LCS\CCV and spike log numbers. Press Escape, andEscape again to exit the Edit menu.

12.6.4 Save the schedule (necessary only if are not loading itimmediately)12.6.4.1 Tab over to File.12.6.4.2 Select Write Template (Method)12.6.4.3 Save the file as the LIMs run number or the date.12.6.4.4 Access it by following the directions in 12.6.2

choose the file that was saved rather than nh3_qc.12.7 Place reagent lines, except the Nitropruisside line, into proper containers.

Place the nitropruisside line in DI water. Apply tension on pump tubecassettes. Refer to Lachat Manuals for specific details and a diagram ofthe manifold.

12.8 Pump system until the lines are filled with reagent, then move thenitropruisside line to the proper container. Pump speed should be 35.

12.9 Pump system until a stable baseline is attained.12.10 Place calibration standards and blank in sample tray in descending order

of concentration followed by check standards and unknowns. Theconcentrations of the unknowns (samples) as well as the check standardsand other QC will be evaluated in relation to the absorbencies of thecalibration standards. The Lachat program prints out the raw data inmg/L.

12.11 Submit the schedule.12.11.1 Under Submit select Submit Current Tray.12.11.2 Type “Y” for Submit Current Tray Now? The calibration will

automatically run for the first tray of samples of the day. If thecalibration has shifted and re-calibration is desired change the “N”to a “Y” next to Should a new calibration be started? To start thetray in the middle of the schedule enter the schedule line numberthat is the desired starting point after start processing tray at. . .

12.11.3 If the calibration passes (r > 0.995) the Lachet will automaticallybeginning processing the sample tray.

12.11.4 If the calibration fails refer to section 14.0 Troubleshooting andMaintenance

12.12 Monitor the Lachat for failing QC and over range samples.12.12.1 Sample results can be viewed as they are calculated by pressing

Control, Shift and the number 1 simultaneously. To return to themain page press Control, Shift and the number 2 simultaneously.

12.12.2 For samples that have results higher than the highest calibrationstandard, dilute samples using reagent water and reanalyze.


12.12.3 If QC fails refer to section 14.0.12.13 At the end of run, place all feedlines in DI water, flush system and pump

dry.12.14 Turn off pump, all modules, and release levers on pump tube cassettes.

13.0 DATA CAPTURE13.1 Return to the main page by pressing Control, Shift, 2 if necessary.13.2 Tab over to Results Approval13.3 Select View Calibration and Sample Results13.4 Tab over to Tray Selection

13.4.1 Select Calibration Trays13.4.1.1 Choose the correct tray by the date. For example

January 23, 2003 is 030123xx where xx is the number ofthe calibration. The first successful calibration tray will be03012301 and the second will be 03012302

13.4.1.2 Tab over to Reports and select Print Report13.4.1.3 Tab over to Calibration Graphs and Stats and select

Print Calibration Stats13.4.2 Select Sample Trays

13.4.2.1 Choose the correct tray by the date. See 13.4.1.1.13.4.2.2 Tab over to Reports. Under Choose Report

Definition select limsexp. Then select Print Report.Finally Select Save Report to Disk. Change Path to Reportto I:\LachetAE\ and type Y to save.

14.0 TROUBLESHOOTING AND MAINTENANCE14.1 If the calibration fails.

14.1.1 Tab over to Program Results Approval14.1.2 Under Tray Selection choose calibration trays. Scroll to tentative

and press Enter.14.1.3 Tab over to Calibration Graphs and Stats and select Calibration

Graphs.14.1.4 Beneath the graph the Full Value must be > 0.995.

14.1.4.1 If the failing calibration is reasonably close to therequired value, press Escape.14.1.4.1.1 Type “N” for approve tentative calibration.14.1.4.1.2 Type “Y” for should another calibration be

started now.14.1.4.1.3 If calibration fails again repeat steps 14.1.1 –

14.1.4.1.2 and/or refer to 14.1.4.2 below.14.1.4.2 If the failing calibration is not at all linear.

14.1.4.2.1 Check that all the reagent lines are in the correctreagents

14.1.4.2.2 Check that the reagent lines are not flat.14.1.4.2.3 Make sure that the heat is on and at 60 degrees

Celcius.


14.1.4.2.4 Make sure there are no leaks in the manifold.14.1.4.2.5 Confirm that the wavelength filter is for 630nm.14.1.4.2.6 Confirm that the correct backpressure coil is

being used.14.1.4.2.7 Ensure that the flow is smooth, not pulsing

indicating a clog. Clean if necessary, Section14.2.

14.1.4.2.8 Refer to Lachat manual to confirm that themanifold is plumbed correctly.

14.1.4.2.9 If no problems are found re-make the reagentsto eliminate the possibility of contamination.

14.1.4.2.10 If problem persists refer to the Lachat operationManual.

14.2 If baseline drifts, peaks are too wide, or other problems with precisionarise, clean the manifold by the following procedure:14.2.1 Place all reagent lines in DI water and pump to clear reagents.14.2.2 Place reagent lines and carrier in 1 M hydrochloric acid (1 volume

conc. HCl added to 1L volume of DI water) and pump for severalminutes

14.2.3 Place all lines in DI water and pump until the HCl is thoroughlywashed out.

14.2.4 Resume pumping reagents.14.3 Refer to Lachat operation manual for further troubleshooting and

maintenance instructions.

13.0 DATA ACQUISITION, CALCULATIONS AND REDUCTION13.1 Accuracy- MS-MSDSpike Concentration, mg/L = (mLs of spike used) (conc. of spiking soln, mg/L)

(combined vol. of sample + spike, mL)

% Spike Recovery = [spike + sample] - [sample x C.F.*]spike value

*C.F (volume correction factor) = Volume of sample, mLs vol. of sample + spike, mLs

13.2 Accuracy- check standards and LCS

% Recovery = measured value X 100 true value

13.3 Precision- Relative percent difference (RPD):

% RPD = Abs.** [sample conc. - dup conc.] x 100ave. of sample & dup conc.

**Absolute Value


14.0 COMPUTER HARDWARE AND SOFTWARE14.1 Computer with StarLIMS14.2 Lachat QuickChem AE software

15.0 DATA MANAGEMENT AND RECORD MANAGEMENT15.1 After data has been captured by LIMS, it is reviewed by the analyst for




contents of the file cabinet are archived

16.0 QUALITY CONTROL/ QUALITY ASSURANCE16.1 The analyst must show an initial demonstration of capability (IDC) to

generated acceptable data, by successfully analyzing four replicates.16.2 ICV (initial calibration verification ): This mid range check standard is

analyzed immediately after calibration. Control limits are +/- 10% of thetrue value. If the recovery is outside of this range, terminate the run andcorrect the problem before proceeding.

16.3 ICB (initial calibration blank): Analyzed immediately after the ICV. Thevalue of the ICB must be below the method LOD. If not, terminate theanalysis and correct the problem before proceeding.

16.4 LCS (lab control sample): Analyze one LCS ( reference obtained from asource external to the lab) per analytical run. Control limits are +/- 10% ofthe true value. An out of control LCS may indicate that the calibrationstandard stock solution is inaccurate. If the recovery exceeds this,terminate the analysis and correct the problem before proceeding

16.5 CCV (continuing calibration verification): Analyze a CCV followingevery ten samples and at the end of the analysis. Control limits are +/-10% of the true value. If recovery is outside these limits, recalibrate andreanalyze all samples back to the last acceptable CCV or ICV.

16.6 CCB (continuing calibration blank): Analyzed immediately after the CCV.The value of the CCB must be below the method LOD. If not, terminatethe analysis and correct the problem before proceeding.

16.7 MS-MSD (matrix spike-matrix spike duplicate):A MS-MSD is requiredevery analytical run at a frequency of 5% (1 for every 20 samples) permatrix type. Refer to the quarterly control limits for acceptance criteria forboth accuracy and precision. If no limits have been established, use 80-120% for accuracy and 20% RPD for precision as interim limits until oneis calculated. The spikes are prepared by adding an appropriate aliquot of1000 mg/L working standard to the sample prior to analysis. Anappropriate spike level may vary, but should be high enough to be


detected above the sample concentration, yet should not be less than 4times the MDL.

16.8 Method blank: analyze one method blank per digestion batch. This is areagent water blank that is taken through all of the processes that thesamples are.


17.0 REFERENCES17.1 Methods for the Determination of Inorganic Substances in Environmental

Samples, EPA-600/R-93/ 100, August 1993, Method 350.1.17.2 Standard Methods for the Examination of Water and Wastewater, 18th

Edition, 1992, APHA-AWWA-WEF, Method 4500-NH3 H.17.3 Lachat QuickChemAE Operating Manual, Issued: 10/01/9317.4 Lachat QuickChem Methods Manual, Revision Date: 18 January 199617.5 Lachat QuickChemAE Software Reference Manual, 24 January 1994

release.


SUMMARY OF QUALITY CONTROL REQUIREMENTS



Five-point initial calibration plusblank (ICAL)

Initially and asneeded

r > 0.995 for regression line Repeat until acceptable

Initial calibration verification(ICV)

After each ICAL,prior to sample

analysis%R: 90-110% for all analytes

Remake and reanalyze ICVstandard once, if still

unacceptable, repeat ICAL

Initial calibration blank (ICB)After each ICV, prior

to sample analysis < RL

Remake and reanalyze CBonce, if still unacceptable

investigate and correctproblem or qualify if sample

results are >RL and <20times the ICB

Lab Control Standard (LCS)One per distillation

batchIn-house derived limitsDefault: 90% < %R < 110%

Reanalyze, if stillunacceptable and the failurecan not be determined to be

restricted to the LCS, allassociated samples must be

redistilled.

Method Blank (MB)One per distillation

batch < RL

Reanalyze, if stillunacceptable and the failurecan not be determined to be

restricted to the MB, allassociated samples must beredistilled or all results lessthan 20 times the MB and

greater than the RL must bequalified.

Continuing calibration verification(CCV)

Daily, prior tosample analysis, after

every 10 samples,and at end of run

%R: 90-110% for all analytes

Remake and reanalyze CCVonce, if still unacceptable

investigate and correctproblem, cannot proceed

until valid CCV obtained orICAL repeated.

Continuing calibration blank(CCB)

After each CCV andat end of analysis

< RL

Remake and reanalyze CBonce, if still unacceptable

investigate and correctproblem or qualify if sample

results are >RL and <20times the CCB

Capability demonstration sample(IDC)

Four (4) preparedsamples analyzed

one time prior to anysample analyses

In-house determined criteriafor LCS recovery and

precisionRepeat until acceptable

Sample duplicate (DUP) or matrixspike duplicate (MSD)

One (1) peranalytical batch per

matrix

In-house derived limitsDefault: RPD < 20% if

analytes > RL

Investigate problem, ifsystem precision in controlqualify results. If systemprecision out of controlreanalyze entire batch

Matrix spike sample (MS)One (1) per

analytical batch permatrix

In-house derived limitsDefault: 80% < %R < 120%

Investigate problem, ifsystem accuracy in controlqualify results. If systemaccuracy out of controlreanalyze entire batch


CT Laboratories SOP No: CC-18 Rev.3Inorganics Laboratory Section Page 13 of 14 1/27/03Data Validation Checklist

LIMS #: Method: Ammonia automated EPA 350.1


Yes … No



IndependentReview

Comments:



2. Was the calibration performed using the required number of standards? Four plus a blank



4. Were the ICV and ICB run immediately after the calibration curve? ---



7. Was the method blank within acceptable limits? (if run includes distilled samples) <LOD

8. Were the CCV’s and the CCB’s analyzed at the required frequency? 1per 10 samples

9. Were the CCV recoveries acceptable? 90 – 110 %

10. Were the CB results acceptable? < LOD

11. Was a LCS ran at the required frequency? 1 per 20 samples

12. Was the LCS recovery acceptable? 90-110 %


14. Were the MS and MSD prepared at the required frequency? 1per 20 field samples

15. Were the MS and MSD recoveries acceptable? Within in house QClimits

16. Was the RPD between the MS and MSD acceptable? Within in house QClimits


CT Laboratories SOP No: 6105B-Trace Rev. 8Metals Laboratory Section Page 1 of 28 05/05/04

CT LaboratoriesBaraboo Laboratory Divison

Title: Inductively Coupled Plasma Emission—Trace 61E

SOP Number: 6105B—Trace

Prepared by: ___________________________________Date






1.0 SCOPE AND APPLICATIONMetals in solution can be readily analyzed by atomic emission using an InductivelyCoupled Plasma (ICP) spectrometer. This method is applicable to the determinationof various metals in drinking water, surface water, groundwater, sludge, soils, andindustrial wastes. All matrices, excluding filtered groundwater samples anddrinking waters with a turbidity less than 1 NTU, will require a digestion prior toanalysis.

2.0 METHOD SUMMARY2.1 If necessary, prior to analysis, samples are digested using an approved

method. See SOPs 6205B, 6225B, 6230B, M200.2, and M-soluble forfurther information on sample digestion.

2.2 This method describes multielement determinations using a TJA 61ETrace ICP. This instrument measures characteristic emission spectra byoptical spectrometry. The samples are first nebulized using a glassnebulizer and transported to plasma. Element specific emission spectraare produced by the plasma. The spectra are dispersed by a diffractiongrating and the intensity of the emission lines are monitored byphotomuliplier dectors that contain individual exit slits for eachwavelength being determined. Samples are routinely analyzed using aninternal standard of Yttrium to eliminate certain interference problems.

2.3 The data is exported to the LIMS system and reviewed by the analyst.Following analyst review, the data is given to a qualified reviewer forcomplete data review. After the data has been reviewed and it isdetermined that it is valid data, the reviewer sends the data to the“validated” mode in the LIMS system.

3.0 DEFINITIONS -3.1 Reagent Blank- A solution of de-ionized water, (containing in correct

proportion, all reagents required by the method), used with the calibrationstandards to standardize the instrument, as a calibration blank, and forsample dilution.

3.2 Calibration Standards - A series of known standard solutions, which shallinclude the reagent blank, used for calibration of the instrument within themeasurable linear range. Calibration standards shall contain, in correctproportion, all reagents required by the method. Acceptance of thecalibration requires a correlation coefficient of 0.995 or better. No samplesshall be analyzed without acceptable calibration.

3.3 Calibration Verification Standard-Initial (ICV) & Continuing (CCV) - Amidpoint calibration standard which is analyzed at the beginning of the run(ICV), at a frequency of 1 per 10 samples during a run (CCV), and at theend of a run to verify calibration throughout the run. The ICV must be froma second source different than that of the calibration standards. Note formethod 200.7 that limits for ICV are tighter than those for CCV (seesection 16).


3.4 CB (Calibration Blanks- Initial and Continuing) - A reagent blank solution,which is analyzed immediately following the ICV (Initial CalibrationBlank-ICB), at a frequency of 1 per 10 samples during a run (ContinuingCalibration Blank-CCB), and at the end of a run to check for drifts incalibration, or possible analyte carry-over. Warning criteria include that theabsolute value be less than or equal to the three times the IDL for a givenanalyte for SW-846 work or less than ½ the MRL for ACOE work. Controlcriteria consist of the absolute value being less than or equal to 2 times theMDL for a given analyte for SW-846 and is determined by the QAPP forACOE work. If this range is exceeded, a new calibration will be necessary.

3.5 LCS (Laboratory Control Sample)- A mid-range standard, prepared from asource different from that used for calibration standards, that is carriedthrough the entire preparation and analytical method. The LCS is used toverify the accuracy of the preparation method. A minimum of one LCS isprepared per batch and is analyzed at the beginning of an analytical batch.

3.6 MB (Method Blank) - A Reagent Blank (see 3.1) which is carried throughthe entire preparation and analytical method. The method blank is used todetect possible contamination that may occur prior to or during the samplepreparation. A minimum of one MB is prepared per batch and is analyzedat the beginning of an analytical batch. Blank recovery should be less than2x MDL for SW846, less than the MDL for SWDA samples and isdetermined by the QAPP for ACOE samples.

3.7 MS-MSD ( Matrix Spike-Matrix Spike Duplicate): - Two separate samplealiquots to which a known concentration of analyte has been added which iscarried through the entire preparation and analytical procedure. The purposeof a matrix spike is to reveal any matrix effect from the sample on therecovery of the analyte by the method being used. An MS-MSD pair isprepared for every 20 samples of a given matrix per day for 6010B and oncefor every 10 samples of a given matrix per day for 200.7. For ACOE workonly an MS is prepared and a duplicate sample is prepared rather than anMSD. Failure to meet criteria may be due to poor recovery during thepreparation method or due to matrix interference within the digestate. To beconsidered acceptable, MSD must meet both the same % recovery criteriaas an MS, and the same % RPD as a duplicate sample.

3.8 Duplicate sample- A separate sample aliquot which is carried through theentire preparation and analytical procedure. A duplicate is prepared forevery 20 samples for ACOE work.

3.9 Method Reporting Limit (MRL) or Contract Required Detection Limit(CRDL) Standard: Detection level standard at a level near the reportinglimit, or at a level specified by client contract. When required, it is to beanalyzed following the ICB, and prior to the last CCV standard in the run.

3.10 Interelement Correction Factors (IEC) – These correction factors aredetermined by analyzing a concentration range of known interferents (Al,Ca, Co, Cr, Cu, Fe, Mg, Mn, Ni, V and Zn) and examining all other lines fora significant linear response. A line is considered to be significantly affectedwhen the correlation coefficient for the interference is 0.99 or better and the


correction factor multiplied by ten is greater than the MDL of the affectedline. For interferents known to occur at high levels in environmentalsamples (Al, Ca, Cr, Cu, Fe, Mg and Zn) the interference will be consideredto be significant when the correction factor multiplied by 100 is over theMDL of the affected line and the correlation coefficient in 0.99 or better.Interelement correction is used where applicable.

3.11 Linear Dynamic Range (LDR) – The upper limit of the linear dynamicrange is established for each wavelength utilized by determining the signalresponses from a minimum of three different concentration standards acrossthe range. One of these will be near the upper limit of the range. Theranges used for the analysis of samples are judged by the analyst from theresulting data. The data and calculations are kept on file. The upper rangelimit is an observed signal no more than 10% below the level extrapolatedfrom the lower standards. Determined analyte concentrations above theupper range limit are diluted and reanalyzed. Note: for ACOE work,analyte concentrations above the upper calibration limit are dilutedand reanalyzed. New dynamic ranges are determined whenever there is asignificant change in instrument response. For analytes that routinelyapproach the upper limit of the range, the range will be checked biannually.For analytes that are known interferents and exceed the dynamic range, theanalyst will check that IEC’s have been correctly applied.

3.12 ICS-A (Interelement Correction Standard-A): A standard containing theelements Al, Ca, and Mg at 500mg/L and Fe at 200mg/L for non-ACOEwork and Al, Ca, Mg and Fe at 500mg/L for ACOE work. This standard isanalyzed when using method 200.7 or performing ACOE work followingthe ICV at the beginning of the run to determine that interelement correctionfactors are correctly compensating for interference from these elements onother analyte lines. The ICSA may be required to be run before the lastCCV of the run for ACOE work. Check the QAPP to determine if this isnecessary. For ACOE work, the ICSA should be within the absolutevalue of two times the MDL for all analytes except Al, Ca, Fe and Mgunless a different requirement is specified within the contract.

3.13 ICS-AB (Interelement Correction Standard-AB): A standard containing theelements Al, Ca, Mg at 500mg/L, Fe at 200mg/L for non-ACOE work, Al,Ca, Mg and Fe at 500mg/L for ACOE work and all other elements at500ug/L. This standard is analyzed following the ICV at the beginning ofeach run. It is analyzed to determine that the IEC are correctly preventinginterference by these elements on the measurement of other analytes. TheICSAB may be required to be run before the last CCV of the run for ACOEwork. Check the QAPP to determine if this is necessary

3.14 PDS (Post Digestion Spike): For CLP protocol, when a matrix spike fallsoutside of the acceptance limits a post digestion spike is used to determine ifthe sample digestion matrix is interfering with the analysis of the analyte.The sample is spiked at a level similar to that of the matrix spike. ForACOE work, a PDS will be conducted at a minimum rate of one perprep batch per unique matrix.


3.15 SD (Serial Dilution Analysis): A sample is diluted x5 with method blanksolution and analyzed. The diluted result and the undiluted result shouldagree within a limit of precision defined by the program (SW846, CLP,200.7) or client QAPP. For ACOE work, a SD will be conducted at aminimum rate of one per prep batch per unique matrix.

3.16 Batch- A batch consists of 20 samples of the same matrix analyzed on thesame day or 20 samples of the same medium that have been preparedtogether.


unnecessary exposure to hazardous chemicals and contaminants in samples.All activities performed while following this procedure should utilizeappropriate laboratory safety systems.

4.2 Insure that waste collection vessels contain enough room to accommodateall wastes that will produced during the operation of the instrument.

5.0 CAUTIONS5.1 Samples must be preserved and analyzed within holding times stated in

chart.

Aqueous SolidsPreservative: pH <2 with HNO3 cool 4oCHold Time: 180 days 180 days

6.0 INTERFERENCES6.1 Background emission and stray light are corrected using background

correction. See TJA operator’s manual for further instructions onbackground correction application.

6.2 Spectral overlaps are corrected for using interelement correction factors(IEC). When IEC are used, the interfering elements must be analyzedalong with the elements of interest. The accuracy of IEC shall be verifieddaily by analyzing the ICSAB. All IEC factors shall be updatedevery six months or when an instrumentation change occurs, such aschanging a torch, nebulizer, injector or plasma conditions.

6.3 Physical interferences such as viscosity are minimized by using an internalstandard. Post digestion spike and serial dilutions help to determine ifphysical interferences are present.

6.4 Chemical interferences include molecular compound formation, ionizationeffects, and solute vaporization effects. Chemical interferences are notnormally seen during ICP analysis and are highly matrix dependent.

6.5 Memory interferences occur when a sample of high analyte concentrationdoes not thoroughly rinse prior to the analysis of the next sample. Thiscauses elevated readings for that analyte in the subsequent sample.Memory effects can be minimized by rinsing at least 60 seconds betweensamples.


7.0 PERSONNEL QUALIFICATIONSPersonnel operating the ICP shall have background knowledge of the scientificprinciples used during this application. All operators shall perform an initialdemonstration of capability (IDC) prior to analyzing any samples. It is preferablefor the operator to have at least two semesters of college chemistry.

8.0 APPARATUS AND MATERIALS8.1 Equipment and supplies

8.1.1 TJA Trace 61E ICP, autosampler, computer, printer.8.1.2 Argon: liquid high purity or gaseous pre-purified grade.8.1.3 Class A volumetric flasks and pipettes.8.1.4 Disposable 15-mL polystyrene culture tubes.8.1.5 100 uL eppendorf pipette.8.1.6 10-mL oxford pipette.

8.2 Reagents8.2.1 Mixed and single element stock metals standards. See Section 9and Appendix A, B, C and D for instructions on making the workingstandards.8.2.2 Nitric acid, conc. (Trace Metals grade)8.2.3 Hydrochloric acid, (Trace Metals Grade)8.2.4 Deionized water

9.0 INSTRUMENT CALIBRATIONThe default calibration for routine work is a single-point calibration using a silver

calibration standard, multi-element calibration standard and a calibration blank. Seesection 11.0 for further instructions on how to perform the calibration.

Note: For samples requiring a multipoint calibration use the ACOE-LCGmethod instead of the Yttrium internal standard method. See Appendix A forpreparations of calibration standards and blank for the multipoint calibration. SeeAppendix B for the preparation of the calibration standards and blank for the“Shell” method. See Appendix C for the preparation of the calibration standardsand blank for the Sodium and Potassium calibrations. See Appendix D for thepreparation of the calibration standards and blank for the Boron calibration.

9.1 Multi-element calibration standard: (Called the High Std in the TJAmethod) Into a 1000mL volumetric flask, add 500mL of Milli-Q H2O,10mL of conc. HNO3, and 10mL conc. HCl. Add 10mL each of SPEXQC-21 standard and SPEX QC-7, 2.4mL each of 10,000 mg/L Al, Ca, andMg(ULTRA SCIENTIFIC or equivalent), 0.90mL of 10,000 mg/LFe(ULTRA SCIENTIFIC or equivalent). Dilute to volume with Milli-QH2O and mixby inverting several times. Transfer to a clean 1L Nalgene bottle. Prepareevery 6 months or as needed.

Concentration: 1000 ug/LAnalytes: Al, As, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Pb,Sb, Se, Tl, V, Zn


9.2 Silver Calibration Standard: (Called Standard #3 in the TJA method) Intoa 1000mL volumetric flask, add 500mL of Milli-Q H2O, 10mL of conc.HNO3, and 10mL conc. HCl. Add 1mL of 1000 mg/L Ag Std(ULTRASCIENTIFIC or equivalent). Dilute to volume with Milli-Q H2O and mixby inverting several times. Transfer to a clean 1L Nalgene bottle. Prepareevery 6 months or as needed.

Concentration: 1000 ug/L Analytes: Ag9.3 Calibration Blank: Into a 1 L. volumetric flask, add 750 mL of Milli-Q

water and 10mL of conc. HNO3 and 100mL HCl. Mix, dilute to volumewith Milli-Q H2O. Transfer to a clean 1 L. nalgene bottle. Prepare every6 months or as needed.

9.4 Yttrium Internal std : Into a 1000mL volumetric flask, add 500mL ofMilli-Q H2O, 1mL 10,000 mg/L Yttrium std Dilute to volume with Milli-Q H2O and mix by inverting several times. Transfer to a clean 1LNalgene bottle. Prepare every 6 months or as needed. Note: for Na/K usethe Lithium/Yttrium internal standard- see Appendix C forpreparation instructions.

Concentration: 10mg/L Yttrium solution.9.5 Initial/Continuing Calibration Verification (ICV/CCV): Into a 1000mL

volumetric flask, add 500mL of Milli-Q water, 10 mL of conc. HNO3 and10mL HCl. Add the following:10 mL SPEX Spike Sample Standard 1 or Equivalent0.5mL Mo 1000mg/L2mL Interferents-A-SPEX or equivalentDilute to volume with Milli-Q water, mix and transfer to a clean 1 LNalgene bottle. Make new every 6 months or as needed.Concentration: Analyte:50ug/L Cd, Be50ug/L Ag200ug/L Cr250ug/L Cu500ug/L Co, Mn, Mo, Ni, Pb, Sb, V, Zn2000ug/L Ba, As, Tl, Se5,000ug/L Fe10,000ug/L Ca, Mg12,000ug/L Al

9.6 ACOE Initial/Continuing Calibration Verification (ACOE ICV/CCV):Into a 1000mL volumetric flask, add 250mL of Milli-Q water, 10 mL ofconc. HNO3 and 10mL HCl. Add the following:10 mL SPEX Spike Sample Standard 1 or Equivalent0.5mL Mo 1000mg/L50mL SPEX Interferent A solution or EquivalentDilute to volume with DI, mix and transfer to a clean 1 L Nalgene bottle.Make new every 6 months or as needed.Concentration: Analyte:


50ug/L Cd, Be50ug/L Ag200ug/L Cr250ug/L Cu500ug/L Co, Mn, Mo, Ni, Pb, Sb, V, Zn2000ug/L Ba, As, Tl, Se50,500ug/L Fe125000ug/L Ca, Mg126,000ug/L Al

9.7 Interference Check Solution (ICSA): Into a 500 mL volumetric flask, add300 mL of Milli-Q H2O, 5 mL of conc. HNO3 and 5mL conc. HCl. Addthe following stock solutions in the volumes listed:50 mL Spex Interferent A or equivalentDilute to volume with Milli-Q H2O and mix by inverting several times.Transfer to a clean 500 mL Nalgene bottle. Prepare every 6 months or asneeded.Concentration: Analyte:500,000 ug/L Al, Ca, Mg200,000 ug/L Fe

9.8 Interference Check Solution (ICSAB): Into a 500 mL volumetric flask,add 300 mL of Milli-Q H2O, 5 mL of conc. HNO3 and 5 mL conc. HCl.Add the following stock solutions in the volumes listed:50 mL Spex Interferent A or equivalent2.5 mL Spex QC-21 or equivalent0.25 mL Ultra Ag 1000 mg/L or equivalent0.25 mL Ultra Ba 1000 mg/L or equivalentDilute to volume with Milli-Q H2O and mix by inverting several times.Transfer to a clean 500 mL Nalgene bottle. Prepare every 6 months or asneeded.Concentration: Analyte:500,000 ug/L Al, Ca, Mg200,000 ug/L Fe500 ug/L Ag, As, Ba, Be Cd, Co, Cr, Cu, Mn, Mo, Ni,

Pb, Se, Sb, Tl, V, Zn9.9 CLP/ACOE ICSA solution: Into a 500 mL volumetric flask, add 300 mL

of Milli-Q H2O, 5 mL of conc. HNO3 and 5 mL conc. HCl. Add thefollowing stock solutions in the volumes listed:50 mL Spex Interferent A or equivalent2.5 mL Spex QC-21 or equivalent150mL Ultra Fe 10000mg/L or equivalentDilute to volume with Milli-Q H2O and mix by inverting several times.Transfer to a clean 500 mL Nalgene bottle.Prepare every 6 months or as needed.Concentration: Analyte:500,000 ug/L Al, Ca, Fe, Mg


9.10 CLP/ACOE ICSAB solution: Into a 500 mL volumetric flask, add 300 mLof Milli-Q H2O, 5 mL of conc. HNO3 and 5 mL conc. HCl. Add thefollowing stock solutions in the volumes listed:50 mL Spex Interferent A or equivalent2.5 mL Spex QC-21 or equivalent150mL Ultra Fe 10000mg/L or equivalent0.25 mL Ultra Ag 1000 mg/L or equivalent0.25 mL Ultra Ba 1000 mg/L or equivalentDilute to volume with Milli-Q H2O and mix by inverting several times.Transfer to a clean 500 mL Nalgene bottle.Prepare every 6 months or as needed.Concentration: Analyte:500,000 ug/L Al, Ca, Fe, Mg500 ug/L Ag, As, Ba, Be Cd, Co, Cr, Cu, Mn, Mo, Ni,

Pb, Se, Sb, Tl, V, Zn

9.11 CRI/CRDL/MRL solution: Concentrations needed depend on theCRDL/MRL of a given contract.

10.0 SAMPLE COLLECTION, HANDLING AND PRESERVATION

Aqueous SolidsPreservative: pH <2 with HNO3 cool 4oCHold Time: 180 days 180 days

11.0 SAMPLE ANALYSIS11.1 Instrument start-up procedure:

11.1.1 Open valve at argon tank.11.1.2 Inspect sample and rinse pump tubing and change if necessary.11.1.3 Fill DI rinse reservoir with DI water.11.1.4 Open up ThermoSpec software on the PC. Go to SETUP, then

PLASMA CONTROL PANEL.11.1.5 Plasma startup: Press STARTUP. The purge time should be set for

90 sec. The start up power should be set to the first value to beused in the analysis.

11.1.6 Press ‘CONTINUE’ to light the plasma.11.1.7 Set the plasma conditions as follows:

RF power: 950Nebulizer pressure: 0.70 L/MinPump speed: 130rpm

11.1.8 After a 30-minute warm-up period, perform a polychromatorprofile using a 2mg/L Arsenic Standard. The peak should becentered on zero. Record the resultant peak intensity. It should begreater than 700. Record this in the instrument run logbook.


11.1.8.1 Check the optics vacuum reading on front panel ofinstrument. Vacuum should be <20 millitor. If not, inspectvacuum pump oil reservoir and fill to halfway mark oninspection window if necessary.

11.1.8.2 Check condition of nebulizer: put pump tube into a100mg/L Yttrium Std. With the lights off and after enoughtime has elapsed for the Yttrium standard to reach theplasma, a red cone should be noticeable in the center of theplasma. If the nebulizer is in good condition and thenebulizer gas flows are set properly, the red cone shouldproject about ¼” beyond the coils. If not, check thesettings, the pump tubes, and inspect the nebulizer under amicroscope.

11.1.9 Create Autosampler Table:11.1.9.1 Go to method; Choose method to analyze samples with.11.1.9.2 Press AUTOSAMPLER ,then,11.1.9.3 CREATE TABLESAMPLES11.1.9.4 Press STANDARDS: Inputs the entire standard set into the

table.11.1.9.5 Add QC SAMPLES in order. The standard order is ICV,

ICB, ICSA (if necessary, such as for ACOE work orSDWA samples. See section 16.0 for further information),and then ICAB

11.1.9.6 Add all samples, LCS, Blanks, MS-MSD, etc. in order.11.1.9.7 Insert continuing QC into the table. A CCV followed by a

CCB is placed after every 10 samples/batch QC samplesand at the end of the run. The ICSA and ICSAB count assamples for ACOE work. For some ACOE work, aCRDL/MRL, an ICSA and an ICSAB may need to beanalyzed prior to the last CCV, CCB- consult project QAPPfor details.

11.1.9.8 All ICV, CCV, and ICSAB are compared to check tablesconstructed in the method. Make sure to designate these inthe autosampler table so that they will be marked pass orfail as the analysis proceeds.

11.1.9.9 SAVE (F9), save 3 times in succession while exiting thescreens to get back out to Analysis.

11.1.9.10 Print Autosampler Table: This will be used when preparingall samples and standards.

11.1.9.11 Using the printed autosampler table sheet, prepare allstandards, QC samples, and samples in their designatedpositions in the autosampler. Prepare any bench spikes andplace them in autosampler. Calibration standards, CCV,ICV, CCB, ICB and ICSAB all go into glass vials and areplaced where designate by the table in the “L” rack portionof the autosampler. All others are poured into plastic vials


and go into the designated areas within the 48 positionblocks.

11.2 Calibration and AnalysisOnce all calibration standards have been placed in the autosampler, beginthe calibration and prepare the remaining samples as the calibration isbeing carried out.11.2.1 Press 'ANALYZE'.11.2.2 Prepare a serial dilution for new or unusual matrices by performing

a 1:5 dilution on the sample.11.2.3 Arrange the standards on the autosampler according to the

autosampler table positions.11.3 Instrument shutdown

11.3.1 If run will not be finished during work hours, program theinstrument to shutdown at the end of the analytical run. Whensetting up on the ANALYSIS page set the “end of analysiscondition” to TERMINATE. This will shut off the plasma theargon and the pump.

11.3.2 For manual shutdown go to PLASMA STARTUP and selectSHUTDOWN. After a 30 second cooling off period, the systemwill be in complete shutdown mode. Release the pump tubetensioners.

12.0 INSTRUMENT MAINTENANCE AND TROUBLESHOOTING12.1 Pump tubing and rollers: Ensure that the pump rollers turn freely. Inspect

pump tubing daily and replace when it starts failing to retain its shape.12.2 Drain line: Spray chamber drain line must flow unimpeded directly down

into the waste jug. Hose must be under water to maintain atmosphericpressure inside spray chamber. When emptying jug, always add back inabout 6” of clean water for hose to be submerged in. Drain line forautosampler in separate jug. Make sure line is draining properly.

12.3 Spray Chamber: If the spray chamber becomes dirty, the sample wastemay not drain properly. Remove and wash with hot soapy water, thenrinse with DI H2O.

12.4 Torch and O-rings: The O-rings surrounding the torch may need to bereplaced if the plasma becomes unstable or internal standard emissioncounts fall off. See TJA manual for technique. Torch needs to be cleanedoccasionally with aqua regia followed by sonication.

12.5 Vacuum system. Must maintain <20 millitorr vacuum. Change oil every 6months. Pump needs a minor rebuild every 2 years (new gaskets, anti-suckback valve) or as needed, and a major rebuild every 4 years ( gaskets,seals, anti-suckback valve, vanes, springs).

13.0 DATA ACQUISITION, CALCULATIONS, AND DATA REDUCTION13.1 See SOP FO-DCICP for instructions on Data Capture13.2 Sample Calculations:


Liquid Concentration (ug/L) = A x C

Solid Concentrations (mg/kg) = A x B x C , D x E

where A = instrument reading for sample (ug/L)B = total volume of digestion (L)C= analyst dilution factor, if necessary (ex. For a 1 to 10 dilution, C = 10)D = amount of sample used in digestion (g)E = percent solids/100, if necessary

Spike Recovery (%) = (Spiked sample concentration – Sample concentration) x 100 (Spike amount)

%RSD = (MS – MSD) x 100 , (MS + MSD)/2

where MS = Matrix spike concentrationMSD = Matrix spike duplicate concentration

14.0 COMPUTER HARDWARE AND SOFTWARE14.1 Computer with StarLIMS14.2 Computer with ThermoSPEC software

15.0 DATA MANGEMENT AND RECORD MANAGEMENT15.1 After data is captured by LIMS, the data is reviewed by the analyst to

insure data validity. See checklist for data review guidance.15.2 After the analyst reviews data, it is given to a technical reviewer, usually

the Inorganic Lab Supervisor, to review for validity of data. See checklistfor data review guidance.

15.3 After data is deemed acceptable by both the analyst and the technicalreviewer, it is sent to “validated” in LIMS.

15.4 Raw data, bench sheets and spreadsheets are stored in the file cabinet.Contents of the file cabinet are periodically archived to storage.

16.0 QUALITY CONTROL 16.1 For the routine analysis of groundwater, wastewater, leachate, surface

water, soil, sludge, TCLP/SPLP extracts following method 6010B:Required QC following instrument calibration is as follows :16.1.1 ICV (initial calibration verification); The ICV is prepared from an

alternate source standard whose concentrations are within thelinear working range of the instrument. The results of the ICVshould agree within 10% of the expected value for a given analyte.The relative standard deviation (RSD) between the two replicateintegrations should be <5%. If results are outside of this range,corrective action must be taken before samples can be analyzed.


This would include recalibration, repouring standard, or re-mixingstandard.

16.1.2 ICB (initial calibration blank); analyze the calibration blank. Theresults of the initial calibration blank must be < 3x IDL for a givenanalyte. If the average of the two replicates is not < 3x IDL,terminate the analysis, correct the problem and recalibrate orappropriately qualify the data. If the blank is less than 1/10th theconcentration of the action level of interest and no sample is withinten percent of the action limit, analyses need not be rerun and re-calibration is not necessary before continuing with the analysis.

16.1.3 ICSAB (interference check solution); analyze a solution containing500 mg/L Al, Ca, Mg, 200 mg/L Fe and all other analytes ofinterest at 0.50 mg/L. Recovery for analytes of interest is +/- 20%true value. If recovery is outside this range, corrective action mustbe taken before samples can be analyzed. Check placement ofbackground correction points and IECs as a place to starttroubleshooting .

16.1.4 LCS (laboratory control sample); analyze an alternate sourcereference sample. Control limits are +/- 20% of true value or in-house limits, whichever is more restrictive, or as specified in aclient QAPP.

16.1.5 MB (method blank); analyze a reagent blank. The method blank isa reagent blank that has been taken through the preparations stepsalong side the samples being analyzed. Control limits are + theMDL. If the average of the two replicates is not < MDL, terminatethe analysis, correct the problem and recalibrate or appropriatelyqualify the data that falls within the MDL and twenty times theconcentration of the analyte in the method blank.

16.1.5 CCV (continuing calibration verification); analyze a checkstandard after every ten samples and following the last sample inthe run. This standard should be at a level approximately mid-scale. Control limits are +/- 10% of true value. If values falloutside this range, all samples back to the last acceptable ICV orCCV must be repeated.

16.1.6 CCB (continuing calibration blank); The results of the continuingcalibration blank must be < 3x IDL for a given analyte. If theresult falls outside this, reanalyze all samples back to the lastacceptable CCB or qualify all sample <20 times the blank andgreater than the MDL.

16.1.7 MS/MSD (matrix spike/matrix spike duplicate); for non-digestedsamples, prepare a bench spike in duplicate at a frequency of 5%or per analytical batch, whichever is more frequent. Control limitsare +/- 25% of true value, and 20% RPD, or use calculated limits,whichever is tighter. See Sec. 18.0 for bench spike preparation. Fordigested samples, see “Predigestion Spike” chart in section 18.0.For digested samples, analyze the MS/MSD samples as they apply


to each digestion set. Follow the above for control limits. Fordigested spikes with sample results greater than four times thedigested spike level, prepare and analyze a PDS sample if the MSand/or MSD is outside the control limits. Prepare the PDS at alevel approximately two times the sample level.

16.2 For SDWA analysis following method 200.7:Required QC following instrument calibration is as follows :16.2.1 ICV: Referred to in 200.7 as LPC (laboratory performance check);

analyze the mid-cal standard. Control limits are +/- 5% of truevalue. If values fall outside this range, recalibrate for the affectedanalytes.

16.2.2 ICB (initial calibration blank); analyze the calibration blank. Theabsolute value of the result should be below the LOD for theanalyte(s) of interest. If the blank result falls outside this, evaluatethe effect on the sample results and/or recalibrate for the affectedanalytes. Samples with results >10x the associated blank valueneed not be reanalyzed.

16.2.3 ICSA (interference check solution: interference only) analyze asolution containing 500 mg/L Al, Ca, Mg, and 200 mg/L Fe. Thissample must be analyzed at the beginning of the analytical runbefore the ICSAB. Recovery for interfering analytes is +/- 20%true value. All other analytes need to be + 2X MDL. Ifrecovery/result is outside the acceptable range, corrective actionmust be taken before samples can be analyzed. Check placementof background correction points and IECs as a place to starttroubleshooting .

16.2.4 ICSAB (interference check solution); analyze a solution containing500 mg/L Al, Ca, Mg, 200 mg/L Fe and all other analytes ofinterest at 0.50 mg/L. Recovery for analytes of interest is +/- 20%true value. If recovery is outside this range, corrective action mustbe taken before samples can be analyzed. Check placement ofbackground correction points and IECs as a place to starttroubleshooting .

16.2.5 LCS (laboratory control sample); analyze an alternate sourcereference sample per batch of 20 samples of the same matrix.Control limits are +/- 10% of true value, or manufacturer’s limits,whichever is tighter.

16.2.6 MB (method blank); analyze a reagent blank per 20 samples of thesame matrix. The method blank is a reagent blank that has beentaken through the preparations steps along side the samples beinganalyzed. Control limits are + the MDL. If the average of the tworeplicates is not < MDL, terminate the analysis, correct theproblem and recalibrate or appropriately qualify the data that fallswithin the MDL and twenty times the concentration of the analytein the method blank.


16.2.4 CCV: Referred to in 200.7 as LPC (laboratory performance check);analyze the mid-cal standard after every 10 samples. Control limitsare +/- 10% of true value. If values fall outside this range,reanalyze all samples back to the last acceptable ICV or CCV.

16.2.5 CCB (continuing calibration blank); analyze the calibration blankimmediately after each CCV. The absolute value of the resultshould be below the LOD for the analyte(s) of interest. If the resultfalls outside this, evaluate the effect on the sample results. Sampleresults >10x the associated blank value need not be reanalyzed.Otherwise, reanalyze all samples back to the last acceptable CCBor qualify data that is >LOD and <10x the associated blank.

16.2.6 MS/MSD (matrix spike/matrix spike duplicate); for non-digestedsamples, prepare a bench spike in duplicate at a frequency of 5%or per analytical batch, whichever is more frequent. Control limitsare +/- 25% of true value, and 20% RPD, or use calculated limits,whichever is tighter. See Sec. 18.0 for bench spike preparation. Fordigested samples, see “Predigestion Spike” chart in section 18.0.For digested samples, analyze the MS/MSD samples as they applyto each digestion set. Follow the above for control limits. Fordigested spikes with sample results greater than four times thedigested spike level, prepare and analyze a PDS sample if the MSand/or MSD is outside the control limits. Prepare the PDS at alevel approximately two times the sample level.

16.3 For the CLP-like level 4 analysis of groundwater, surface water,wastewater and soil:A default of three replicate exposures per sample should be used forACOE work unless specified differently in QAPP.Required QC following instrument calibration:16.3.1 ICV (initial calibration verification): analyze the alternate source

check standard immediately following calibration. Control limits+/- 10 % true value.

16.3.2 ICB (initial calibration blank): analyze the calibration blank. Theabsolute value of the result must be below the contract requireddetection limit (CRDL) or the limit stated within the QAPP for theproject. If a result falls outside this, recalibrate for the affectedanalytes.

16.3.3 CRDL (contract required detection limit standard) or MRL(Method Required Limit): analyze a standard at a level two timesthe contract-required detection limits (CRDL) or at the level statedwithing the QAPP for the project. Follow limits stated within theQAPP as there are no EPA specified control limits for thisstandard. This sample must be analyzed at the beginning and theend of the run.

16.3.4 ICSA (interference check solution: interference only) analyze asolution containing 500 mg/L Al, Ca, Mg, and Fe. This samplemust be analyzed at the beginning of the analytical run prior to the


ICSAB. Refer to QAPP for acceptablility criteria. For ACOEwork, the default criteria is the absolute value of two times theMDL for all analytes except Al, Ca, Mg and Fe which must have arecovery between 80-120%. Refer to QAPP to determine if theICSA must also be analyzed at the end of the run.

16.3.5 ICSAB (interference check solution: interference plus analytes);analyze a solution containing 500 mg/L Al, Ca, Mg, and Fe, andall other analytes of interest at 0.50 mg/L. Recovery for analytesof interest is +/- 20% true value. If recovery is outside this range,corrective action must be taken before samples can be analyzed.Check placement of background correction points as a place tostart troubleshooting. This sample must be analyzed at thebeginning of the run. Refer to the QAPP to determine if theICSAB must be analyzed at the end of the run.

16.3.6 Digested Sample set to include MB (S or W), LCS (S or W), MS,DUP.

16.3.7 Serial Dilution: Analyze a x5 dilution of a sample from thedigestion set. For sample results > 50x the MDL, the %RSDbetween the serial dilution result and the sample result must be <10.

16.3.8 Post digestion spike addition (bench spike): An analyte spikeadded to a portion of a prepared sample, or its dilution, should berecovered to within +/- 25% of the known value or as specified bythe client QAPP. The spike addition should produce a minimumlevel of 10 times the instrumental detection limit. If the spikerecovery falls outside the limits, a matrix effect should besuspected.

16.3.9 CCV (continuing calibration verification): Analyze a mid-levelstandard after every ten samples. The CRDL/MRL, ICSA, ICSABand batch QC all count as samples. Control limits are +/- 10% oftrue value. If any result falls outside this, all samples back to thelast acceptable ICV/CCV must be reanalyzed.

16.3.10 CCB (continuing calibration blank); Analyze the calibration blankafter the CCV. Refer to the QAPP for CCB acceptance limits. Ifany result falls outside the limits, all samples with results less 20times the CCB must be reanalyzed back to the last acceptable CCBor appropriately qualified.

16.3.11 MS/DUP (matrix spike/matrix duplicate); for non-digestedsamples, prepare a bench spike and a duplicate at a frequency of5% or per analytical batch, whichever is more frequent. Controllimits are specified in client QAPP. See Sec. 18.0 for bench spikepreparation. For digested samples, see “Predigestion Spike” chartin section 18.0. For digested samples, analyze the MS/DUPsamples as they apply to each digestion set. Follow the above forcontrol limits.

16.4 New or unusual matrices:


It is recommended that whenever a new or unusual sample matrix isencountered, a serial dilution and post digestion (bench) spike beperformed prior to reporting results. These tests will ensure that neitherpositive nor negative interferences are affecting sample results.

Note: For ACOE work, a serial dilution and a post digestion spike willbe performed at a rate of one per matrix with each prep batch.

16.4.1 Serial Dilution: If the analyte concentration is sufficiently high(minimally a factor of ten above the instrumental detection limitafter dilution), an analysis of a 1:5 dilution should agree within +/-10% of the original determination. If not, a chemical or physicalinterference effect should be suspected.

16.4.2 Post digestion spike addition (bench spike): An analyte spike addedto a portion of a prepared sample, or its dilution, should berecovered to within +/- 25% of the known value. The spike additionshould produce a minimum level of 10 times and a maximum of 100times the instrumental detection limit. If the spike recovery fallsoutside these limits, a matrix effect should be suspected.

17.0 REFERENCES17.1 Test Methods for Evaluating Solid Waste, EPA, SW-846, Method 6010B,

1996.17.2 Methods for the Determination of Metals in Environmental Samples,

EPA/600/4-91/010, Method 200.7 rev 4.4, 1991.17.3 USEPA - Contract Laboratory Program, Statement of Work for Inorganic

Analysis, ILM04.0.17.4 ICAP 61 Operator’s Manual, Thermo Jarrell Ash, January 1998 (part

number 125791-01)


18.0 TablesMS-MSD Preparation

SPIKE, LCS, & LFB ANALYSIS- ICPPre-digestion Spikes-LCS & LFB

Element

Spike Amt.mL of

SpikeStock

A, B, C

Stock Conc.mg/L

Final Vol.mL

Expected Conc.ug/L

Aluminum 1 A 200 50 4000Antimony 1 A 50 50 1000Arsenic 1 A 200 50 4000Barium 1 A 200 50 4000Beryllium 1 A 5 50 100Cadmium 1 A 5 50 100Calcium 0.5 C 20,000 50 200000Chromium 1 A 20 50 400Cobalt 1 A 50 50 1000Copper 1 A 25 50 500Iron 1 A 100 50 2000Lead 1 A 50 50 1000Manganese 1 A 50 50 1000Magnesium 0.5 C 10,000 50 100000Molybdenum 0.1 B 1000 50 2000Nickel 1 A 50 50 1000Selenium 1 A 200 50 4000Silver 1 A 5 50 100Thallium 1 A 200 50 4000Vanadium 1 A 50 50 1000Zinc 1 A 50 50 1000

.Spike Solutions

Supplier Lot #/ std Stock

SPEXCertiprep

SPIKE 1-500

A

Molybdenum 1000 mg/L BCustom Std SPEX C


Bench SpikeSPIKE ANALYSIS-ICP

Post Digestion/ Bench Spikes

ElementSpike Amt.

ML ofSpikeSoln.

Stock Conc.mg/L

FinalVol.mL

Expected Conc.ug/L

Aluminum 0.2 A 200 10 4000Antimony 0.2 A 50 10 1000Arsenic 0.2 A 200 10 4000Barium 0.2 A 200 10 4000Beryllium 0.2 A 5 10 100Cadmium 0.2 A 5 10 100Calcium 0.2 B 20,000 10 400000Chromium 0.2 A 20 10 400Cobalt 0.2 A 50 10 1000Copper 0.2 A 25 10 500Iron 0.2 A 100 10 2000Lead 0.2 A 50 10 1000Manganese 0.2 A 50 10 1000Magnesium 0.2 B 10,000 10 200000Molybdenum 0.02 C* 1000 10 2000Nickel 0.2 A 50 10 1000Selenium 0.2 A 200 10 4000Silver 0.2 A 5 10 10Thallium 0.2 A 200 10 4000Vanadium 0.2 A 50 10 1000

Zinc 0.2 A 50 10 1000

Standard SourceSupplier

SPEX ASPEX Custom Std B

Molybdenum-1,000 mg/L Std C* C*: substock of 1,000 mg/L std.(1:10dilution.)


Standard Quality Control Requirements and Corrective Action Guidelines

QCType Frequency Conc. Level Acceptance Criteria Corrective Action

ICV 1 per calibration Mid.Cal RangeSDWA: 95-105%SW846:90-110%

Terminate run. Correctthe problem before

proceeding

ICB

Immediately afterthe ICV <MDL

SW846:ABSvalueof 3x IDLSDWA: ABS LOD

CLP:ABS<1/2 MRL or as statedin QAPP.

Terminate analysis andcorrect the problembefore proceeding.

MB1 per batch of 20

samples <MDL

SDWA: < MDLSW846: < 2x MDL

CLP:ABS<1/2 MRL or as statedin QAPP

Flag: Analyte detected inMethod Blank or reprep

LCS1 per batch of 20

samplesmid cal. Range

In-house limits or, default80-120%

SDWA; 90-110%

Terminate analysis:correct problem before

proceeding.

CCV1 after every 10th

samplemid calrange

SW846: 90-110%SDWA: 90-110%

CLP:90-110%

Recalibrate and reanalyzeall samples back to thelast acceptable CCV or

ICV

CCBImmediately

following eachCCV

<MDL

SW846:ABSvalueof 3x IDLSDWA: ABS LOD

CLP:ABS<1/2 MRL or asstated in QAPP

Reanalyze all samplesback to the last acceptable

CCB or ICB or flaganalyste detected

ICSA

ImmediatelyAfter LCS (&before

final CCV ifrequired by QAPP)

500mg/L Al,CA, Mg

200mg/L Fe(non –ACOE)or 500mg/L Fe

(ACOE)

80-120% for InterferenceElements

ABS of analytes not includedmust be < 2X MRL or as stated

in QAPP

Terminate analysis,correct problem &

reanalyze all samplesback to last good

ICSA/ICSAB

ICSAB

ImmediatelyAfter ICSA ( &

before final CCVifrequired by QAPP)

500mg/L Al,CA, Mg

200mg/L Fe(non-ACOE)or 500 mg/LFe (ACOE)

Other elements500ug/L

80-120% for All Elements

Terminate analysis,correct problem &

reanalyze all samplesback to last good

ICSA/ICSAB


MS-MSD5% (1 in 20) of

samplesper batch per matrix

See attachedspike chart

In-house limits or, default of 75-125 when spike level is >25% of

original analyte levelPerform PDS

SerialDilutionAnalysis

1 per digestionbatch per matrix

5 fold dilutionof chosen

sample

RPD within 10% of value ofdiluted and undiluted sample, but

only if sample conc.>/= 50 X’s LOD

Flag data only if sampleconc. Is within range

(>50X’s LOD)

PostDigestionSpike(PDS)

Upon failure of MSand/or

1 per batch forACOE work

Same level asMS

85-115%Flag: Matrix interference

orMethod of Std. Additions


Appendix A.Standard prep for multipoint calibration of ICP.A1 Calibration Standard #1: Into a 100mL volumetric flask, add 50mL of Milli-Q

H2O, 1mL of conc. HNO3 and 1mL conc. HCl. Add 1 mL of CalibrationStandard #4. Dilute to volume with Milli-Q H2O and mix by inverting severaltimes. Transfer to a clean Nalgene bottle. Prepare every 6 months or as needed.Concentration: 1ug/L

A2 Calibration Standard #2: Into a 100mL volumetric flask, add 50mL of Milli-QH2O, 1mL of conc. HNO3 and 1mL conc. HCl. Add 10uL of SPEX QualityControl Standard 7 and 10uL of SPEX Quality Control Standard 21. Dilute tovolume with Milli-Q H2O and mix by inverting several times. Transfer to a cleanNalgene bottle. Prepare every 6 months or as needed. Concentration: 10 ug/L

A3 Calibration Standard #3: Into a 100mL volumetric flask, add 50mL of Milli-QH2O, 1mL of conc. HNO3 and 1mL conc. HCl. Add 50uL of SPEX QualityControl Standard 7 and 50uL of SPEX Quality Control Standard 21. Dilute tovolume with Milli-Q H2O and mix by inverting several times. Transfer to a cleanNalgene bottle. Prepare every 6 months or as needed.Concentration: 50 ug/L

A4 Calibration Standard #4: Into a 100mL volumetric flask, add 50mL of Milli-QH2O, 1mL of conc. HNO3 and 1mL conc. HCl. Add 100uL of SPEX QualityControl Standard 7 and 100uL of SPEX Quality Control Standard 21. Dilute tovolume with Milli-Q H2O and mix by inverting several times. Transfer to a cleanNalgene bottle. Prepare every 6 months or as needed.Concentration: 100 ug/L

A5 Calibration Standard #5: Into a 100mL volumetric flask, add 50mL of Milli-QH2O, 1mL of conc. HNO3 and 1mL conc. HCl. Add 0.5mL of SPEX QualityControl Standard 7 and 0.5mL of SPEX Quality Control Standard 21. Dilute tovolume with Milli-Q H2O and mix by inverting several times. Transfer to a cleanNalgene bottle. Prepare every 6 months or as needed. Concentration: 500 ug/L

A6 Calibration Standard #6: Into a 100mL volumetric flask, add 50mL of Milli-QH2O, 1mL of conc. HNO3 and 1mL conc. HCl. Add 1mL of SPEX QualityControl Standard 7 and 1mL of SPEX Quality Control Standard 21. Dilute tovolume with Milli-Q H2O and mix by inverting several times. Transfer to a cleanNalgene bottle. Prepare every 6 months or as needed.Concentration: 1000 ug/L

A7 Calibration Standard #7: Into a 100mL volumetric flask, add 50mL of Milli-QH2O, 1mL of conc. HNO3 and 1mL conc. HCl. Add 10mL of SPEX QualityControl Standard 7 and 10mL of SPEX Quality Control Standard 21. Dilute tovolume with Milli-Q H2O and mix by inverting several times. Transfer to a cleanNalgene bottle. Prepare every 6 months or as needed.Concentration: 10000 ug/L

A8 Calibration Standard #8: Into a 100mL volumetric flask, add 50mL of Milli-QH2O, 1mL of conc. HNO3 and 1mL of HCl. Add 1mL of 10,000 mg/L Al, 1mLof 10,000 mg/L Ca, 1mL of 10,000 mg/L Fe and 1mL of 10,000 mg/L Mg. Diluteto volume with Milli-Q H2O and mix by inverting several times. Transfer to aclean Nalgene bottle. Prepare every 6 months or as needed.Concentration:100,000ug/L Al, Ca, Fe and Mg

A9 Calibration Standard #9: Into a 100mL volumetric flask, add 50mL of Milli-QH2O, 1mL of conc. HNO3 and 1mL of HCl. Add 5mL of 10,000 mg/L Al, 5mLof 10,000 mg/L Ca, 5mL of 10,000 mg/L Fe and 5mL of 10,000 mg/L Mg. Dilute


to volume with Milli-Q H2O and mix by inverting several times. Transfer to aclean Nalgene bottle. Prepare every 6 months or as needed.Concentration:500,000ug/L Al, Ca, Fe and Mg

A10 Calibration Blank: Into a 1 L. volumetric flask, add 750 mL of Milli-Q water and10 mL of conc. HNO3 and 10mL HCl. Mix, dilute to volume with Milli-Q H2O.Transfer to a clean 1 L. nalgene bottle. Prepare every 6 months or as needed.


Appendix BStandard Preparation for “Shell” Method

B1. Calibration Standard 1: Into a 100mL volumetric flask, add 50mL of Milli-QH2O, 1mL of conc. HNO3 and 1mL conc. HCl. Add 10mL SPEX QualityControl 7 and 10mL of SPEX Quality Control 21. Dilute to volume with Milli-QH2O and mix by inverting several times. Transfer to a clean Nalgene bottle.Prepare every 6 months or as needed. Concentration: 10,000ug/LAs, Be, Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Pb, Sb, Se, Tl, V, Zn, Ag, Al,Ba

B2. Calibration Standard 2: Into a 100mL volumetric flask, add 50mL of Milli-QH2O, 1mL of conc. HNO3 and 1mL conc. HCl. Add 5mL 10,000mg/L Ca, 5mL10,000 Fe, 5mL 10,000 Al and 5mL 10,000 Mg. Dilute to volume with Milli-QH2O and mix by inverting several times. Transfer to a clean Nalgene bottle.Prepare every 6 months or as needed. Concentration: 500,000 ug/L Al, Ca, Feand Mg.

B3. Calibration Standard 3: Into a 100mL volumetric flask, add 50mL of Milli-QH2O, 1mL of conc. HNO3 and 1mL conc. HCl. Add 1mL SPEX Quality Control7 and 1mL of SPEX Quality Control 21. Dilute to volume with Milli-Q H2O andmix by inverting several times. Transfer to a clean Nalgene bottle. Prepare every6 months or as needed. Concentration: 1,000ug/LAs, Be, Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Mo, Ni, Pb, Sb, Se, Tl, V, Zn, Ag, Al,Ba

B4. Calibration Standard 4: Into a 100mL volumetric flask, add 50mL of Milli-QH2O, 1 mL of conc. HNO3 and 1mL conc. HCL. Add 0.2mL of Ultra Zn1000ug/L standard or equivalent. Dilute to volume with Milli-Q H2O and mix byinverting several times. Transfer to a clean Nalgene bottle. Prepare every 6months or as needed. Concentration: 2000ug/L Zn.


Appendix CStandard Prep for Sodium and Potassium analysis.C1 Calibration Standard #1: Into a 200mL volumetric flask, add 100mL of Milli-Q

H2O, 2mL of conc. HNO3 and 2mL conc. HCl. Add 0.2mL Sodium 1000mg/Land 0.2mL Potassium 1000mg/L. Dilute to volume with Milli-Q H2O and mix byinverting several times. Transfer to a clean Nalgene bottle. Prepare every 6months or as needed. Concentration: 1 mg/L Na, K.

C2 Calibration Standard #2: Into a 200mL volumetric flask, add 100mL of Milli-QH2O, 2mL of conc. HNO3 and 2mL conc. HCl. Add 1mL Sodium 1000mg/L and1mL Potassium 1000mg/L. Dilute to volume with Milli-Q H2O and mix byinverting several times. Transfer to a clean Nalgene bottle. Prepare every 6months or as needed. Concentration: 5 mg/L Na, K.

C3. Calibration Standard #3: Into a 200mL volumetric flask, add 100mL of Milli-QH2O, 2mL of conc. HNO3 and 2mL conc. HCl. Add 2mL Sodium 1000mg/L and2mL Potassium 1000mg/L. Dilute to volume with Milli-Q H2O and mix byinverting several times. Transfer to a clean Nalgene bottle. Prepare every 6months or as needed. Concentration: 10 mg/L Na, K.

C4. Calibration Standard #4: Into a 200mL volumetric flask, add 100mL of Milli-QH2O, 2mL of conc. HNO3 and 2mL conc. HCl. Add 5mL Sodium 1000mg/L and5mL Potassium 1000mg/L. Dilute to volume with Milli-Q H2O and mix byinverting several times. Transfer to a clean Nalgene bottle. Prepare every 6months or as needed. Concentration: 25 mg/L Na, K.

C5. Calibration Standard #5: Into a 200mL volumetric flask, add 100mL of Milli-QH2O, 2mL of conc. HNO3 and 2mL conc. HCl. Add 10mL Sodium 1000mg/Land 10mL Potassium 1000mg/L. Dilute to volume with Milli-Q H2O and mix byinverting several times. Transfer to a clean Nalgene bottle. Prepare every 6months or as needed. Concentration: 50 mg/L Na, K.

C6. Calibration Standard #6: Into a 200mL volumetric flask, add 100mL of Milli-QH2O, 2mL of conc. HNO3 and 2mL conc. HCl. Add 20mL Sodium 1000mg/Land 20mL Potassium 1000mg/L. Dilute to volume with Milli-Q H2O and mix byinverting several times. Transfer to a clean Nalgene bottle. Prepare every 6months or as needed. Concentration: 100 mg/L Na, K.

C7. ICV/CCV: Into a 200mL volumetric flask, add 100mL Milli-Q water, 2mL ofconc. HNO3 and 2mL of conc. HCl. Add 1.0mL 10,000mg/L Na and 1.0mL10,000 K. Dilute to volume with Milli-Q water and mix by inverting severaltimes. Transfer to a clean Nalgene bottle. Prepare every 6 months or as needed.Concentration: 50 mg/L

C8. ICSAB: Into a 200mL volumetric flask, add 100mL Milli-Q water, 2mL of conc.HNO3 and 2mL of conc. HCl. Add 25 mL of SPEX Interferents A or equivalent,


2.0mL 10,000mg/L Na and 2.0mL 10,000 K. Dilute to volume with Milli-Qwater and mix by inverting several times. Transfer to a clean Nalgene bottle.Prepare every 6 months or as needed. Concentration: 100mg/L Na and K,500,000ug/L Al, Ca and Mg, 200mg/L Fe.

C9. Lithium/Yttrium internal standard: Into a 1L volumetric flask, add 500mL Milli-Q water, 1mL conc HCl and 4mL conc. HNO3. Add 1mL 10,000 mg/L Yttriumand 20g of Lithium Nitrate. Dilute to volume with Milli-Q water and mix until allLithium Nitrate is dissolved. Transfer to a clean Nalgene bottle. Prepare every 6months or as needed.


Appendix DStandard Prep for Boron AnalysisD1. Calibration Standard #1: Into a 100mL plastic volumetric flask, add 50mL of

Milli-Q H2O, 1mL of conc. HNO3 and 1mL conc. HCl. Add 0.2 mL 1000mg/LBoron. Dilute to volume with Milli-Q H2O and mix by inverting several times.Transfer to a clean Nalgene bottle. Prepare every 6 months or asneeded.Concentration: 2000 ug/L

D2. Calibration Standard #2: Into a 100mL plastic volumetric flask, add 50mL ofMilli-Q H2O, 1mL of conc. HNO3 and 1mL conc. HCl. Add 0.1 mL 1000mg/LBoron. Dilute to volume with Milli-Q H2O and mix by inverting several times.Transfer to a clean Nalgene bottle. Prepare every 6 months or asneeded.Concentration: 1000 ug/L

D3. Calibration Standard #3: Into a 100mL plastic volumetric flask, add 50mL ofMilli-Q H2O, 1mL of conc. HNO3 and 1mL conc. HCl. Add 0.02 mL 1000mg/LBoron. Dilute to volume with Milli-Q H2O and mix by inverting several times.Transfer to a clean Nalgene bottle. Prepare every 6 months or asneeded.Concentration: 200 ug/L

D4. ICV/CCV: Into a 100mL plastic volumetric flask, add 50mL of Milli-Q water, 1mL of conc HNO3 and 1mL conc. HCl. Add 0.1mL of 1000mg/L Boron(alternate source from calibration source). Dilute to volume with Milli-Q waterand mix by inverting several times. Transfer to a clean Nalgene bottle. Prepareevery 6 months or as needed. Concentration: 1000 ug/L.

D5. ICSAB: Into a 100mL plastic volumetric flask, add 50mL of Milli-Q water, 1mL of conc HNO3 and 1mL conc. HCl. Add 0.05mL of 1000mg/L Boron and10mL of SPEX Interferent A or equivalent. Dilute to volume with Milli-Q waterand mix by inverting several times. Transfer to a clean Nalgene bottle. Prepareevery 6 months or as needed. Concentration: 500 ug/L B, 500,000 ug/L Mg, Caand Al, 200,000ug/L Fe.


Trace 61E ICAP Data Review Checklist Analysis Date: Data File: Date review:Cal Std ID: LIMS # : Analyst: Reviewer: Approved? Yes NoCalibration Parameters - 6010 200.7 YES NO YES NO Comments:1) Calibration linearity - r > 0.9952) ICV 90-110% 95-105%3) ICB ABS 3X DL ABS DL4) ICSAB 80-120% True Value5) ICSA +/- 2X RL6) CRI - (2X CRDL or LOD) 50-150%7) CCV1/CCB1-90-110% / 3X DL ABS DL8) CCV2/CCB29) CCV3/CCB310) CCV4/CCB411) CCV5/CCB512) CCV6/CCB613) CCV7/CCB714) CCV8/CCB815) CCV9/CCB916) CCV10/CCB10Preparation BatchParameters

YES NO YES NO Comments:

Prep Batch ID#:_______ Dig. Meth.______Prep. Blank - <LOD or RLLCS - generated limits;attached listSpiked samples in batch:a)____________ matrix = ________b)____________ matrix = ________c)____________ matrix = ________d)____________ matrix = ________e)____________ matrix = ________PDS 75-125% sample#_____________Prep Batch ID#:_______ Dig. Meth.______Prep. Blank - <LOD or RLLCS - generated limits;attached listSpiked samples in batch:a)____________ matrix = ________b)____________ matrix = ________c)____________ matrix = ________d)____________ matrix = ________e)____________ matrix = ________PDS 75-125% sample#_____________Prep Batch ID#:_______ Dig. Meth.______Prep. Blank - <LOD or RLLCS - generated limits;attached listSpiked samples in batch:a)____________ matrix = ________b)____________ matrix = ________c)____________ matrix = ________d)____________ matrix = ________e)____________ matrix = ________PDS 75-125% sample#_____________Prep Batch ID#:_______ Dig. Meth.______

CT Laboratories SOP No: CC-TOC Rev. 0Inorganics Laboratory Section Page 1 of 12 9/14/04

CT LaboratoriesBaraboo Laboratory Division

Title: Total Organic Carbon in Water

SOP Number: CC-TOC H2O

Prepared by: ___________________________________Date






1.0 SCOPE AND APPLICATION1.1 This SOP is used to determine the concentration of organic carbon in

ground water, surface and saline waters, and domestic and industrialwastes.

1.2 The detection limit for this method is approximately 1 mg/L.

2.0 METHOD SUMMARY2.1 Organic carbon is measured using a carbonaceous analyzer. The

instrument converts the organic carbon in a sample to carbon dioxide(CO2) by catalytic combustion. The CO2 formed is then directly detectedby an infrared detector. The amount of CO2 in a sample is directlyproportional to the concentration of carbonaceous material in the sample.

2.2 Carbonate and bicarbonate are inorganic forms of carbon and must beseparated from the total organic carbon value. The carbonate andbicarbonate are removed by converting them to CO2 with degassing priorto analysis.

3.0 DEFINITIONS3.1 Initial Calibration Verification (ICV): A midrange check standard

analyzed after the calibration has been completed, to evaluate calibrationcurve and or instrument performance. The ICV is from a different sourcethan the calibration standards.

3.2 Lab Control Sample (LCS): A known concentration obtained from asecond source.

3.3 Continuing Calibration Verification (CCV): A check standard analyzedafter every ten samples and at the end of the analytical run, to evaluateinstrument performance.

3.4 Matrix spike-matrix spike duplicate (MS-MSD): To two of three aliquotsof a given sample a known amount of spike solution is added. Matrixspikes and matrix spike duplicates are taken through all steps of analysis,exactly like a sample. The amount of spike recovered helps to assess theeffect of the sample matrix on the analysis. The precision of the method isalso determined, by calculating the relative percent difference (RPD) ofthe two spiked aliquots. An MS-MSD should be prepared for every 10samples in each matrix.

3.5 Calibration Blank (ICB or CCB): A blank standard analyzed after everyICV or CCV to evaluate instrument contamination or carry over.

4.0 HEALTH AND SAFETY4.1 The toxicity or carcinogenicity of each reagent used in this method has not

been fully established. Each chemical should be regarded as a potentialhealth hazard and exposure should be as low as reasonable achievable.

4.2 Gloves and protective clothing should be worn to protect againstunnecessary exposure to hazardous chemicals and contaminants in samples.


All activities performed while following this procedure should utilizeappropriate laboratory safety systems.

5.0 CAUTIONS5.1 Use Milli-Q water for doing all dilutions and reagents.5.2 Samples must be analyzed in quadruplicate.

6.0 INTERFERENCES6.1 Carbonate and bicarbonate carbon represent an interference under the

terms of this test and must be removed or accounted for in the finalcalculation.

6.2 This procedure is applicable only to homogeneous samples which can beinjected into the apparatus reproducibly by means of a microliter syringe.The opening of the syringe limits the maximum size of particle which maybe included in the sample.

6.3 Removal of carbonate and bicarbonate by acidification and purging withnitrogen, or other inert gas, can result in the loss of volatile organicsubstances.

7.0 APPARATUS AND MATERIALS7.1 Equipment and Supplies

7.1.1 Shimadzu TOC-5000A7.1.2 TOC Catalyst- Shimadzu part number 638-92069-017.1.3 Combustion tube- Shimadzu part number 638-413237.1.4 Shimadzu ASI -5000A7.1.5 Analytical Balance7.1.6 Eppendorf micropipettors or equivalent- various sizes7.1.7 Class A volumetric flasks- various sizes

7.2 Reagents and Materials7.2.1 Milli-Q water7.2.2 25% Phosphoric Acid- Into a 1L volumetric flask, add 250 mL

concentrated Phosphoric Acid (Fisher catalog number A242SK-212 or equivalent) and dilute to volume with Milli-Q water. Storeon shelf.

7.2.3 2N Hydrochloric Acid- Into a 1L volumetric flask, add 167mLconcentrated HCl (Fisher catalog number A508SK212 orequivalent) and dilute to volume with Milli-Q water. Store onshelf.

7.2.4 Calibration Curve, Stock Standard: Into a 100 mL volumetricflask, dissolve 0.2128g of Potassium Hydrogen Phthalate (Fishercatalog number AC424061000 or equivalent) and dilute to volumewith Milli-Q water. True Value is 1000 mg/L TOC. Store at 40C.Stock standard expires after one year.

7.2.5 Calibration Curve : Into 4-25mL volumetric flasks add thefollowing:mLs Stock (7.2.4) mLs Milli-Q Water True Value (mg/L)


0 25 00.25 24.75 101.25 23.75 502.5 22.5 100Calibration standards should be stored at at 40C and standardsexpire after 28 days.

7.2.6 LCS, Stock Standard: Into a 100 mL volumetric flask, dissolve0.2128g of Potassium Hydrogen Phthalate (Fisher catalog numberP243-100 or equivalent) from a source secondary to the calibrationstandards and dilute to volume with Milli-Q water. True Value is1000 mg/L TOC. Store at 40C. Stock standard expires after oneyear.

7.2.7 LCS : Into a 100mL volumetric flask, add 5mL of LCS stockstandard (7.2.6) and dilute to volume with Milli-Q water. TrueValue is 50 mg/L. LCS should be stored at at 40C and standardsexpire after 28 days.

8.0 INSTRUMENT OR METHOD CALIBRATION8.1 Turn on compressed air to the instrument. Set pressure to 40psi.8.2 Turn on instrument. Power button is located on the left side of the

instrument.8.3 Check to verify that the carrier gas flow rate is 150 mL/min. Gas flow

regulator is located on the upper left portion of the front of the instrument.Open door and adjust to 150 mL/min if necessary.

8.4 Check the water levels in the IC pot and the humidifier. Add water to thehumidifier if necessary. See manual for how to adjust water level in ICpot.

8.5 Once the screen powers up, press F5 to initialize the autosampler. If thisoption is not available, go to 8.6.

8.6 Press F1 to go to the main menu.8.7 Using the arrow keys on the front of the instrument, arrow down to 3

(General Conditions) and press enter. This will take you to the generalconditions screen.8.7.1 Under general conditions, make sure the following options are set:

8.7.1.1 TC Catalyst should be 1 (normal)8.7.1.2 Syringe size should be 1 (250ul)8.7.1.3 Number of Washes should be 48.7.1.4 Unit of concentration should be 3 (mg/L)8.7.1.5 Auto ranging and injection volume should be 1 (on)8.7.1.6 Autoregeneration of IC solution should be 1 (on)8.7.1.7 Auto printout should be 1 (data only)8.7.1.8 Furnace on/off should be 1 (on)8.7.1.9 Buzzer should be 2 (not used)8.7.1.10 Injection speed should be 3 (0.8mm)8.7.1.11 ESU option should be 2 (not used)8.7.1.12 Bubble Removal should be 1 (on)


8.7.1.13 Syringe wash should be 1 (std)8.7.1.14 Cell length should be 1 (std)8.7.1.15 TOC or SSM should be 1 (TOC)8.7.1.16 Printer device should be 2 (Internal-New)8.7.1.17 Page length should have an *8.7.1.18 Calibration curve form should be 2 (least squares)8.7.1.19 POC option is 1 (not used)8.7.1.20 Press F1 to go to the next screen8.7.1.21 Set measurement interval for TOC/NPOC to 480s8.7.1.22 Set measurement interval for IC/POC to 360s8.7.1.23 Press F2 to return to the main menu

8.8 Press 9 and enter to go to the autosampler screen.8.8.1 On the screen next to the number 1, highlight the TC. Choose 4

(NPOC) and press enter8.8.2 Arrow over to the IS column, press 1 and enter.8.8.3 Arrow over to the FS column, press 1 or your last vial number if

you are analyzing samples and enter.8.8.4 Place an autosampler vial with Milli-Q water in autosampler

position 1 or place your samples in the autosampler in theappropriate order. Cover vials with parafilm.This will be analyzedafter the calibration curve is run.

8.8.5 Arrow over to the C1 column, press 1 and enter. A calibrationcurve screen will appear.8.8.5.1 Choose 1 for TC8.8.5.2 Type in 0 for the first standard concentration and S1 for the

tube number8.8.5.3 Type in 10 for the second standard concentration and S2 for

the tube number8.8.5.4 Type in 50 for the third standard concentration and S3 for

the tube number8.8.5.5 Type in 100 for the fourth standard concentration and S4

for the tube number8.8.5.6 Set the range to x58.8.5.7 Set the injection volume to 50uL8.8.5.8 Set the number of injections to 48.8.5.9 Set the maximum number of injections to 6.8.8.5.10 Accept the default numbers for the SD and CV.8.8.5.11 Set the sparge time to 10 min.8.8.5.12 Set shift to origin to 2 (off)8.8.5.13 Set acid addition to 1 (on)8.8.5.14 Press F2 to return to the autosampler screen.

8.8.6 Arrow over to the RG column. Enter 5 under that column ifnecessary.

8.8.7 Arrow over to the VOL column. Enter 50 under that column.8.8.8 Arrow over to the NO column. Enter 4 under that column.8.8.9 Arrow over to the W colume. Enter 4 under that column.


8.8.10 Arrow over to the MAX column. Enter 5 under that column.8.8.11 Arrow over to the SP column. Enter 10 under that column.8.8.12 Press F1 to go to the next screen. The ASI Condition screen will

appear.8.8.12.1 Set the rinse to 1 (rinse)8.8.12.2 Set the No of needle washes to 28.8.12.3 Set the Flow line washes to 28.8.12.4 Set Calibrate before to 1 (All Sample Groups)8.8.12.5 Set Print Information to 3 (Cal and Data)8.8.12.6 Set Auto addition of acid to 1 (on)8.8.12.7 Set Acid volume to 508.8.12.8 Set Rinse after addition to 1 (rinse)8.8.12.9 Set Key Lock to 2 (unlock)8.8.12.10 Set Finish or Running to 3 (no change)

8.8.13 Press F1 to go to the next screen.8.9 Fill autosampler vials with standards and place 2N HCl (7.2.3) in large

vial in position S8. Cover vials with parafilm. Place standards inappropriate vial positions.

8.10 Make sure rinse water vessel is full with Milli-Q water.8.11 Press Start.8.12 When analysis is complete, press F2 to return to main menu.8.13 Choose 4- Calibration curve file list

8.13.1 Highlight the calibration curve and press enter to display the curve.8.13.1.1 Press F to print curve.8.13.1.2 Confirm R value displayed is >0.995. If it is not, fix

problem and repeat calibration.8.13.1.3 Press F1 to return to the Calibration curve list.

9.0 SAMPLE COLLECTION, HANDLING AND PRESERVATION9.1 Sampling and storage of samples in glass bottles is preferable but plastic is

allowable if it does not contribute to TOC content of sample.9.2 The sample should be acidified (pH < 2) with HCl or H2SO4.9.3 Samples should be stored at 40C until analysis.9.4 Hold time for preserved samples is 28 days.

10.0 SAMPLE PREPARATION AND ANALYSIS10.1 Turn on compressed air to the instrument. Set pressure to 40psi.10.2 Turn on instrument. Power button is located on the left side of the

instrument.10.3 Check to verify that the carrier gas flow rate is 150 mL/min. Gas flow

regulator is located on the upper left portion of the front of the instrument.Open door and adjust to 150 mL/min if necessary.

10.4 Check the water levels in the IC pot and the humidifier. Add water to thehumidifier if necessary. See manual for how to adjust water level in ICpot.


10.5 Once the screen powers up, press F5 to initialize the autosampler. If thisoption is not available, go to next step.

10.6 Press F1 to go to the main menu.10.7 Using the arrow keys on the front of the instrument, arrow down to 3

(General Conditions) and press enter. This will take you to the generalconditions screen.10.7.1 Under general conditions, make sure the following options are set:

10.7.1.1 TC Catalyst should be 1 (normal)10.7.1.2 Syringe size should be 1 (250ul)10.7.1.3 Number of Washes should be 410.7.1.4 Unit of concentration should be 3 (mg/L)10.7.1.5 Auto ranging and injection volume should be 1 (on)10.7.1.6 Autoregeneration of IC solution should be 1 (on)10.7.1.7 Auto printout should be 1 (data only)10.7.1.8 Furnace on/off should be 1 (on)10.7.1.9 Buzzer should be 2 (not used)10.7.1.10 Injection speed should be 3 (0.8mm)10.7.1.11 ESU option should be 2 (not used)10.7.1.12 Bubble Removal should be 1 (on)10.7.1.13 Syringe wash should be 1 (std)10.7.1.14 Cell length should be 1 (std)10.7.1.15 TOC or SSM should be 1 (TOC)10.7.1.16 Printer device should be 2 (Internal-New)10.7.1.17 Page length should have an *10.7.1.18 Calibration curve form should be 2 (least squares)10.7.1.19 POC option is 1 (not used)10.7.1.20 Press F1 to go to the next screen10.7.1.21 Set measurement interval for TOC/NPOC to 300s10.7.1.22 Set measurement interval for IC/POC to 300s10.7.1.23 Press F2 to return to the main menu

10.8 Press 9 to go to the autosampler screen.10.8.1 On the screen next to the number 1, highlight the TC. Choose 4

(NPOC) and press enter10.8.2 Arrow over to the IS column, type in the position of the first tube

for your run and press enter.10.8.3 Arrow over to the FS column, type in the position of the last tube

of the run and press enter.10.8.4 Fill vials with appropriate samples and cover with a small piece of

parafilm. Place filled vials in autosampler. For MS and MSD, use0.25 mL of stock standard (7.2.4) and 4.75mL of sample. Truevalue is 50 mg/L.

10.8.5 Arrow over to the F1 column, press 1 (or the appropriate cal curvenumber) and enter.

10.8.6 Arrow over to the RG column. Enter 5 under that column ifnecessary.

10.8.7 Arrow over to the VOL column. Enter 50 under that column.


10.8.8 Arrow over to the NO column. Enter 4 under that column.10.8.9 Arrow over to the W column. Enter 4 under that column.10.8.10 Arrow over to the MAX column. Enter 5 under that column.10.8.11 Arrow over to the SP column. Enter 10 under that column.10.8.12 Press F1 to go to the next screen. The ASI Condition screen will

appear.10.8.12.1 Set the rinse to 1 (rinse)10.8.12.2 Set the No of needle washes to 210.8.12.3 Set the Flow line washes to 210.8.12.4 Set Calibrate before to 1 (All Sample Groups)10.8.12.5 Set Print Information to 3 (Cal and Data)10.8.12.6 Set Auto addition of acid to 1 (on)10.8.12.7 Set Acid volume to 5010.8.12.8 Set Rinse after addition to 1 (rinse)10.8.12.9 Set Key Lock to 2 (unlock)10.8.12.10 Set Finish or Running to 3 (no change)

10.8.13 Press F1 to go to the next screen.10.9 Place 2N HCL in vial position S8. Cover vial with parafilm.10.10 Make sure rinse water vessel is full with Milli-Q water.10.11 Press Start.10.12 When analysis is complete, press F2 to return to main menu.10.13 Shut instrument down by turning off power button and compressed air

supply.11.0 TROUBLESHOOTING AND MAINTENANCE

11.1 Refer to the Shimadzu TOC 5000-A instruction manual for maintenanceinstructions.

12.0 DATA ACQUISITION, CALCULATIONS AND DATA REDUCTIONLiquid Concentration (mg/L) = A x B

where A = instrument reading for sample (mg/L)B= analyst dilution factor, if necessary (ex. For a 1 to 10 dilution, B = 10)

Spike Recovery (%)= (Spiked sample concentration – Sample concentration) x 100 (Spike amount)

%RPD = (MS – MSD) x 100 (MS + MSD)/2

where MS = Matrix spike concentrationMSD = Matrix spike duplicate concentration

13.0 COMPUTER HARDWARE AND SOFTWARE13.1 Computer with StarLIMS

14.0 DATA MANAGEMENT AND RECORD MANAGEMENT


14.1 After data has been entered into LIMS, it is reviewed and validated by theanalyst for accuracy and completeness. See checklist for data reviewguidance.

14.2 Once analyst has reviewed and validated the data, it is given to a peer orsupervisor for review on 10% or more of the data.

14.3 The original data is filed by test in the file cabinet and periodically thecontents of the file cabinet are archived.

15.0 QUALITY CONTROL AND QUALITY ASSURANCE15.1 The analyst must show an initial demonstration of capability (IDC) to

generated acceptable data, by successfully analyzing four replicates of aknown standard and having acceptable results for a blind sample.

15.2 ICV/LCS (initial calibration verification/Laboratory control standard):This mid range secondsource check standard is analyzed aftercalibration.. ICV/LCS is at the mid-point of the calibration curve. Controllimits are +/- 10% of the true value. If the recovery is outside of this range,terminate the run and correct the problem before proceeding.

15.3 ICB (initial calibration blank): Analyzed immediately after the ICV. Thevalue of the ICB must be below the method LOD. If not, terminate theanalysis and correct the problem before proceeding or qualify results lessthan 20 times the ICB with a ‘B’ flag.

15.4 CCV/LCS (continuing calibration verification/laboratory controlstandard): Analyze a CCV/LCS following every ten samples and at theend of the analysis. CCV/LCS is at the mid-point of the calibration curve.Control limits are +/- 10% of the true value. If recovery is outside theselimits, recalibrate and reanalyze all samples back to the last acceptableCCV or ICV.

15.5 CCB (continuing calibration blank): Analyzed immediately after the CCV.The value of the CCB must be below the method LOD. If not, terminatethe analysis and correct the problem before proceeding. If CCB is outsidethese limits, recalibrate and reanalyze all samples back to the lastacceptable CCB or ICB or qualify results less than 20 times the CCB witha ‘B’ flag.

15.6 MS-MSD (matrix spike-matrix spike duplicate):A MS-MSD is requiredevery analytical run at a frequency of 10% (1 for every 10 samples) permatrix type. Refer to the control limits for acceptance criteria for bothaccuracy and precision. Unless otherwise specified in a contract ifrecovery is outside of acceptable range, flag the sample with an ‘M’qualifer. If the RPD is outside of the acceptable range, flag the samplewith a ‘Y’ qualifier.


16.0 REFERENCES


17.1 Methods for the Determination of Inorganic Substances in EnvironmentalSamples, 1974, Method 415.1.

17.2 Standard Methods for the Examination of Water and Wastewater, 18thEdition, 1992, APHA-AWWA-WEF, Method 5310B.

17.3 SW 846, 3rd Edition, Update III, 1997 Method 9060.17.4 Shimadzu Instruction Manual Total Oranic Carbon Analyzer Model TOC-

5000A.17.5 Shimadzu Autosampler ASI-5000A for Total Organic Carbon Analyzer

TOC 5000(A)/5050(A) Instruction Manual., 1994.

CT Laboratories SOP No: CC-TOC Rev. 0Inorganics Laboratory Section Page 11 of 12 9/14/04SUMMARY OF QUALITY CONTROL REQUIREMENTS

Procedure Frequency ofProcedure Acceptance Criteria Corrective Action if

UnacceptableSix-point initialcalibration plus blank(ICAL)- two different4 point curves

Initially and as needed r > 0.995 for each regression line Repeat until acceptable

Initial calibrationverification (ICV)

Second source standardrun after each ICALand daily prior tosample analysis

%R: 90-110% for all analytes Remake and reanalyze ICV standard, ifstill unacceptable repeat ICAL

Laboratory ControlStandard (LCS)

Standard run afterevery 20 samples

Within in house limitsDefault: 80-120%

Remake and reanalyze CCV, if stillunacceptable investigate and correctproblem. Reanalyze all samples afterlast acceptable LCS.

Initial calibrationblank (ICB)

After each ICV, priorto sample analysis < RL

Remake and reanalyze CB once, if stillunacceptable investigate and correctproblem or flag results less than 20 X’sthe ICB with a ‘B’ qualifier

Continuing calibrationverification (CCV)

Daily, prior to sampleanalysis, after every 10samples, and at end ofrun

%R: 90-110% for all analytes

Remake and reanalyze CCV, if stillunacceptable investigate and correctproblem. Reanalyze all samples afterlast acceptable CCV.

Continuing calibrationblank (CCB) After each CCV <RL or <20 times less than the

lowest sample result

Remake and reanalyze CB once, if stillunacceptable investigate and correctproblem then reanalyze all samples afterthe last acceptable CCB or flag resultsless than 20 X’s the CCB with a ‘B’qualifier

Method Blank (MB) After each LCS <RL or <20 times less than thelowest sample result

Remake and reanalyze MB once, if stillunacceptable investigate and correctproblem then reanalyze all samples afterthe last acceptable MB or flag resultsless than 20 X’s the MB with a ‘B’qualifier

Capabilitydemonstration sample(IDC)

Four (4) preparedsamples analyzed onetime prior to anysample analyses andone blind sample

80-120% Recovery< 20% RPD Repeat until acceptable

Matrix SpikeDuplicate (MSD)

One (1) per 10 samplesper matrix

In-house derived limitsDefault = 80-120%

20% RPD

Investigate problem, if LCS in controlqualify results. Qualify results with a‘M’ or‘Y’ flag if necessary

Matrix spike sample(MS)

One (1) per 10 samplesper matrix

In-house derived limitsDefault = 80-120%

Investigate problem, if LCS in controlqualify results. Qualify results with a‘M’ flag if necessary

CT Laboratories


LIMS #: Method: Total Organic Carbon Method 415.1/9060


Yes … No

Instructions: Complete one checklist per analytical run. Enter the appropriate response for each question. Each “No” response requires an explanation in the Comments section, and mayrequire the initiation of a Nonconformance Report.




1. Were the samples preserved prior to analysis? pH <2

2. Was the calibration curve performed using the required number of standards? 3 standards and ablank



4. Was LCS standard run at the beginning of the run prior to sample analysis? ---

5. Was the LCS recovery acceptable? 90 – 110 %


7. Were the CCV/LCS’s and the CCB’s analyzed at the required frequency? 1per 10 samples

8. Were the CCV/LCS recoveries acceptable? 90 – 110 %



11. Were all positive results that were reported within the calibration curve? ---

12. Were matrix spike and matrix spike duplicate samples run at the required frequency? 1 per 10 of the samematrix

13. Was the matrix spike and matrix spike duplicate recovery acceptable? Within in house QClimits

14. Was the RPD of the matrix spike and matrix spike duplicate acceptable? Within in house QClimits

15. Were all samples and QC analyzed in quadruplicate? (For all solid samples). ---


CT Laboratories SOP No: CC-32 Rev. 3Inorganics Laboratory Section Page 1 of 6 6/13/02

CT LaboratoriesBaraboo Laboratory Division

Title: Sulfide, Titrimetric Method

SOP Number: CC-32

Prepared by: ______________________________________Date

Technical Review by: ______________________________________Date

Reviewed by: ______________________________________Quality Assurance Date

______________________________________Laboratory Director Date

SOP Manual Control Number:


1.0 SCOPE AND APPLICATION1.1 This method is applicable to the measurement of total and dissolved

sulfides in drinking waters, surface and saline waters, domestic andindustrial wastes.

1.2 Acid insoluble sulfides are not measured by the use of this test. (Coppersulfide is the only common sulfide in this class).

1.3 This method is suitable for the measurement of sulfide in concentrationsabove 1mg/L.

2.0 METHOD SUMMARY2.1 Excess iodine is added toa sample which may or may not have been

treated with zinc acetate to produce zinc sulfide. The iodine oxidizes thesulfide to sulfur under acidic conditions. The excess iodine is backtitratedwith phenylarsine oxide.

3.0 DEFINITIONS3.1 Duplicate Analysis : Two aliquots of a given sample are analyzed. The

relative percent difference (RPD) is then determined from the two resultsand compared to the lab control limits for that particular matrix.


unnecessary exposure to possibly hazardous chemicals and contaminantsin samples. All activities performed while following this procedureshould utilize appropriate laboratory safety systems (see CTI Health andSafety Manual).

5.0 CAUTIONSThere are no cautions

6.0 INTERFERENCES6.1 Reduced sulfur compounds, such as sulfite, thiosulfate and hydrosulfite,

which decompose in acid, may yield erratic results. Also, volatile iodine-consuming substances will give high results.

6.2 Samples must be taken with a minimum of aeration. Sulfide may bevolatilized by aeration and any oxygen inadvertently added to the samplemay convert the sulfide to an unmeasurable form.

6.3 If the sample is not preserved with zinc acetate and NaOH, the analysismust be started immediately.

7.0 PERSONNEL QUALIFICATIONS7.1 All personnel need to demonstrate capability by completing a valid IDC,

initial demonstration of capability, study prior to performing analyses onactual samples

8.0 APPARATUS AND MATERIALS


8.1 25 ml buret, borosilicate glass, with 0.1 ml or 0.01 ml graduations8.2 Stir plate, magnetic with teflon stir bar.8.3 Oxford pipet, 10 ml capacity.8.4 Oxford pipet, 5 ml capacity.8.5 500 – 1000 mL glass bottles with stoppers: For use in the analysis of

dissolved sulfide.8.6 REAGENTS

8.6.1 Zinc Acetate Preservative (2N): Dissolve 220 gm of Zn(C2H3o2)2 -H2o in 870 mL of DI water. Dilute to 1000 mL.

8.6.2 Hydrochloric acid, HCl, 6 N: Prepare by adding 10 mls ofconcentrated HCl to 10 mls of DI water.

8.6.3 Standard iodine solution, 0.0250 N: Commercially available8.6.4 Phenylarsine oxide 0.0250 N: Commercially available8.6.5 Starch indicator: Commercially available.8.6.6 Sodium hydroxide solution, NaOH, 6N: into a 500 ml volumetric,

dissolve 120 g of NaOH pellets and bring up to vol with DI water.8.6.7 Aluminum chloride solution: Commercially available

9.0 INSTRUMENT OR METHOD CALIBRATIONThere is no calibration for this method.

10.0 SAMPLE COLLECTION, HANDLING AND PRESERVATION10.1 Collect at a minimum 500 mL of sample and preserve with zinc acetate

plus sodium hydroxide to pH >9. Keep refrigerated at 4 C. Hold time 7days.

10.2 Keep aeration of sample to a minimum.

11.0 SAMPLE PREPARATION AND ANALYSIS11.1 Total sulfides:

11.1.1 Place a known amount of standard iodine solution into a 500 mlflask. The amount should be estimated to be in excess of theamount of sulfide expected.

11.1.2 Add distilled water, if necessary, to bring the volume toapproximately 20 ml.

11.1.3 Add 2 ml of 6 N HCl.11.1.4 Pipet 200 ml of sample into the flask, keeping the tip of the pipet

below the surface of the sample.11.1.5 If the iodine color disappears, add more iodine until the color

remains. Record the total number of milliliters of standard iodineused in performing steps 11.1.1 and 11.1.5.

11.1.6 Titrate with 0.0250 N phenylarsine oxide solution using a starchindicator until the blue color disappears. Record the number ofmilliliters used.

11.2 Dissolved Sulfides:11.2.1 Unless the sample is entirely free from suspended solids,

(dissolved sulfide equals total sulfide), to measure dissolved


sulfide first remove insoluble matter. This can be done byproducing an aluminum hydroxide floc that is settled, leaving aclear supernatant for analysis.

11.2.2 To a 100-mL glass bottle add 0.2 mL (4 drops) 6N NaOH. Fillbottle with sample and add 0.2 mL (4 drops) AlCl3 solution.Stopper bottle with no air under stopper. Rotate back and forthabout a transverse axis vigorously for 1 min or longer to flocculatecontents. Vary volumes of these chemicals to get goodclarification without using excessively large amounts and toproduce a pH of 6 to 9. If a 500 or 1000 mL bottle is used, addproportionally larger amounts of reagents.

11.2.3 Let settle until reasonably clear supernatant can be drawn off.With proper flocculation, this may take 5 to 15 min. Do not waitlonger than necessary.

11.2.4 Perform steps 11.1.1 through 11.1.6.

12.0 INSTRUMENT MAINTENANCE AND TROUBLESHOOTINGThere is no maintenance or troubleshooting for this method.

13.0 DATA ACQUISITION, CALCULATION AND REDUCTION13.1 One ml of 0.0250 N standard iodine solution (5.2) reacts with 0.4 mg of sulfide present

in the titration vessel.13.2 Use the formula: mg/L sulfide = 400 (A - B)

ml samplewhere: A = ml of 0.0250 N standard iodine solution

B = ml of 0.0250 N standard reducing phenylarsine oxide solution

14.0 COMPUTER HARDWARE AND SOFTWARE14.1 Computer with StarLIMS

15.0 DATA MANAGEMENT AND RECORD MANAGEMENT15.1 After data has been entered into LIMS, it is reviewed by the analyst for




contents of the file cabinet are archived.

16.0 QUALITY CONTROL AND QUALITY ASSURANCE16.1 A blank should be titrated with each run to verify the absence of reagent

contamination and to confirm the possible presence or absence of samplematrix interference. Blanks should measure less than the limit of detection(0.2 mg/L).

16.2 Duplicate analyses are done every 20 samples. The relative percentdifference between the two sample results should be no more than 20%.


17.0 REFERENCES17.1 Methods for Chemical Analyses of Water and Wastes, EPA - 1983. EPA-

600/4-79-020, Method 376.1.17.2 Standard Methods for the Examination of Water and Wastewater, 18th

Edition. 1992, APHA-AWWA--WPCF. Method 4500-S2-.



Sample duplicate (DUP) One (1) per analyticalbatch per matrix

In-house derived limits Default:RPD < 20% if analytes > RL

Investigate problem, ifsystem precision in controlqualify results, if systemprecision out of controlreanalyze entire batch

Method Blank (MB) One (1) per analyticalbatch Analytes < RL

Clean analytical system,repeat until MBs are incontrol

Commonwealth Technology, Inc.


LIMS #: Method: Sulfide EPA 376.1


Yes … No



IndependentReview

Comments:


1. Does a titration bench sheet accompany the run? ---


3. Was a blank titrated along with the samples? ---

4. Was the blank result acceptable? < LOD

5. Were duplicates analyzed at the required frequency? 1 per 20 samples ofthe same matrix

6. Was the RPD of the duplicates acceptable? Within in house QClimits


CTLaboratories. SOP NO: 5200 Rev. 1Organics Laboratory Section Page 1 of 10 03/26/04

PROPRIETARY 1

CT Laboratories .Baraboo Laboratory Division

Title: Dissolved Methane, Ethene, Ethane, Acetylene and Carbon Dioxide in Water

SOP Number: 5200

Prepared by: ______________________________________Date






PROPRIETARY 2

1.0 Identification of Test Method

1.1 This method is designed to follow procedures and QC requirements consistent with other GCmethods utilized by this laboratory

2.0 Applicable Matrix or Matrices

2.1 This method is used to quantify Methane, Ethane, Ethene, Acetylene and Carbon dioxide inwater. Results are reported in µg/L. Results can be converted to units that may better satisfyclient or program needs.

3.0 Detection Limits

3.1 The reported levels of detection (RL) are 0.5µg/L for each compound (the RL currently usedfor Carbon dioxide is 200 ug/L).

4.0 Scope and Application

4.1 Target compounds for this method include Methane (CH4), Ethane (C2H6), Ethene (C2H4),Acetylene (C2H2) and Carbon dioxide (CO2). With proper detector configurations, oxygen (O2)and carbon monoxide (CO), as well as other dissolved gases, may be prepared and analyzed bythis procedure.

5.0 Method Summary

5.1 Gas chromatographic conditions are utilized for the detection of dissolved gases. Quantificationis achieved through analysis of headspace created in each sample vial. The gas chromatograph(GC) is temperature programmed to facilitate separation of organic compounds. The GC uses aflame ionization detector (FID).

5.2 Identification of the dissolved gases is performed by comparison of samples with commerciallypurchased external standards. Quantification is achieved through calibration of the instrumentusing the FID’s response to the external standards.

6.0 Definition

6.1 Dissolved gas quantification is based on a direct comparison of the areas of each constituent.

6.1.1 An initial calibration check verification standard (ICV) is analyzed immediately followinga calibration curve to verify the linearity of the curve and as a check on the integrity ofthe calibration standard.

6.1.2 An initial calibration blank (ICB) is analyzed after calibrating the instrument todemonstrate that the instrument, purge gas, and preparation water are free fromcontamination.

6.1.3 A calibration check verification standard (CCV) is analyzed at the beginning of asequential run of 20 or fewer samples, and again after every ten samples. The CCVfunctions in verifying the compliance of the calibration curve and the stability of retentiontimes.

6.1.4 A laboratory control spike (LCS) is analyzed with each batch of samples as a system


PROPRIETARY 3

control and method control check. An LCS should be analyzed with every batch ofsamples (20 or fewer).

6.1.5 A method blank (MB) is run with each batch of 20 or fewer samples to ensure theinstrument, purge gas, and preparation water are free from contamination.

6.1.6 A matrix spike, matrix spike duplicate (MS/MSD) pair are run with every batch of 20 orfewer samples as a matrix interference and control check. If not enough sample isavailable to run an MS and MSD a laboratory control spike duplicate (LCSD) can beanalyzed along with the LCS.

6.1.7 One sample per batch (20 or fewer) is also prepared in duplicate and is used as aprecision sample preparation check.

6.1.8 A particularly dirty sample can possibly contaminate sampling syringes. After a dirtysample, the syringe should be flushed with the inert purge gas.

7.0 Interferences

7.1 High levels of heavy hydrocarbons may contain constituents that fall among the dissolved gasretention times. These contaminants may adversely affect the baseline during analysis. In thiscase, dilute the sample and reanalyze to confirm hydrocarbon contamination.

7.2 Moisture can interfere with analysis. Procedures to minimize the injection of moisture into theGC are advisable.

8.0 Safety

8.1 Gloves, safety goggles, and protective clothing should be worn to protect against unnecessaryexposure to hazardous chemicals and contaminants in samples. All activities performed whilefollowing this procedure should utilize appropriate laboratory safety systems.

9.0 Equipment and Supplies

9.1 10 uL, 25µL, 100µL, 500µL, and 1mL gas-tight syringes (Hamilton or equivalent).

9.2 40mL VOA vials with Teflon-lined caps (QEC or equivalent).

9.3 Ring stand with three-finger clamps.

9.4 15mL graduated vial (Fisher brand or equivalent).

9.5 Thermometer (NIST traceable).

9.6 Water bath (ambient temperature).

9.7 Gas chromatographs (Hewlett Packard 5890 or SRI 8610) equipped a packed column (Supelco,Haysep D, 80/100 mesh size) and a FID.

9.8 Data management system (EZ Chrom-Elite, ver. 3.1 or Peak Simple II).

10.0 Reagents and Materials


PROPRIETARY 4

10.1 200ppmV CH4, C2H6, and C2H4 certifide gas standard (Scotty II or equivalent), prepared inhelium.

10.2 200ppmV C2H2 certifide gas standard (Scotty II or equivalent) prepared in helium.

10.3 10,000ppmV certifide CO2 (Scotty II or equivalent) prepared in helium.

10.4 Deionized water (Milipore).

10.5 Inert gas (He or N2) for purging (4.7 grade or better, 99.999%)

11.0 Sample Preservation and Storage

11.1 Samples to be analyzed for methane, ethane, ethene, and acetylene require preservation byacidification (pH < 2). Samples requiring CO2 analysis are to be analyzed unpreserved. Allsamples are to be stored in the volatiles double door refrigerator, inverted, at 4°C ±2°. Hold timeis 14 days from sample collection except for CO2 which requires analysis within 7 days fromsampling.

12.0 Quality Control

12.1 Table 1 is designed to outline the control steps and provisions required to produce acceptabledata.

13.0 Calibration and Standardization

13.1 Six injections of varying standard concentrations are introduced into the GC via the directinjection port. The standards range from 2ppmV to 100ppmV. The results are then plotted on acalibration curve by the instrument’s computer software. Procedures for programming thecalibration are outlined in the reference manuals supplied with the EZChrom software. Theplotted curves for each compound should have a correlation coefficient (r2) of 0.990 (or r ≥0.995) in order for the curve to be considered valid.

13.1.1 The standard concentrations are made using the 200ppmV dissolved gas standard (or10,000 ppmV for CO2), as follows:

Methane/Ethene/Ethane and Acetylene

Standard Concentration Standard added (in µL)2ppmV 105ppmV 25

10ppmV 5020ppmV 10050ppmV 250100ppmV 500

Carbon dioxide


PROPRIETARY 5

Standard Concentration Standard added (in µL)50ppmV 5100ppmV 10250ppmV 25500ppmV 50

1000ppmV 1002500ppmV 250

An ICV is analyzed immediately following a successful calibration. To analyze an ICV, inject250µL of the dissolved gases standard directly into the GC (concentration = 50ppmV) forMethane, Ethene, Ethane, and Acetylene. Inject 50 ul of the gases standard for CO2 (conc. = 500ppmV).

13.2 An ICB should follow the ICV, before samples are analyzed. The ICB is prepared in the sameway as a method blank, with the same requirements.

14.0 Procedures

14.1 Samples are collected in 40mL VOA vials with zero headspace. Following login, they arestored inverted in the volatiles refrigerator (<4°C ± 2°).

14.2 To prepare the samples for analysis, each sample is purged with an inert gas in order to obtaina 4mL headspace. The sample vial is placed in a 3-finger clamp, at an inverted 45° angle. Alarge bore needle is inserted through the septum, directly over the graduated collection device. Another needle (connected to the purge gas source) is inserted through the septum. The purgegas pressurizes the sample, expelling the 4mL (the purge rate should be no faster than5mL/min).

14.3 When all samples have been prepared, they are shaken for five minutes on a shaker table,allowing the gas and liquid phases to equilibrate. Before analysis, the samples should be placedin an ambient temperature water bath, to allow samples to reach a constant temperature.

14.4 A method blank (MB) is to be analyzed with each batch of samples (one per 20 samples).Method blanks are prepared by reversing the flow of the purge gas through the system, fillingthe VOA vial with degassed water. The vial should have no headspace, and should then beprepared in the same manner as the other samples.

14.5 An LCS is prepared in the same manner as a method blank. Once the 4mL headspace hasbeen provided, withdraw 500µL of the headspace and immediately inject 500µL of the a 200ppmV dissolved gases standard (Methane, Ethane, Ethene, and Acetylene) into the headspace. Analyze 1mL of the spiked headspace by directly injecting it into the GC (final concentration: 25ppmV). For CO2 withdraw 100 uL of the headspace and immediately inject 100 uL of the10,000 ppmV CO2 gas standard. Analyze 1mL of the spiked headspace by directly injecting itinto the GC (final concentration: 250ppmV). The final concentration values are converted toug/L via a series of calculations (see sec. 15.0) to obtain recoveries values in the LIMSsystem.

14.6 If sample volume is sufficient (e.g. the client has provided at least three to four vials for asample), an MS/MSD set should be analyzed. This sample is prepared in the same way as theother samples. Withdraw 500µL of the headspace and immediately inject 500µL of the


PROPRIETARY 6

200ppmV dissolved gas standard (Methane, Ethane, Ethene, and Acetylene). Analyze 1mL ofthe spiked headspace by directly injecting it into the GC (final concentration: 25ppmV). ForCO2 withdraw 100 uL of the headspace and immediately inject 100 uL of the 10,000 ppmVCO2 gas standard. Analyze 1mL of the spiked headspace by directly injecting it into the GC(final concentration: 250ppmV). The final concentration values are converted to ug/L via aseries of calculations (see sec. 15.0) to obtain recoveries and precision values in the LIMSsystem.

14.7 A CCV analysis begins and ends each sequential run (also injected after every ten sampleanalyses) 250µL of dissolved gas standard is directly injected into the GC. Inject 50 ul of thegases standard for CO2 (conc. = 500 ppmV).

All target compound recoveries must be within QC limits in order for analysis to continue. Amethod blank follows the CCV, and samples analyses follow the MB.

14.8 The GC’s are either run isothermally at 95°C or slightly ramped to facilitate sample peakseparation. The CO2 sample are currently analyzed on the SRI GC equipped with a methanizer(set at approximately 380°C) used for catalytically reduce CO2 to Methane in order to get anFID response. Helium or Nitrogen are typically used as carrier gases and hydrogen mix within-house compressed air is used as the reaction gas to burn in the FID. To better separateAcetylene from Ethene two Haysep D columns are connected in series. Carrier flow rates areadjusted for optimum separation (usually between 15 and 20 mL/minute).

15.0 Calculations

15.1 EZChrom will produce results in ppmV (or partial pressure result). Peak Simple II provides apeak area that is converted into partial pressure. An Excel spreadsheet is set up in which theresults in ppmV are converted to µg/L. This is achieved, in part, by the use of Henry’s LawConstant. Each analyte has a different value for this constant, as seen in Table 2. Thespreadsheet contains several other values. Vial volume (ave. vol. = 43mL), the headspacevolume (normally 4mL), sample temperature (°C), equilibrium mole fractions , moles of gas,saturation concentrations, and densities must all be known or calculated to obtain the correctfinal result. Each gas also has a unique molecular weight (as outlined in Table 3).

15.2 The partial pressure of each compound is found using the linear equation:

Pg = mx + b

Where:• Pg = partial pressure• m = slope of calibration curve• x = area obtained from sample analysis• b = y-intercept of calibration curve

15.3 The partial pressure is converted to a decimal equivalent. For instance, 10ppm = 0.000010 (1.0× 10-5).

15.4 The equilibrium mole fraction is then determined by dividing the partial pressure by theHenry’s Law Constant for that compound (see Table 2).

Xg = Pg. ÷ H


PROPRIETARY 7

Where:• Xg = equilibrium mole fraction• Pg = partial pressure• H = Henry’s Law Constant

15.5 The moles of gas (Ng) is found by multiplying the equilibrium mole fraction (Xg) by 55.5, where 55.5 = gram⋅moles of 1L of water.

15.6 The saturation concentration C of the gas is calculated as follows:

C = Ng (MW)(1000mg/g)

Where:• MW = molecular weight of gas (see Table 3)

15.7 To adjust gas density for pressure:

D = (MW) ÷ (22.4 L⋅mol)(T/273)

Where:• T = sample temperature in Kelvin

15.8 Determine the milliliters of analyte in the headspace (Ah):

Ah = (mL of headspace)(Pg)

15.9 To determine the amount of analyte in the liquid phase:

A1 = (Ah/V)(D)(1000mg/g)(1L/1000mL⋅L)

Where:• V = volume of water (vial volume – headspace volume) in liters

15.10 Finally, the total concentration(TC) of an analyte in the original sample is found by adding theconcentration in water to the saturation concentration. This result will be in mg/L. Convert toµg/L.

TC = A1 + C

TC (mg/L) × 1000 = TC (µg/L)

16.0 Method Performance

16.1 Certified standards, properly maintained instrumentation, and analyst experience and expertiseare critical elements in producing accurate results.

16.2 Initial demonstration of capability (IDC) is a technique used to ensure acceptable methodperformance. An analyst must demonstrate initial precision and accuracy through the analysis


PROPRIETARY 8

of five laboratory control spikes. After analysis, the analyst determines the average recovery inµg/L, as well as the relative standard deviation (RSD of the recoveries for each analyte. Thedefault criteria of 70-130% recovery and 20% RSD are used until internal limits are generated.

16.2.1 IDCs are analyzed in the same way as a laboratory control spike.

17.0 Data Assessment and Acceptance Criteria for QC Measures

17.1 If the initial analysis of a sample or a dilution of the sample has a concentration of a particularanalyte that exceeds the calibration range, the sample must be reanalyzed at a higher dilution(i.e. smaller injection volume). If the blank analysis is not free of interferences, the system mustbe decontaminated. Sample analyses cannot resume until a blank that is free of interferencescan be analyzed.

17.2 When the analysis of an analytical batch or sequence has completed, the data is processed andprepared for reporting. Assessments of all spiked and calibration control samples and standardsshould also be finalized before reporting the data. When the analyst has finished processing theanalytical batch, the results are manually entered into the LIMS system where dilution factoradjustments are made. Once the final results have been verified, the data is turned over toanother qualified analyst for final validation. The second analyst confirms the results andelectronically validates them. Finally, the validated results are made available to the clientservices personnel in order for the data to be given to the client or appropriate agencies.

18.0 Waste Management

18.1 Samples are routinely held (refrigerated) for up to six weeks from analysis date before theyenter the waste stream. Waste disposal of samples and standards follows the proceduresdocumented in the Laboratory Waste Disposal SOP (Quality Assurance Section, SOP No. FO-8, Rev. 4).

19.0 References

19.1 USEPA, Methane, Ethane, Ethene Analysis Guidance, Rev. 1, February 21, 2002

19.2 RSK SOP 175, Analysis of Dissolved Methane, Ethane, and Ethylene in Ground Water byStandard Gas Chromatographic Technique. Region 1 Library, 1997

Table 1-QC RequirementsQC Item Frequency Acceptance Criteria Corrective Actions


PROPRIETARY 9

Initial calibration (ICAL) Each time the instrument isset up. Establishedinitially with a minimum offive concentration levels,with the low standard at orbelow the reporting limit(RL).

Coefficient ofdetermination (r2) shouldbe > 0.990. (r > 0.995)

Correct system andrecalibrate. Criteria shouldbe met before sampleanalyses can begin.

Continuing CalibrationCheck Standard (CCV) andInitial CalibrationVerification (ICV)

Analyzed at the beginningand end of each sequentialrun and after every 10samples. ICV analyzedafter intial calibration.

Within 20% of spikedvalue or withinproject/program specifiedcriteria.

Reanalyze CCV andaffected samples. If CCVrecoveries are stillunacceptable, correctproblems and recalibrate.

Method Blank (MB) andInitial Calibration Blank(ICB)

Analyzed with each batchof samples (20 or less).

Recoveries less thanadjusted reporting limit. Blank subtraction is notallowed.

Reprep with fresh waterand reanalyze.

Matrix Spike/Matrix SpikeDuplicate (MS/MSD)

Analyzed with each batchof samples (one set per 10samples).

Recoveries: Default 70 to130%. Precision: Default20%. Or use internallygenerated or project/program specific limits.

Repeat injection, checkcalculations. Recoveriesreported exceeding limitsshould be qualified (M)

Laboratory Control Spike(LCS)

Analyzed if sample volumeis insufficient for MS/MSDanalysis (every 10samples). Second sourcestandard is optionalbecause of difficulty ofobtaining a second source.

Default: 70-130%Recovery. Or useinternally generated orproject/ program specificlimits.

Reanalyze LCS andaffected samples. If LCSrecoveries are stillunacceptable, correctproblems and recalibrate.Sample results reportedwith associated LCSrecoveries exceeding limitsshould be qualified (Q).

Qualitative/QuantitativeIssues

If analyte(s) in a sampleexceeds the workingcalibration range of theinstrument, the samplemust be diluted andreanalyzed so that thecompound(s) fall aroundthe midpoint of thecalibration curve. If theconcentration of the targetanalyte that exceeded thecalibration range is presentin the subsequentsample(s) (>RL but<20xRL), the sample(s)should be reanalyzed toconfirm the sample syringeis clean.

The detection level of allcompounds must be withinthe working range of thecalibration curve. Potential carryover mayoccur only if the samplesyringe contains thecontamination from onesample to the next. Properflushing of the syringeswith an inert gas willeliminate this problem.

Dilute the sample to bringthe level of the highestconcentration of targetcompounds within theworking range of thecalibration curve.If a sample is reanalyzed todetermine whether or not ccarryover has occurred,and the results do notconfirm in the secondanalysis, then report onlythe second analysis. Oncemore than 10 % of thehead space is removedfrom a vial for analysisthen another vial shouldbe prepared beforereanalyzing the sample.

Table 2-Henry’s Law Constants


PROPRIETARY 10

Compound Temperature Range (in °C) Henry’s Law Constant

Methane13-1617-2223-27

3.37 × 104

3.76 × 104

4.13× 104

Ethane13-1617-2223-26

2.26 × 104

2.63 × 104

3.02 × 104

Ethene13-1617-2223-26

8.95 × 103

1.02 × 104

1.14 × 104

Acetylene13-1617-2223-27

1.08 × 105

1.21 × 105

1.33 × 105

Carbon Dioxide13-1617-2223-26

1.22 × 103

1.42 × 103

1.64 × 103

Table 3-Molecular WeightsCompound Molecular Weight (in amu)

Methane 16Ethane 30Ethene 28

Acetylene 26Carbon Dioxide 44

CT Laboratories SOP No: SS-4 Rev. 5Sample Receiving Section Page 1 of 8 3/30/05

CT LaboratoriesBaraboo Laboratory

Title: Restrictive Sample Handling and Documentation

SOP Number: SS-4

Written by: ______________________________________

Technical Review by: ______________________________________Quality Assurance Manager

Approved by: ______________________________________Laboratory Director

SOP Manual Control Number: _____________________


Restrictive Sample Handling and Documentation

1.0 SCOPE AND APPLICATION

1.1 The following procedure applies to samples submitted for analysis that require restrictivehandling. Typically, samples that require this handling are from USEPA or DOD projects,samples that have a high probability of legal proceedings, or are sensitive in nature. Theprocedure and accompanying forms should meet most needs that are not specificallyaddressed in other documents.

1.2 Upon prior notification, all samples requiring restrictive handling, whether analyzed at thislaboratory or subcontracted, will be handled in a prescribed manner and documented.

1.3 Due to the legal nature of enforcement driven investigations, possession of samples must betraced from time of collection until introduced as evidence in a legal proceeding ordestroyed. To maintain and document sample possession, restrictive internal procedures arefollowed. The following operating procedure outlines the steps that must be followed tomeet these requirements.

2.0 DEFINITIONS

2.1 A sample is in your custody if:2.1.1 it is in your possession, or2.1.2 it is in your view, after being in your possession, or2.1.3 it was in your possession and you returned it, or2.1.4 it is in a designated secure area.

2.2 LIMS – Laboratory Information Management System

3.0 PROCEDURES

3.1 Field Custody

3.1.1 The field sampler or designated field person is personally responsible for the propercare and custody of the field samples until they are properly transferred ordispatched to the laboratory.

3.1.2 Sample labels or tags must be completed for each sample and any subsample thatwould make up a sample. At a minimum, the labels or tags should contain thesampling location, date, time and samplers name.

3.1.3 Sample containers or shipping containers can be secured with a custody seal. Ifused, the seal must be made in such a manner that visually shows a break,destruction or change in nature if the seal is tampered with.


3.1.4 All samples must be accompanied by proper documentation in the form of a CHAINOF CUSTODY record. This document must clearly identify the samples and/orsubsamples, the designation of the intended testing to be performed on each sample,the sampler, the person relinquishing the custody of the samples, to whom thesamples are relinquished to and the dates/time of the events.

3.2 Transfer of Custody and Transport/Shipment

3.2.1 Samples must be properly packaged for shipment. For samples requiringtemperature preservation, sufficient ice should surround samples to assure ice ispresent when the samples reach the lab. Internal packaging should be in place toassure container integrity and comply with shipping requirements.

3.2.2 The original Chain of Custody will accompany the samples. Each shipping containershould be accompanied by a Chain of Custody form. A copy of the form should beretained by the field personnel.

3.2.3 A Chain of Custody record must accompany all samples. If the samples are shippedvia common carriers (UPS, FedEx, Airborne, etc.) the mode of shipping should benoted in the “Remarks” section of the form. The person relinquishing the samplescan sign, date and note the time in the first “Relinquished by” portion on the form.The shipping document (Air Bill, etc.) will serve as documentation of custodypossession. The Chain of Custody should accompany the samples by placing it in awaterproof container directly in the shipping container.

3.2.4 Laboratory courier transferred samples should have the person relinquishing thesamples sign, date and note the time in the first “Relinquished by” portion on theform. The laboratory’s courier should take possession of the samples andimmediately sign the “Received by” portion of the corresponding line on the form.

3.3 Sample Receipt

3.3.1 Upon receipt by the laboratory Sample Entry will take possession of the sample asfollows:

3.3.1.1Samples shipped by common carrier, and signed for by Sample EntryTechnician, will have the carrier’s paperwork retained and attached to theback of the Chain of Custody.

3.3.1.2Samples in the possession of couriers will have the courier transferpossession to Sample Entry Technician by signing the Chain of Custody inthe next available “Relinquished by” line on the form.

3.3.1.3Once the samples are in the possession of sample entry the Chain of Custodyis signed, dated and time noted in the “Received by Laboratory” portion ofthe form.


3.3.2 The Sample Entry Technician will observe condition of Shipping container,accompaning paperwork and samples to record in the sample condition function ofLIMS.

3.3.2.1 Examine the shipping container and record the following;• CT Laboratories cooler tracking number• Date and time cooler was received• Sample Entry Technician who received cooler• Presence or absence of a custody seal on the shipping container• The condition of the seal (intact, damaged, open, etc.)• Shipping method and tracking number of shipping container• Obvious damage or leaking shipping containers

3.3.2.2Open the shipping container, remove the enclosed accompanying documentsand record;

• The presence or absence of a Chain of Custody• The Chain of Custody must be complete

3.3.2.3 Remove the sample from the shipping container and record the following;• The temperature of temperature blank or melt water temperature• Ice present or absent, or melt water• Adequate packaging of samples• Condition of each sample, subsample or container by the

following codes• ( 1 ) Intact• ( 2 ) Too Many Containers• ( 3 ) Broken Container• ( 5 ) Missing Bottle• ( 7 ) Wrong Container• ( 8 ) Past Hold Time• ( 9 ) Incorrectly Preserved• (10) Insufficient Volume• (11) Labels Missing/Unreadable• (12) Air bubbles in VOA vials

3.3.2.4Compare documents to verify agreement between;• Chain of Custody records• Sample tags or labels• Air Bills or Bills of Lading

3.3.2.5A Sample Condition Report will be generated in LIMS and sent to the ProjectManager via internal e-mail.


LIMS Sample Condition function screen


Sample Condition Report

Folder #: 29071 Coolers: 12345 Date: 9/12/2002 Time: 09:23Client: CT Laboratories Received Date/Time: 9/12/2002 0930 Received By: DJEProject Name: 2002 PT Log-In Date/Time: 9/12/2002 0945 Logged By: DJEProject #: WP-92 PM: PML

Temperature: 2.0 C On Ice: Y COC Present: Y Complete: YCustody Seals Present: Y Intact: Y Numbers: 123456789Ship Method: FedEx Tracking Number: 123456789Adequate Packaging: Y Temp Blank Enclosed: Y

Notes: One of three VOC vials broke in shipping. Client contacted by DJE at 0940 on 09/12/02.

Sample ID/Description Container # Condition Filtered Tests Code

148568 574 AMBER GL 1 1 Y HG

148569 580 HNO3 1 11 Y ICP

148570 582 AMBER HCL 1 9 N O&G

148572 586 HNO3 1 7 Y ICP

148573 830 VOA HCL 3 3 N VOC

1 Sample Received OK3 Broken Container7 Wrong Container9 Incorrectly Preserved

11 Label Missing/Unreadable


3.4 Sample LIMS Log-in

3.4.1 Samples are processed through the routine log-in procedure (found in SOP # SS-5)with the exception of distribution noted below.

3.5 Restrictive Sample Storage

3.5.1 Samples will be stored in a secured area, appropriately designated and conditionsrequired for proper preservation.

3.5.2 Damaged samples will be disposed of appropriately and the method of disposaldocumented.

3.5.3 The laboratory and sample storage areas are secure with strict limited access bylaboratory personnel.

3.5.4 Whenever samples are removed / returned from storage that fact will be documentedon an Internal Chain of Custody.

3.5.5 The location of stored sample extracts will be appropriately recorded.

3.5.6 VOC samples will be stored separately from other samples, extracts, standards orany source of possible contamination.

3.5.7 Standards will be stored separately from samples and extracts.

3.5.8 After completion of analysis, samples and extracts will be stored in compliance withthe contract or until otherwise instructed by the appropriate authority.

3.6 Sample Security

3.6.1 Samples will be stored in a secure area within the laboratory.

3.6.2 Access to the laboratory is through locked doors.

3.6.3 Visitors will be escorted at all times while in the laboratory.

3.6.4 Samples will remain in secure sample storage until removed for analyticalpreparation or analysis. All transfers of samples into and out of storage will bedocumented on an Internal Chain of Custody form.

3.6.5 When samples are removed from secure storage by the analyst, the analyst isresponsible for the custody of the sample. The analyst will return the sample tosecure storage before the end of the work day.

3.6.6 Internal Chain of Custody forms will be retained in the associated sample file.


3.7 Internal Chain of Custody Procedures

3.7.1 VOC samples requiring temperature preservation will be stored in the VOCrefrigerator. Non-VOC samples will be stored in the Semi-Volatile refrigerator.

3.7.2 The refrigerators will remain secure during periods restrictive samples are present.

3.7.3 Restrictive samples will remain in the secured areas until removed for samplepreparation or analysis.

3.7.4 All transfers of restrictive samples into and out of secure storage will be documentedon an Internal Chain of Custody. These records are maintained by the QualityAssurance Officer.

3.7.5 When a sample is removed from secure storage the analyst taking custody of it willdocument the action on the Internal Chain of Custody. The sample will remain in thecustody of that analyst until it is returned to the secured area. If the contents of thesample container are completely used, this fact will be documented on the InternalChain of Custody. If the contents of a sample container are used by more than oneanalysis (multiple tests) this fact will be documented on the Internal Chain ofCustody.

3.7.6 All restrictive samples will be returned to secure storage at or before the end of thework day.

3.7.7 When sample analysis and reporting is completed by the laboratory, or after threemonths time, whichever is longer, the unused portion of the sample will be disposedof properly. All forms, data sheets and records will be retained as permanentdocumentation, as directed by the contract or regulations.

4.0 REFERENCES

4.1 NEIC Policies and Procedures, May 1978 (Rev. March 1986)

4.2 EPA-330/9-78-001-R

4.3 EPA Central Regional Laboratory (communications)

4.4 US ACOE – EM 200-1-3

CT Laboratories SOP NO: 5280B Rev. 6Organics Laboratory Section Page 1 of 37 02/05/04

1

CT Laboratories .Baraboo Laboratory Division

Title: Analysis of Volatile Organic Compounds by GC/MS

SOP Number: 5280B

Prepared by: ______________________________________Date






2

1.0 Method

1.1 This method is designed to follow procedures and QCrequirements found in EPA SW-846 methods 5030, 5035, 8000and 8260 in order to determine quantities of volatile organiccompounds found in a variety of different sample matrices.

2.0 Applicable Matrix or Matrices

2.1 Volatile organic compounds are quantitated from a variety of matrices. This method isapplicable to nearly all types of samples regardless of water content, including groundwater, surfacewater, wastewater, soils and sediments, as well as other matrices noted inSW-846 method 8260B.

3.0 Detection Limits

1.1 Method detection limits (MDLs) are determined annually and results vary from compound tocompound. Water MDLs typically fall in the range of 0.10 to 10 ug/L (5.0 mL purge) or 0.02to 2.0 ug/L (25 mL purge). Soil MDLs are usually found to be between 0.0001 to 0.005mg/kg (low-level soils) or 0.005 to 0.50 mg/kg (methanol preserved). Procedures forconducting MDL studies can be found in CT Laboratories Initial Method Performance andReporting SOP.

4.0 Scope and Application

4.1 This method is used to quantify Volatile Organic Compounds (VOCs) with boiling pointsbelow 200° Celsius (°C) in water and soils. See Table 1 for typical target analyte list(TAL).

4.2 Examples of other compounds which have been analyzed by this method include:

Iodomethane, 2,3-Dichloro-1-propene, 1-Chlorohexane, Acrolein, Acrylonitrile, and 2-Chloroethylvinyl ether. SW-846, method 8260B notes a number of other compoundsamenable to this test.

5.0 Method Summary

5.1 A Purge & Trap system (including autosampler), a Gas Chromatograph (GC), and a MassSpectrometer (MS) are utilized for the detection of VOCs. The autosampler introducesthe sample to the purge and trap concentrator. The concentrator then removes thevolatile constituents by purging the sample with an inert gas (Helium). The constituentsare then collected onto an adsorption trap. The trap is then rapidly heated and thevolatilized compounds are introduced to the GC. The GC is temperature programmed tofacilitate separation of the individual organic compounds. Finally the separatedcompounds enter the MS (which is interfaced with the GC) for quantitative andqualitative analyses.

5.2 Utilizing computer software, identification of target analytes is accomplished by comparingthe mass spectra of the sample constituent with that of commercially purchasedstandards. Quantitation is achieved by comparing the response of a quantitation ionrelative to an internal standard using a five point (minimum) calibration curve.

6.0 Definitions


3

6.1 4-Bromofluorobenzene (BFB), is used to verify that the GC/MS is properly tuned andready for calibration and sample analyses. BFB is directly injected at 25-50 ng andprecedes all other analyses. A twelve hour analysis time window is used before anotherBFB injection is required.

6.2 An initial calibration verification standard (ICV) is analyzed before the analysis of samplesas a check on the calibration curve. The ICV should be of a second source, meaning aseparate vendor and/or lot # should be used to prepare this standard. A second source isneeded to validate the integrity and concentration of the standards used for calibration.

6.3 An initial calibration blank (ICB) is also analyzed before samples to confirm that thedeionized water (DI H2O) used for standards, blanks, and dilutions is free fromcontamination. An ICB for soil samples also includes organic free sand and/or methanolused for standard and QC preparation, as well as sample dilutions and volumeadjustments; the control sand and methanol must also be documented as free fromcontamination.

6.4 A calibration check verification standard (CCV) is analyzed at the beginning of eachsequence (following the BFB injection) shift and every 12 hour shift thereafter. A CCVis made up from the same standards used for calibration and is used to ensure that thecalibration and retention times are stable.

6.5 An analytical batch is defined as a group of samples (not to exceed 20 samples) analyzedper sequential run. Depending on client or program requirements, an analytical batch mayor may not include matrix spikes as part of the 20 samples.

6.6 Internal standards (ISTD) are added to each sample, blank, spike, and check standard.The ISTDs used are Fluorobenzene, Chlorobenzene-d5, and 1,4-Dichlorobenzene-d4. TheISTD is used for internal calibration as a reference peak and to check purging efficiency.

6.7 Surrogate standards (SSTD) are also added to each sample, blank, spike, and checkstandard. The SSTDs used are Toluene-d4, 4-Bromofluorobenzene, 1,2-Dichloroethane-d4,and Dibromofluoromethane. The SSTD is used as matrix interference and as a methodcontrol check.

6.8 A method blank (MBW = water, MBS = soil) is analyzed with every batch of samples toensure the instrument is free from contamination. Method blanks are also used todemonstrate that the DI H2O, organic free sand, and methanol used in sample preparationis also free from contamination.

6.9 A continuing calibration blank (CCB) is analyzed every 12 hour shift after the MB hasbeen analyzed and before sample reanalyses to ensure the system is still free fromcontamination.

6.10 Instrument blanks (IB) are analyzed whenever instrument contamination is a suspectedpossibility. The purpose of an IB is to prevent carry over from a standard, spike, orcontaminated sample into another sample or blank. The acceptance criteria for an IB isthe same as for a MB or CCB (for example: if an IB contains detections aboveacceptance criteria and a MB and/or sample following the IB exhibit the samecontamination above acceptance criteria, then the instrument should be consideredcontaminated). The samples and/or MBs should be reanalyzed after the instrument isconfirmed free from contamination.

6.11 A matrix spike and matrix spike duplicate (MS/MSD) are analyzed with every batch of


4

samples as a matrix interference and control check.

6.12 A laboratory control spike (LCS) is analyzed with every sample batch as a system controland method control check.

7.0 Interferences

7.1 Volatile materials in the laboratory and impurities in the purging gas and sorbent trap cancause significant amounts of background contamination. Improper tubing such as certainplastics and rubber should not be used. The analysis of IBs and MBs should indicate asto whether or not this type of contamination is present. Since subtraction on backgroundcontamination is not allowed, care should be taken to eliminate this type of contamination.

7.2 Carry over contamination is a problem when a highly contaminated sample is followed bya clean sample. Rinsing the autosampler and concentrator and adequate baking of thetrap can greatly reduce contamination from carry over.

7.3 Some samples contain a lot of water soluble materials, suspended solids, compounds withhigh boiling points, or target analytes with very high concentrations which maycontaminate some or all of the analytical system. Removing components of the system forcleaning or cleaning of the entire system may be required to eliminate the interferences.

7.4 Compounds with poor purging efficiencies may remain in the purge system, particularlywith 25 ml purges. Ensuring adequate rinsing and increased line temperatures will helpreduce this problem.

7.5 All chromatography gas/purge lines should be stainless steel or copper to prevent permeation from possible background contaminants (i.e. Methylene chloride). Background levels of Methylene chloride are possible so care should be taken to reducethis possibility. Analyst clothing previously exposed to methylene chloride should not beworn and isolating the instruments from possible airborne contamination is essential inreducing Methlyene chloride background contamination.

7.6 A trip blank normally accompanies sample in shipment and storage as a check on possiblecontamination from volatile organics by diffusion through the septum seal in samplevials/containers.

7.7 Mass spectrometer sensitivity, column degradation, and contamination can also contributeto background interferences. Proper maintenance procedures on instrumentation isessential to continually producing quality data. Maintenance manuals are provided witheach piece of equipment and are essential for proper instrument care. The manuals usedare as follows: Autosampler (Archon Purge and Trap Autosampler System Operator’Manual, Varian Model 5100;4552), Concentrator (LCS 2000 User Manual Tekmar andPurge & Trap Concentrator, Tekmar 3000), Gas Chromatograph--HP 5890 Series IIOperating Manual, and Mass Spectrometer--HP 5972A MSD Hardware Manual). Thepresence of semi-volatile hydrocarbons should also be taken into consideration, soappropriate post analysis bake out times should be incorporated.

8.0 SAFETY

8.1 Gloves and protective clothing should be worn to protect against unnecessary exposure tohazardous chemicals and contaminants in samples. All activities performed whilefollowing this procedure should utilize appropriate laboratory safety systems.


5

8.2 The toxicity and carcinogenicity of the chemicals used in this method are not preciselydefined. Each chemical and sample should be treated as a potential health hazard, so careshould be taken to prevent undue or extensive exposure.

9.0 Equipment and Supplies

9.1 40 mL screw cap “VOA” vials-borosilicate glass with a Teflon faced silicone septum (QEC or equivalent).

9.2 2 oz., 4 oz., or 60- mL Teflon lined screw top sample jars (QEC or equivalent).

9.3 5 g or 25 g samplers for low level soils (Encore)

9.4 Top loading balance sensitive to 0.01 g (Mettler-Toledo, BD202).

9.5 pH paper to confirm water sample preservation(Color pHast, EM Reagents)

9.6 Stainless steel spatulas

9.7 10, 25, 50, 100, 500, and 1000 uL gas tight syringes for sample dilutions and standardpreparation (Hamilton or equivalent).

9.8 5.0, 10.0, 25.0, 50.0 mL syringes with luer-lok tips for methanol preserved soil samplepreparation and sample dilutions (Hamilton/SGE or equivalents).

9.9 10, 50 100, 200, 1000, and 2000 mL Volumetric flask for sample dilutions and standardpreparation (Class A, Pyrex/Kimble or equivalents).

9.10 Auto pipetter – 2.5 to 25.0 ml – for dispensing methanol (Dispensette).

9.11 Sonicator used for methanol-preserved soil sample extraction (Fisher, FS-28).

9.12 Auto sampler used for sample introduction to the Purge and Trap (EST, Archon).

9.13 Purge and Trap concentrator (Tekmar, 2000/3000)

9.13.1 The glass purging tubes are of 5 mL or 25mL size. The all-glass purging deviceshould be designed to accept 5 or 25 mL samples with a water column at least 5cm deep. The smaller (5 mL) purging device is recommended if the GC/MSsystem has adequate sensitivity to obtain the method detection limits required fora specific project or program.

9.13.2 The trap currently used is Supelco Type K. As required by SW-846 methods,the trap must be at least 25 cm long and have an inside diameter of at least 0.105inches. Starting from the inlet, the trap should contain 1.0 cm of methyl siliconecoated packing and the following amounts of adsorbents: 33% of 2,6-diphenyleneoxide polymer, 33% of silica gel, and 33% of coconut charcoal.

9.14 Gas Chromatograph/Mass Spectrometer/Data System (GC/MS)

9.14.1 Hewlett Packard Series II Gas Chromatograph

9.14.1.1 Column, Supelco (SPB-624), 30 Meter x 0.25 mm ID, 1.4 um film


6

thickness

9.14.2 Hewlett Packard 5972 Mass Spectrometer

9.14.3 Hewlett Packard Chemstation Data Management System (version G1701AA v.A.03.02) with Enviroquant and Prolab data processing software.

10.0 Reagents and Materials

10.1 Purge and trap grade methanol: (Fisher, Purge & Trap grade or equivalent),stored in laboratory warehouse.

10.2 Reagent grade water, organic free (Milipore, 18 megaohm quality).

10.3 Certified Calibration Standards: (VOC Mix--2000 ug/mL, Accustandard--#M-502-10X;Additions--1000/10,000 ug/mL, Protocol--#XCTIVOA-Rev or equivalents), stored inVOC Standards Freezer in Volatiles laboratory at ≤ -10 °C.

10.3.1 A 100 ug/mL1 Continuing Calibration Verification (CCV) working standard isprepared by adding 150 uL of the VOC mix and 300 uL of the Additions mix to2550 uL of methanol in a 3 mL Mininert vial.

10.4 Certified Calibration Check Standards: (VOC Mix--2000 ug/mL, Ultra Scientific--#DWM-588; Additions--1000/10,000 ug/mL, Protocol--#XCTIVOA-Rev or equivalents),stored in VOC Standards Freezer in Volatiles laboratory at ≤ -10 °C.

10.4.1 A 100 ug/mL1 Initial Calibration Verification (ICV) working standard is preparedby adding 150 uL of the VOC mix and 300 uL of the Additions mix to 2550 uL ofmethanol in a 3 mL Mininert vial.

10.5 Certified Internal Standards: (ISTD Mix--2500 ug/mL, Restek--#30241 or equivalent),stored in VOC Standards Freezer in Volatiles laboratory at ≤ -10 °C.10.5.1 An 80 ug/mL ISTD working standard is prepared by adding 320 of the ISTD mix

to a 10 ml volumetric flask and brought to volume with methanol.

10.6 Certified Surrogate Standards: (SSTD Mix, Restek--#30240; 1,2-DCA-d4 Ultra Scientific--#STS210, or equivalents2), stored in VOC Standards Freezer in Volatiles laboratory at ≤-10 °C.

10.6.1 A 100 ug/mL SSTD working standard is prepared by adding 120 uL of the SSTDmix and 150 uL of 1,2-DCA-d4 to 2730 mL of methanol in a 3 mL mininert vial.

10.6.2 An 80 ug/mL ISTD/SSTD working standard is prepared by adding 320 uL of theISTD Mix (sec. 10.5), 320 uL of the SSTD Mix (sec. 10.6), and 400 uL of 1,2-DCA-d4 (sec. 10.6) to a 10 mL volumetric flask and brought to volume withmethanol.

10.7 Certified Tuning Standard: 4- bromofluorobenzene {BFB} (Ultra Scientific—2000 ug/mL,#STS-110N or equivalent), stored in VOC Standards Freezer in Volatiles laboratory at ≤ -10 °C.


7

10.7.1 A 50 ug/mL working standard is prepared by adding 75 uL of the Certifiedstandard to 2925 mL of methanol in a 3 mL mininert vial.

10.8 Sodium bisulfate (JT Baker--#3534-01 or equivalent), stored in cabinet in Volatileslaboratory.

10.9 All certified stock standards use the expiration date provided by themanufacturer/supplier. The subsequent working standards expire one week afterpreparation. When standards used for calibration are prepared from freshly open stockstandard vials, the expiration of working standards used from that point on can beextended. They can be extended if the integrity of those standards can be confirmed anddocumented. For example, if an ISTD/SSTD or a CCV/ICV standard continues toproduce acceptable results after one week from preparation, it can be assumed still valid.The integrity of the stock standards (once opened) must also be confirmed anddocumented; otherwise it also expires in one week.

1 Due to lower response or purging efficiencies, a number of compounds are purchased and prepared atconcentrations greater than 100 ug/mL . Those compounds and concentrations are noted on the calibrationcurve.2 This compound is needed for Method 524.2 and is not used for this method.

11.0 Sample Preservation and Storage

11.1 Water samples are stored at 4° C (+/- 2°). The sample storage area must be free oforganic solvent vapors and direct or intense light. Samples are stored in the Volatiles labin a double door refrigerator (separate from analytical standards).

11.1.1 Analyze properly preserved samples (pH <2) samples within 14 days ofcollection. Samples not analyzed within this period must be discarded andrecollected. If samples are not preserved then they must be analyzed within 7days.

11.1.2 Samples analyzed for Acrolein and Acrylonitrile should be preserved at a ph of 4-5 and analyzed within 14 days (3 days if unpreserved).

11.1.3 If reactive compounds such as 2-Chloroethyl vinyl ether are target compoundsthan no preservatives are added and the sample should be analyzed as soon aspossible.

11.1.4 Samples containing residual chlorine require alternative preservation (ascorbicacid or sodium thiosulfate) to reduce the chlorine. These sample should beanalyzed within 7 days unless they were reduced to a pH of <2 (using HCL orNaHSO4), then 14 day is the hold time.

11.2 Soil samples are stored at 4° C (+/- 2°). The sample storage area must be free of organicsolvent vapors and direct or intense light Samples are stored in a double doorrefrigerator located in the laboratory warehouse.

11.2.1 Samples received for low level analysis in Encore samplers must be preservedwithin 48 hours from time of collection. To preserve a sample, weigh it into a 40mL VOA vial, record the weight, then add 0.2 grams of sodium bisulfate per 1.0gram of sample. Finally add 5.0 mL of DI H2O. Analyze all samples within 14days of collection. Samples not analyzed within this period must be discarded


8

and recollected.

11.2.2 Samples received in filled 2 oz. or 4 oz. jars can be weighed and prepared forlow level analysis as described in section 11.2.1. or they can be weighed into aVOA vial and preserved at a 1:1 ratio with methanol for medium/high- levelanalysis. Analyze all samples within 14 days of collection. Samples notanalyzed within this period must be discarded and recollected.

11.2.3 Samples collected and preserved with methanol in the field in preweighed 60-mljars are weighed as is. The preweighed jar weight, as well as the methanolweight (19.8 grams for 25 mL of methanol) is subtracted from the total weight ofthe jar to determine sample weight. If the weight to volume ratio is more than 1:1then methanol is added using the auto pippetter to correct the ratio to 1:1. Unlessinstructed by the client to do otherwise, the maximum acceptable weight forvolume correction is 35 grams. If samples are being analyzed for the WisconsinLUST program then the hold time is 21 days from collection. Otherwise hold timeshould be considered 14 days.

11.2.4 All soil sample are weighed on the top loading balance which is connected to acomputer so that all weights can be automatically entered onto an Excel spreadsheet. The Excel spreadsheet is set up to record the weights as well as calculatethe methanol to weight adjustments. The spreadsheets are saved so the data canbe transferred electronically to the LIMS system.

11.3 Most samples received are accompanied with a Trip Blank (TB), In most cases the TBsare prepared by the lab and are sent along with the vials used for sample collection. Theintent of the trip blank is to accompany the sample vials through all collection,preservation, shipping, and storage procedures. The infusion of outside contamination inthe trip blank is not common, but can be an indicator of incorrect preparation/samplingprocedures or inadequate sample storage.

12.0 Quality Control

12.1 This SOP is designed to follow a variety of different projects and programs requirements.Table 2. is designed to illustrate the control steps and provisions required to adequatelyproducing acceptable data.


9

13.0 Calibration and Standardization

13.1 To facilitate appropriate separation and provide adequate sensitivity, the entire operatingsystem must be correctly set up and maintained before calibration and analyses canoccur. Proper settings and programming of the GC/MS volatile system greatly increasethe likelihood that calibrations will be acceptable. Generating and reproducing results willalso be affected favorably in a well-maintained system.

13.1.1 The following tables provide instrument settings for the daily use of theArchon/Tekmar Purge and Trap Systems. Any modifications are noted in thespecific instrument’s maintenance log:

PARAMETER SETTINGS FOR TEKMAR2000/3000

Standby 30° C

Preheat 40° C (low level soils only)

Purge 11.00 minutes

Dry Purge 2.0 minutes

Desorb Preheat 245° C

Desorb 2.00 minutes at 250° C

Bake 12.00 minutes at 260 ° C

Auto Drain Off

Valve 150 ° C

Line 150 ° C

Mount

Gas

Flow

40 ° C

Helium

35 ml/minute

13.1.2 An example of the GC temperature program for the SPB-624 column used forthe analysis of samples is as follows:

Start temp °C

End temp °C

Rate °C/minute

Timeminutes


10

32

32

155

32

155

200

0.0

5.0

15.0

3.0

0.00

0.00

13.1.3 The injector is a split/splitless injector operated in split mode ranging from 1:10 to 1:60. The injector temperature is 200 °C.

13.1.4 The MS detector parameters are subject to change to achieve optimumchromatography. See instrument maintenance logbook for recent changesregarding source maintenance, as well as filament and multiplier replacements.Current tune values and EM voltage settings are documented and can be found inthe appropriate instrument’s tuning logbook.

13.1.5 4-Bromofluorobenzene (BFB) Standard - A standard solution containing 50ug/mL is used for the daily tune check. The BFB is directly injected onto thecolumn in 25 to 50 ng injections (0.5 to 1.0 uL).

13.1.5.1 The GC/MS system tune must be verified at the beginning of anycalibration or a sequence run and verified every 12 hours thereafter. The tuning compound is BFB which is injected directly onto the GCcolumn The software is set up to check the tune by using the mean ofthree scans across the apex. Background subtraction is performed usinga single scan no more than 20 scans prior to the elution of BFB. Manualscans can be checked by taking an average of scans across the BFBpeak. The tuning acceptance criteria are listed below (m/z range 35-260):

Mass (m/z) Abundance criteria

50759596

173174175176177

15 to 40% of mass 95.30 to 60% of mass 95.Base Peak, 100% Relative Abundance5 to 9% of mass 95.<2% of mass 174.>50% of mass 95.5 to 9% of mass 174.>95% but <101% of mass 174.5 to 9% of mass 176.

13.1.6 The preparation of working standards is routinely performed each week unlessintegrity is shown to be intact. All standards are assigned a unique identification


11

number and preparations are documented in a Standards Logbook.

13.1.6.1 Calibration Standards - Calibration standards are prepared at a minimumof five concentration levels (in most instances, seven levels are currentlyused) and are prepared from the working standard dilutions of stockstandards. One of the concentration levels should be at a concentrationnear, but above, the detection limit and at or below the reporting limit. The remaining concentration levels should correspond to the expectedrange of concentrations found in real samples and should contain eachanalyte for detection by this method. For low-level soil calibrations,sodium bisulfate is added at a 0.2 g/1.0 g sample to the water to matchsample matrix /acidity if the samples were collected and preserved withsodium bisulfate. Med/high-level soil calibrations have MeOH added at a0.1 ml /5.0 ml H2O to match sample matrix/preservation. All finalconcentrations are brought to volume with DI water. The following tablesoutline the preparation of a seven level calibration curve for water andsoil samples (all calibration standards are transferred into 40 mL VOAvials for placement on the autosampler):

1) Waters Curve (5.0 mL Purge)

Concentration (ug/L)

Amount added of the 100ug/mL CCV and SSTD (inuL)

Final Volume (mL) (Volumetric flask)

1.0 2.0 5.0 10.0 20.0 30.0 40.0

1.0 2.0 5.0 10.0 20.0 30.0 40.0

100 100 100 100 100 100 100


12

2)Waters Curve (25.0 mL Purge)

Concentration (ug/L)

Amount added of the 100ug/mL CCV and SSTD (inuL)


0.2 0.4 1.0 2.0 4.0 6.0 8.0

1.0 2.0 1.0 2.0 4.0 6.0 8.0

500 500 100 100 100 100 100

3) Low Level Soils Curve

Concentration (mg/kg)

Amount added ofthe 100 ug/mL CCV and SSTD(in uL)

Grams of sodiumbisulfate added (ifneeded)


0.001 0.002 0.005 0.010 0.020 0.030 0.040

1.0 2.0 5.0 10.0 20.0 30.0 40.0

1.0 1.0 1.0 1.0 1.0 1.0 1.0

100 100 100 100 100 100 100

4) Medium/High Soils Curve


13

Concentration (mg/kg)

Amount added ofthe 100 ug/mL CCV and SSTD(in uL)

uL of MeOH added


0.050 0.100 0.250 0.500 1.000 1.500 2.000

1.0 2.0 5.0 10.0 20.0 30.0 40.0

998 996 990 980 960 940 920

100 100 100 100 100 100 100

13.1.6.2 Internal Standards - The internal standards used are Chlorobenzene-d5,1,4-Difluorobenzene, 1,2-Dichloroethane-d4 and Fluorobenzene. Othercompounds may be used as internal standards as long as they haveretention times similar to the compounds being detected by GC/MS. TheArchon autosampler automatically adds approximately 1 uL of the 80ug/mL-working standard (exact amounts are determined and recorded inthe maintenance logbook) to each sample/standard purged.

13.1.6.3 Surrogate Standards - The surrogate standards used are Toluene-d8, 1,2-Dichloroethane-d4, 4-Bromofluorobenzene, and Dibromofluoromethane. Other compounds may be used as surrogates, depending upon theanalysis requirements. The 100 ug/mL-working standard is used forcalibration and is added at the same concentrations as the targetcompounds (see above).

13.1.6.4 ISTD/SSTD Combined Standard - A combination of internal standardand surrogate standard at 80 ug/mL is automatically added by theautosampler to all samples, blanks, CCVs and spikes used for any givensequence after calibration. Limits are generated internally orproject/program limits are used.

13.1.6.5 Calibration curves are prepared fresh from newly made working

standards to ensure accurate concentrations are maintained.

13.1.6.6 Secondary dilution standards (when necessary) - secondary dilutionstandards containing the compounds of interest (usually at 10.0/100ug/mL) for low level and MDL analyses should be prepared in methanoland must be stored with minimal headspace and should be checkedfrequently for degradation. They should be stored for one week only.

13.1.6.7 Preparation of standards is documented in the Volatile standardslogbook. Each standard solution is documented with the standard name,concentration, preparation date, expiration date and a unique numbergiven to that standard for future traceability.


14

13.2 The curve is generated using the relative response factor (RRF or RF). The data systemtabulates the area response of the characteristic ions against the concentration of eachcompound and each internal standard. Calculate response factors for each compoundrelative to one of the internal standards. The internal standard selected for the calculationfor the RF for a compound should be the internal standard that has a retention time closestto the compound being measured. The RF is calculated by the data system as follows:

AS x CISRF = __________

AIS x CS

where:As = Area of the characteristic ion for the compound being

measured in the calibration standard.AIS = Area of the characteristic ion for the specific internal

standard.CIS = Concentration of the specific internal standard.Cs = Concentration of the compound being measured in the

calibration standard.

13.2.1 The average response factor (ARF) for all calibration levels is used whendetermining sample concentration and is calculated (along with thestandard deviation) to evaluate the linearity of the curve (SW-846 Method8000. Sec. 7.5.1).

13.3 When ARFs are not acceptable, results are sometimes calculated using linear (1st

order) regression curves and/or quadratic (2nd order) curves. Internal standardquantitation is also used when generating linear and non-linear calibrations. Allequations and acceptance critria follow the examples in SW-846, Method 8000 (sec.7.5.2 and sec. 7.5.3).

13.4 A system performance check should be made before the calibration curve is used. Five compounds (the System Performance Check Compounds, or SPCCs) are usedfor system performance check. These compounds are used to check compoundinstability and check for degradation caused by contaminated lines or active sites inthe system. Examples of these occurrences are as follows (Method 8260B sec.7.3.5):

Minimum RF Comment

Chloromethane >0.10 This compound is the most likely compound to belost if the purge flow is too fast.

Bromoform>0.10

This compound is one of the compounds most likelyto purge poorly if the purge flow is too slow. Coldspots and/or active sites in the transfer lines may


15

adversely affect response. Response of thequantitation ion (m/z 173) is directly affected by thetuning of BFB at ions m/z 174/176. Increasing them/z 174/176 ratio relative to m/z 95 may improvebromoform response.

Chlorobenzene >0.30

1,1,2,2Tetrachloroethane

>0.30 The response of this compound is degraded bycontaminated transfer lines in purge and trapsystems and/or active sites in trapping materials.

1,1 Dichloroethane >0.10 The response of this compound is also degraded bycontaminated transfer lines in purge and trapsystems and/or active sites in trapping materials.

13.5 The RSD for the RFs for each individual calibration check compound (CCC) must be lessthan 30%. For the calibration to be valid, this criterion must be met for each CCCcompound even if it is not a target compound for the project of concern or for the samplesbeing analyzed. The CCC compounds are Vinyl chloride, 1,1-Dichloroethene, Chloroform,1,2-Dichloropropane, Toluene, and Ethylbenzene. If the RSD of any CCC is greater than30%, then corrective action must be taken and the system re-calibrated.

13.5.1 If the RSD of the RFs is less than 15%, then the RF is assumed to be constantover the calibration range, and the average response factor may be used forquantitation. If the RSD of any analyte or surrogate mean RF exceeds 15% but isless that 30% than linear regression or second order curves may be used forquantitation. If the RSD of the RFs is greater than 30%, either analyze additionalaliquots of appropriate calibration solutions to obtain an acceptable RSD of RFsover the entire concentration range, or take action to improve GC/MSperformance. Surrogate compounds are present at the same concentration onevery sample, CCV, LCS, MS, MSD and all types of blanks.

13.6 All calibrations are confirmed by the analysis of a “second source” Initial CalibrationVerification (ICV) standard before daily checks and analyses are performed. The criteriafor the SPCCs is the same as stated above (sec.13.3), but the CCCs must be ≤ 20 %RSD. If these criteria are not met and a reanalysis of the ICV confirms thenonconformities, then corrective actions must be taken and the instrument recalibrated.The RSD limit for all other target compounds is also 20%. Any outliers suggest a problemand poor performers should be addressed. The concentrations of the ICV should be nearthe mid point of the curve (10/100 ug/L for water-5 mL purge, 2.0/20 ug/L for water-25mL purge, 0.010/0.10 mg/kg for low level soils, and 0.50/5.0 mg/kg for MeOH preservedsoils). The preparation of ICVs are as follows:

Water (5 mL purge)--Spike 50 mL of DI water(volumetric flask) with 5.0uL of the 100/1000 ug/mL ICV standard, invert three times and transfer to aVOA vial for analysis.

Water (25 mL purge)-- Spike 50 mL of DI water(volumetric flask) with 1.0uL of the 100/1000 ug/mL ICV standard, invert three times and transfer intoa VOA vial for analysis.

Low-level Soils--Spike 50 mL of DI water(volumetric flask) with 5.0 uL of


16

the 100/1000 ug/mL ICV standard, invert three times and transfer 5.0 ml intoa VOA vial (containing and a stir bar) for analysis. As an alternative,prepare a 10.0/100 ug/mL working standard, then add 5.0 uL of this to 5.0mL of DI water and transfer into a VOA (containing and a stir bar) foranalysis.

Med/high-level soils-- Spike 49 mL of DI water (volumetric flask) with 1.0mL of MeOH and 5.0 uL of the 100/1000 ug/mL ICV standard, invert threetimes and transfer into a VOA vial for analysis.

13.6 Finally an Initial Calibration Blank (ICB) is analyzed to confirm that the instrument is freefrom contamination. Any detects in the ICB should be less than the method detection limitand/or less than ½ the program/project limits. Any detects above MDL or program limitsmust be addressed before sample analyses begins. To prepare an ICB fill a 40 mL VOAvial preserved with 5% HCL with DI water.

13.7 Demonstration and documentation of an acceptable initial calibration is required before anysamples are analyzed. Refer to EPA SW-846, Method 8000B, Section 7, for a detaileddiscussion of calibration procedures.

14.0 Procedure

14.1 Prior to sample anlaysis a GC/MS tune and calibration check must made. Verify the MStune and initial calibration at the beginning of each 12-hour work shift during whichanalyses are performed.

14.1.1 Introduce into the GC (by direct injection) 25 to 50 ng of BFB and acquire amass spectrum that includes data for m/z 35-260. If the spectrum does not meetall criteria, the MS must be retuned and adjusted to meet all criteria beforeproceeding with the continuing calibration check.

14.1.2 The calibration curve integrity for each analyte must be confirmed with the use ofa CCV standard once every 12 hours of analysis time. The calibration checkverification standard should be at concentrations near the midpoint of thecalibration curves (10/100 ug/L for water-5 mL purge, 2.0/20 ug/L for water-25mL purge, 0.010/0.10 mg/kg for low level soils, and 0.50/5.0 mg/kg for MeOHpreserved soils). The CCV is placed on the autosampler in the same manner asthe samples (sec. 14.2.3). The SPCC and CCC criteria must be met before thecalibration is considered still valid. Preparation of CCVs is as follows:

Water (5 mL purge)--Spike 50 mL of DI water(volumetric flask) with 5.0uL of the 100/1000 ug/mL CCV standard, invert three times and transfer to aVOA vial for analysis.

Water (25 mL purge)-- Spike 50 mL of DI water(volumetric flask) with 1.0uL of the 100/1000 ug/mL CCV standard, invert three times and transfer intoa VOA vial for analysis.

Low-level Soils--Spike 50 mL of DI water(volumetric flask) with 5.0 uL ofthe 100/1000 ug/mL CCV standard, invert three times and transfer 5.0 ml into


17

a VOA vial (containing and a stir bar) for analysis. As an alternative,prepare a 10.0/100 ug/mL working standard, then add 5.0 uL of this to 5.0mL of DI water and transfer into a VOA vial (containing and a stir bar) foranalysis.

Med/high-level soils-- Spike 49 mL of DI water (volumetric flask) with 1.0mL of MeOH and 5.0 uL of the 100/1000 ug/mL CCV standard, invert threetimes and transfer into a VOA vial for analysis.

14.1.2.1 System Performance Check Compounds (SPCCs) - A systemperformance check must be made each 12 hour shift. If the SPCCcriteria are met, a comparison of response factors is made for allcompounds. This is the same check that is applied during the initialcalibration (sec. 13.3). If the minimum response factors are not met,the system must be evaluated, and corrective action must be takenbefore sample analysis begins. Some possible problems are standardmixture degradation, injection port inlet contamination, contamination atthe front end of the analytical column and active sites in the column orchromatographic system.

14.1.2.2 Calibration Check Compounds (CCCs) - After the system performancecheck is met, CCCs are used to check the validity of the initialcalibration. If the percent difference for any compound is greater than20%, the laboratory should consider this a warning limit (SMFs need tobe checked, as well as program/project criteria met before analysiscontinues). If the percent deviation for each CCC is less than 20%, theinitial calibration is assumed to be valid. If the criterion is not met (>20% D.) for any one CCC, corrective action must be taken. Problemssimilar to those listed under SPCCs could affect this criterion. If nosource of the problem can be determined after corrective action hasbeen taken, a new calibration must be generated. This criterion mustbe met before quantitative sample analysis begins. If the CCCs are notrequired analytes by the permit, then all required analytes must meetthe 20% difference criteria.

14.1.2.3 The internal standard responses and retention times in the CCVstandard must be evaluated immediately after or during data acquisition. If the retention time for any internal standard changes by more than 30seconds from the last check calibration (12 hours), the chromatographicsystem must be inspected for malfunctions and corrections must bemade, as required. If the EICP area for any of the internal standardschanges by a more than a factor of two (-50% to +100%), whencompared to the average from the calibration, then the massspectrometer must be inspected for malfunctions and corrections mustbe made. Reanalysis of CCVs and associated samples while thesystem was malfunctioning is necessary.

14.2 Sample Introduction and Purging

14.2.1 BFB tuning criteria and daily GC/MS calibration criteria must be met beforeanalyzing samples. Currently 18-19 purged samples including QC can be analyzed


18

within 12 hours of the BFB injection. The Archon autosampler can beprogrammed to accommodate the number of samples needed per analytical shift.

14.2.2 After the continuing calibration is verified, the system must be proven to be freeof contamination by analyzing a Method Blank (MB). The MB should not containdetects above the detection limits for any given compound. Some programs allowdetects up to but not exceeding one half the Method Reporting Limits (MRLs). Ifthe method blank contains detects above the detection limits or MRLs, thencorrective actions must be performed to ensure the system is free fromcontamination; all affected samples should also be reanalyzed. The MBs are alsoplaced on the autosampler in the same manner as the samples (sec. 14.2.3).

14.2.3 Analysis of samples begins by allowing the sample to come to ambienttemperature prior to analysis. The VOA vials containing the water samples areplaced on the autosampler where a 5.0 to 25.0 mL aliquot is withdrawn from thevial and added into the appropriate purge vessel. The same procedure is followedfor methanol preserved soils (1.0 mL of soil extract/50.0 mL DI H2O is preparedand added into a 40 ml VOA vial prior to adding the samples to the autosampler).Low level soils are prepared by adding the VOA vial containing a magnetic stirbar and ≈5 g sample/5.0 mL DI H2O to the autosampler (2-5 grams of samplerequired for low-level analysis). The autosampler then adds an additional 5.0-mLof H2O containing the ISTD/SSTD mixture. The sample is heated to 40°C andpurged in the VOA vial while being stirred, and the volatiles are collected onto thetrap.

14.2.3.1 The ISTD/SSTD is added automatically by the Archon autosampler asthe sample is transferred from the 40 mL sample vial to the spargetube; the exception is for low level soils as noted above (sec.14.2.3).

14.2.3.2 The sample is purged for 11 minutes at ambient temperature (40°C forlow-level soils) using helium with a flow of 35 mL/min at a 20 psi purgepressure.

14.2.3.3 During the 11-minute purge time, the purgeable volatile organics areadsorbed onto the Supelco Carbosieve K trap.

14.2.3.4 During desorbtion the trapped materials are rapidly heated while back-flushing the trap with helium at 35 mL/min. for 2 minutes at 250°C andintroduced in the GC/MS. After the valve to the GC is closed the trap isthen baked and back flushed with helium for ≈12 minutes at 260°C.

14.2.3.5 The GC is temperature programmed at 32°C for 3 minutes, thenramped to 155°C at 5°C/min, and finally ramped to 200°C at 15°C/min. The column flow is set at 1 mL/min. constant flow using helium as thecarrier gas.

14.2.3.6 The transfer line to the MS is maintained at 250°C and the ion source ismaintained at ≈260°C while under constant vacuum. The GC injectoris set at 200°C.

14.2.4 For each sample batch a matrix spike (MS), matrix spike duplicate (MSD), andlaboratory control spike (LCS) is prepared and analyzed. The concentrations forwater spikes are 10.0/100 ug/L for 5 mL purge and 2.0/20.0 ug/L for 25 mLpurge. The spiked concentrations for soil samples are ≈0.010/0.10 mg/kg for low


19

level and ≈0.50/5.0 mg/kg for MeOH preserved depending on sample weightsand percent solids. One exception is for the analysis of field collected MeOHpreserved soils. These samples are analyzed with a laboratory control spike anda laboratory control spike duplicate (LCSD). All spikes are transferred into 40mL VOA vials and added to the autosampler.

14.2.4.1 The preparation of the matrix spikes is performed as follows:

Water (5 mL purge)--Spike 40 mL of sample with 4.0 uL of the100/1000 ug/mL ICV standard, invert three times and transfer to a VOAvial for analysis. When adequate sample amounts are not provided, one40 mL aliquot of sample is spiked and split into two separate VOA vialscontaining 15 mL glass inserts.

Water (25 mL purge)-- Spike 50 mL of sample with 1.0 uL of the100/1000 ug/mL ICV standard, invert three times and transfer into aVOA vial for analysis.

Low-level Soils--Spike 50 mL of DI water(volumetric flask) with 5.0 uLof the 100/100 ug/mL ICV standard, invert three times and transfer 5.0mL into a VOA vial containing ≈5 g of sample and a stir bar for analysis. As an alternative, prepare a 10.0/100 ug/mL working standard, then add5.0 uL of this to 5.0 mL of DI water and transfer into a VOA vialcontaining ≈5 g of sample and a stir bar for analysis.

Med/high-level soils--Spike ≈10 g of sample contained in a VOA vialwith 50.0 uL of the 100/1000 ug/mL ICV standard. Add 9.95 mL ofmethanol to the spiked sample and sonicate for 20 minutes. Add 1.0 mLof methanol extract to 49.0 mL DI water in a 50 mL syringe and thentransfer into a VOA vial for analysis.

14.2.4.2 The preparation of laboratory control spikes is performed as follows:


Water (25 mL purge)-- Spike 50 mL of DI water (volumetric flask) with1.0 uL of the 100/1000 ug/mL ICV standard, invert three times and transferinto a VOA vial for analysis.

Low-level Soils--Spike 50 mL of DI water(volumetric flask) with 5.0 uL ofthe 100/1000 ug/mL ICV standard, invert three times and transfer 5.0 ml intoa VOA vial containing 5 g of control and a stir bar for analysis. As analternative, prepare a 10.0/100 ug/mL working standard, then add 5.0 uL ofthis to 5.0 mL of DI water and transfer into a VOA vial containing 5 g ofcontrol sand and a stir bar for analysis.

Med/high-level soils--Spike 10 g of control sand contained in a VOA vialwith 50.0 uL of the 100/1000 ug/mL ICV standard. Add 9.95 mL ofmethanol to the spiked sand and sonicate for 20 minutes. Add 1.0 mL ofmethanol extract to 49.0 mL DI water in a 50 mL syringe and then transferinto a VOA vial for analysis.


20

14.2.5 The data is collected by the Chemstation software using the response factors (orlinear/second order regressions when necessary), and results are calculated usingthe internal standard method of quantitation. Response factors for each detectedcompound are compared with that obtained in calibration, and based on thosecomparisons, results are generated. Software manuals define the procedures forcreating and understanding a specific method (Understanding Your Chemstation,Hewlett Packard, G2070-90100, October, 1994, Environmental Forms Software,Hewlett Packard, G1032-90021, November, 1992, and Productivity EnhancementSoftware for HP Chemstation, Prolab Resources Inc., XMS01A-002, Rev. G,2001).

15.0 Calculations

15.1 Using the following equations, the Chemstation software (used with the GC/MS system)calculates the concentration of target analytes:

Waters AX x IIS

Initial concentration (µg/L) = __________ AIS x RF

Where:AX = Area of characteristic ion for compound being measured in the sample.IIS = Amount of internal standard injected (ug/L). Typical concentrations

used are 20.0 ug/L for 5.0 mL purge, and 4.0 ug/L for 25.0 ml purgeAIS= Area of characteristic ion for the internal standard.RF = Response factor for compound being measured.

Soils AX x IIS

Initial concentration (mg/kg) = __________ AIS x RF

Where:AX = Area of characteristic ion for compound being measured in the sample.IIS = Amount of internal standard injected (mg/kg). Typical concentrations used

are 0.020 mg/kg for low-level soils and 1.0 mg/kg for med/high-level soils.AIS= Area of characteristic ion for the internal standard.RF = Response factor for compound being measured.

15.2 The initial concentration results are then transferred to the laboratory’s LIMS systemwhere the final concentrations are calculated.

15.2.1 The final concentration for water samples is calculated as follows:

Final concentration (ug/L) = Initial concentration x DF

Where:DF = Dilution Factor

15.2.2 The final concentrations for low-level and med/high-level soils are calculated bythe following equation:


21

Initial concentration x Sample volume x DFFinal concentration (mg/Kg) = ___________________________________

Sample weight x Percent solids

Where: Sample volume = 5.0 mL for low-level soils, or volume of MeOH

used for med/high-level soils preservation.

Sample weight = grams of sample place in VOA vial for low- level soils, or total grams of sample preserved for med/high-level soils.

Percent solids = fraction equivalent (e.g. 97.1 % = 0.971)

DF = Dilution factor (applicable for MeOH preserved soils).

15.3 The spike percent recoveries (%R) and relative percent differences (RPD) are calculatedin LIMS as follows:

Water--concentration (conc.) of spike added =

mL of spike added x conc. spiking std.. ug/L = _________________________________ x 100 mL of sample (or DI H2O) spiked

Soil--concentration of spike added =

mL of spike added x conc.spiking std.. mg/kg = __________________________________

grams of sample (or control sand) spiked.

(conc. spike + conc. sample – conc. sample) MS/MSD %R = _______________________________________ x 100 conc. spike added

[conc. MS – conc. MSD]MS/MSD RPD = __________________________ x 100

({conc. MS + conc. MSD}/2)

conc. spikeLCS % R = _________________ x 100 conc. spike added

Notes:--Concentrations (conc.) of samples, MS/MSD, and LCS spikes are obtained directly from calibration curve.--Soil spike concentrations and recoveries are calculated on a dry weight basis.--[ ] Signifies absolute values.


22

16.0 Method Performance

16.1 Certified standard solutions, properly maintained instrumentation, and analyst experienceand expertise are critical elements in producing accurate results. Standards andinstrument performance are continually checked by analyzing external performance testsamples provided by the appropriately accredited agencies. Internal blind spikes are alsoutilized to check analyst performance.

16.2 Initial demonstration of capability (IDC) is another technique used to ensure acceptablemethod performance. An analyst must demonstrate initial precision and accuracy throughthe analysis of 4-5 laboratory control spikes for each matrix and sample type. Afteranalysis, the analyst calculates the average recovery (x) in µg/L and the relative standarddeviation (RSD) of the recoveries for each analyte. In the absence of specific criteriafound in the SW-846 methods or project specific limits, the default criteria of 70-130%recovery and 20 % RSD are used until internal limits are generated (Method 8000B, sec.8.4.9).

16.2.1 Examples of the preparation of IDCs are as follows:


Water (25 mL purge)-- Spike 50 mL of DI water(volumetric flask) with 1.0uL of the 100/1000 ug/mL ICV standard, invert three times and transfer intoa VOA vial for analysis.

Low-level Soils--Spike 50 mL of DI water(volumetric flask) with 5.0 uL ofthe 100/1000 ug/mL ICV standard, invert three times and transfer 5.0 ml intoa VOA vial containing 5 g of control and a stir bar for analysis. As analternative, prepare a 10.0/100 ug/mL working standard, then add 5.0 uL ofthis to 5.0 mL of DI water and transfer into a VOA vial containing 5 g ofcontrol sand and a stir bar for analysis.

Med/high-level soils--Spike 10 g of control sand contained in a VOA vialwith 50.0 uL of the 100/1000 ug/mL ICV standard. Add 9.95 mL ofmethanol to the spiked sand and sonicate for 20 minutes. Add 1.0 mL ofmethanol extract to 49.0 mL DI water in a 50 mL syringe and then transferinto a VOA vial for analysis.

16.3 Many program (i.e. USACOE) require the analysis of method reporting limit (MRL)standards and method detection limit (MDL) check samples as another means ofchecking method performance. The MRLs are analyzed at the beginning and end of each12 hour shift and are typically prepared at concentrations equal to the lowest standard onthe calibration curve. Recovery limits are program specific but are usually set at 70-130%. The MDL check sample is usually spiked at approximately 2x the methoddetection limit. The MDL check sample is analyzed quarterly (as a minimum) to confirminstrument sensitivity (e.g. to verify that the method detection limits are still achievable).The MDL check samples are taken through all preparation and extraction steps used foractual samples (e.g. spiking/preserving control sand for soil samples). In most instances,a method detection limit check sample is analyzed at the end of each sequence requiring


23

an MRL standard. The recovery criteria for MDL check samples is the ability to detect all compounds. If any given compound is not detected, the MDL check is spiked at ahigher level and analyzed again. Detection limits for those compounds not detected on theinitial MDL check analysis need to be raised to match the MDL check analysis at whichthey were detected.

16.4 Creating and monitoring control charts is also important for maintaining and improvingmethod performance. Currently all SSTD, MS, MSD, and LCS recoveries are monitoredwith the use of the LIMS system. The data collected is used to recognize trends inrecovery performance, as well as for generating new in-house QC limits. Defaultaccuracy limits of 70-130 % recovery and a precision limit 20 % RSD are used untilenough data points are generated to provide usable internal limits. Other programs such asthe Shell Document for the USACOE use default LCS limits of 80-120 % recovery forwater samples and 75-125 % for soil samples (SMF 60-140%). The Shell also usesdefault MS/MSD recovery limits for water and soils of 70-130% (SMF 60-140 %), anddefault precision limits of 30% for water samples (SMF 40%, no RPD limits for soils).The WI UST program uses default accuracy and precision limits for surrogates andspikes of 80-120/20 %. Client and/or Project specific limits are also used frequently insample analyses. The Quality Control Requirements chart (Table 2.) also lists recoverylimits specific to the method/project/program.

17.0 Data Assessment & Acceptance Criteria for QC Measures

17.1 If the initial analysis of a sample or a dilution of the sample has a concentration of anparticular analyte that exceeds the calibration range, the sample must be reanalyzed at adilution. Secondary ion quantitation is allowed only when there are sample interferenceswith the primary ion. When a sample is analyzed that has saturated ions from acompound, this analysis must be followed by a blank water analysis. If the blank analysisis not free of interferences, the system must be decontaminated. Sample analyses cannot resume until a blank can be analyzed that is free of interferences.

17.2 After the analyses of water samples, the pH should be taken to verify proper fieldpreservation. pH strips are used to verify the pH which is then documented in the benchsheet logbook.

17.3 Qualitative Analysis (Method 8260B, sec. 7.6)

17.3.1 The qualitative identification of compounds determined by this method is based onretention time and on comparison of the sample mass spectrum (ion scans) afterbackground correction with characteristic ions in a reference mass spectrum.The reference mass spectrum must be generated (by the laboratory) using theconditions of this method. The mass spectral library is updated with each newcalibration and is continually updated with the mass spectra from CCVs.

17.3.2 The characteristic ions from the reference mass spectrum are defined to be thethree ions of greatest relative intensity or any ions over 30% relative intensity iffewer than three such ions occur in the reference spectrum. Table 3 listscompounds along with the Primary Ion (Quantitation ion) used for calculatingresults, and the Secondary Ions (Qualitative ions) used for qualitatively matchingsample spectrums with reference spectrums for positive identifications. Compounds should be identified as present when the criteria below are met.

17.3.2.1 The intensities of the characteristic ions of a compound maximize in the


24

same scan or within one scan of each other. Selection of a peak by adata system target compound search routine where the search is basedon the presence of a target chromatographic peak containing ionsspecific for the target compound at a compound-specific retention timewill be accepted as meeting this criterion.

17.3.2.2 The relative retention time (RRT) of the sample component is within +/-0.06 RRT units of the RRT of the standard component.

17.3.2.3 The relative intensities of the characteristic ions agree within 30% of therelative intensities of these ions in the reference spectrum. (Example:For an ion with an abundance of 50% in the reference spectrum, thecorresponding abundance in a sample spectrum can range between 20%and 80%).

17.3.2.4 Structural isomers that produce very similar mass spectra should beidentified as individual isomers if they have sufficiently different GCretention times. Sufficient GC resolution is achieved if the height of thevalley between two isomer peaks is less than 25% of the sum of the twopeak heights. Otherwise, structural isomers are identified as isomericpairs.

17.3.2.5 Identification is hampered when sample components are not resolvedchromatographically and produce mass spectra containing ionscontributed by more than one analyte. When gas chromatographic peaksobviously represent more than one sample component (i.e., a broadenedpeak with shoulder(s) or a valley between two or more maxima),appropriate selection of analyte spectra and background spectra areimportant. Examination of extracted ion current profiles of appropriateions can aid in the selection of spectra and in qualitative identification ofcompounds. When analytes coelute (i.e., only one chromatographic peakis apparent), the identification criteria can be met, but each analytespectrum will contain extraneous ions contributed by the coelutingcompound.

17.3.3 For samples containing compounds that are not a part of the normal target list, alibrary search may be required for the purpose of tentative identification.Tentative identified compounds (TICs) are needed only when requested orrequired by a particular project or program. Data system library search routinesshould not use normalization routines that would misrepresent the library ofunknown spectra when compared to each other. Use the following a guidance forreporting TICs (Method 8260B, sec. 7.6.6):

1) Relative intensities of major ions in the reference spectrum (ions greaterthan 10% of the most abundant ion) should be present in the samplespectrum

2) The relative intensities of the major ions agree within ± 20%.

3) Molecular ions present in the reference spectrum should be present inthe

sample spectrum.

4) Ions present in the sample spectrum but not in the reference spectrum


25

should be checked for possible background contamination. They shouldalso be reviewed for possible coelution with another compound.

5) Ions present in the reference spectrum but not in the sample spectrumshould be check against the possibility of subtraction from the samplespectrum due to background contamination or co-eluting peaks. Somedata reduction programs can create these discrepancies.

17.4 Quantitative Analysis (Method 8260B, sec. 7.7)

17.4.1 When a compound has been identified, the quantitation of that compoundwill be based on the integrated abundance from the EICP of the primarycharacteristic ion. Quantitation is performed by the data system using theinternal standard technique. The internal standard used shall be the onenearest the retention time of that of a given analyte. Quantitation isperformed using the RF averages from the initial (i.e. 7 pt) calibration,and not the continuing calibration check (ICV).

17.5 When the analysis of an analytical batch or sequence has been completed, the data isprocessed and prepared for reporting. Once the reference spectrums are comparedand the sample spectrums and identifications have been made, the sample data can bereported. Assessments of all spiked and calibration control samples and standardsshould also be finalized before reporting the data.

17.5.1 When the analyst has finished processing the analytical batch, the results areelectronically transferred to the LIMS system where weight to volumecorrections, dilution factors and percent solids adjustments are made. Oncethe final results have been verified, a checklist (Table 4.) is filled out andsigned confirming that all the data has been thorough scrutinized. At this pointthe data is turned over to another qualified analyst for final validation. Thesecond analyst confirms the results and electronically marks them validatedand signs his or her portion of the checklist (an example of the checklist isincluded in this SOP). Finally, the validated results are made available to theclient services personnel in order for the data to be given to the client orappropriate agencies.

17.5.2 A paper hard copy of the data is then filed or archived. The package includesthe checklist, the sequence run log, a copy of the bench sheet, the LIMS runlog, verification of tuning and system performance data, and verification ofcalibration data. For each sample, the chromatogram, quantitation and libraryspectra (ion scans) for all positive target compounds are also included. All thedata is to be initialed and dated by the analyst. Each data file header shouldcontain the sample ID # and the date and time acquired.

18.0 Corrective Measures for Out-of-Control Data

18.1 When data is out of control, a number of corrective actions may need implementing. If thenonconformities involve failing QC within the analytical sequence batch, then reanalysis ofsamples may eliminate any out of control data. If the out of control data is the result ofinstrument malfunctions, then maintenance or repair of the downed instrument followed byreanalysis of affected data may correct the problem. If sample matrix affect orcontamination is the reason for poor data, the instrument may need cleaning anddecontamination, and the sample may need diluting to reduce matrix affect. In all cases,when out of control data presents itself, the appropriate corrective measures need to be


26

enacted to eliminate unusable data. The Quality Control Requirements chart can be usedas a guide as to which corrective actions should be taken for different QC-type failures ornonconformities (Table 2.).

19.0 Contingencies for Handling Out-of-Control or Unacceptable Data

19.1 Due to limited sample volume, expiration of hold times, downed instrumentation, andanalyst error, the sample data may be out of control or unacceptable to report. Sincethese potential instances can arise, contingency plans need to be in place to prevent and/or minimize their affect on data.

19.1.1 The first thing addressed is prevention of producing unacceptable data. Whenlimited sample volume is the issue, the analyst should determine if splitting thesample into lesser volumes or weights is an option. To avoid sample hold timeissues, the analyst’s first responsibility is to plan accordingly. The analyst isresponsible for budgeting enough time for sample analysis, so if a problem arisesreanalysis is an option. Loss of data due to downed or malfunctioninginstrumentation can be addressed with the use of backup instrumentation. If aninstrument becomes unusable, the samples should be analyzed on a differentinstrument system. Analyst error is prevented by second analyst confirmation andvalidation. If the initial analyst makes an analysis error or inadvertently reportsunacceptable data, the second analyst is responsible for finding and/or correctingthose errors.

19.1.2 When out of control or unacceptable data is produced and it is too late forcorrective measures, a number of actions can be taken. The first and foremost isalerting the client service personnel of the problem. Client services will inform theclient and/or responsible parties. In some instances, more sample can be madeavailable or re-sampling can occur, so it is important to alert the appropriatepersonnel as soon as possible.

19.1.2.1 If the out of control data affects only specific analytes, it is important tolet the appropriate person(s) know in case his or her site assessment isbased on a specific target analyte list.

19.1.2.2 In all instances, if results are reported from data that is out of control orunacceptable, that data should be qualified accordingly. Once the clienthas been notified and he or she instructs us to report the data, then flagthe data indicating what type of nonconformity has occurred.

19.1.2.3 Out of control data is still retained by the laboratory and filed andarchived along with acceptable data. The file folder should be labeledas such, indicating that the data is out of control.

19.1.2.4 A non-conformance/corrective action report (CAR) form must be filledout whenever these types of events occur. The information on thereport includes the problem encountered, planned corrective actions,and corrective action follow-up. The form is then discussed with andsigned by the analyst, the client representative, the QA officer, and thelaboratory manager. The purpose of the form is to document problemsin order to eliminate the possibility of repeating nonconformance and toensure that the proper corrective actions are employed.

20.0 Waste Management


27

20.1 Sample are routinely held (refrigerated) for up to six weeks from analysis date beforethey enter the waste stream. Waste disposal of samples and standards follows theprocedures documented in the Laboratory Waste Disposal SOP (Quality AssuranceSection, SOP NO. FO-8, Rev. 4).

21.0 References

21.1 USEPA, SW-846 Methods 8000B, Rev. 2, December, 199621.2 USEPA, SW_846 Method 8260B, Rev. 2, December, 199621.3 USEPA, SW-846 Methods 5030B, Rev. 2, December, 199621.4 USEPA ,SW-846 Methods 5035 (inc. App. A), Rev. 0, December, 199621.5 National Environmental Laboratory Accreditation Program

(NELAP), Quality Systems, Chapter 5, June, 200021.6 USACOE , Shell for Analytical Chemistry Requirements,

EM 200-1-3, February, 200121.7 USEPA, Method 603, Acrolein and Acrylonitrile, July, 1982


28

Table 1. Analyte List

Analyte Analyte

Acetone

BenzeneBromobenzeneBromochloromethaneBromodichloromethaneBromoformBromomethane2-Butanonen-Butylbenzenesec-Butylbenzenetert-ButylbenzeneCarbon disulfideCarbon tetrachlorideChlorobenzeneChloroethane2-Chloroethylvinyl etherChloroformChloromethane2-Chlorotoluene4-ChlorotolueneDibromochloromethane1,2-Dibromo-3-chloropropane1,2-DibromoethaneDibromomethane1,2-Dichlorobenzene1,3-Dichlorobenzene1,4-DichlorobenzeneDichlorodifluoromethane1,1-Dichloroethane1,2-Dichloroethane1,1-Dichloroethenecis-1,2-Dichloroethenetrans-1,2-Dichloroethene1,2-Dichloropropane1,3-Dichloropropane

2,2-Dichloropropane1,1-Dichloropropenecis-1,3-Dichlropropenetrans-1,3-DichloropropeneDiisopropyl etherEthylbenzeneHexachlorobutadiene2-HexanoneIsopropylbenzenep-IsopropyltolueneMethylene chloride4-Methyl-2-pentanoneMethyl tert butyl etherNaphthalenen-PropylbenzeneStyrene1,1,1,2-Tetrachloroethane1,1,2,2-TetrachloroethaneTetrachloroetheneTetrahydrofuranToluene1,2,3-Trichlorobenzene1,2,4-Trichlorobenzene1,1,1-Trichloroethane1,1,2-TrichloroethaneTrichloroetheneTrichlorofluoromethane1,2,3-Trichloropropane1,2,4-Trimethylbenzene1,3,5-TrimethylbenzeneVinyl chlorideVinyl acetateo-Xylenem/p-Xylene


29

Table 2.Volatile Organic Compounds by GC/MS

Quality Control Requirements

Quality Control Item Frequency Acceptance Criteria Corrective Action

Tune Check (BFB) Every 12 hours. Ensure correct mass assignment. BFB % Relativeabundance criteria as specified in method 8260 or useprogram/project specific criteria.

Retune. Do not proceed with analysis until tunemeets criteria.

Initial Calibration (IC) Each time the instrument is set up andwhen CCCs and SPCCs in the continuingcalibration verification (CCV) do notmeet criteria.

Established initially at minimum fiveconcentration levels (six concentrationlevels if a second order {quadratic}curve is used) - low standard at or belowproject required reporting limit (PRRL),near but above method detection limits(MDL).Heated purge for low-level soils.

1. Average relative response factors (RRFs) forSPCCs Chloromethane, 1,1-Dichloroethane, andBromoform >0.10 and for SPCCs Chlorobenzeneand 1,1,2,2-Tetrachloroethane ≥ 0.30.

2. % RSD for RRFs for each CCC ≤30%.

3. % RSD for RRFs for all target compounds ≤15%.IF RF % RSD >15% use linear curve, r =.995, r2= .990.

4. ACOE, NELAC, or other programs/agencies mayrequire different criteria than stated here. Programand/or project specific criteria should be followedas stated in their documents. ACOE maximumallowable limits for %RSD = 30%

Correct system and recalibrate. Criteria must bemet before sample analysis may begin.

Any samples reported from data not meeting thesecriteria must be qualified (Z).

Initial CalibrationVerification standards(ICV)

Every 12 hours.

Should be at or near the mid-point ofcalibration range for all targetcompounds, CCCs, SPCCs andsurrogates and should also be preparedfrom second source standards. Typicallyuse 10/100 ppb for H2O and Low LevelSoils, 0.5/5.0 mg/kg for MeOH preservedsoils. ICVs analyzed for compoundsusing second order (quadratic) curvesneed to be analyzed at levels above andbelow the inflection point.

Heated purges for low-level soils.

1. RRF for SPCCs Chloromethane, 1, 1-Dichloroethane, and Bromoform >0.10 and forSPCCs Chlorobenzene and 1,1,2,2-Tetrachloroethane ≥0.30.

2. % Deviation. for RRFs of each CCC <20%.

3. Non-CCCs - <20% Deviation for RRFs, <20 %Drift for linear curve and non linear curves-Sporadic marginal failure of up to 10 % of targetcompounds = 40% RSD.

4. ACOE, NELAC, or other programs/agencies mayrequire different criteria than stated here. Programand/or project specific criteria should be followedas stated in their documents.


IF % relative standard deviation (RSD) >20%,then system must be inspected and problemcorrected before sample analysis.

If >20% RSD then confirm the integrity of thesecond source standard by reanalysis, and/ordetermine if it’s a sporadic problem involvingcompounds that are typically poor performers.

ACOE allows no tolerances for % D. Problemcompounds need to be addressed on a project toproject basis.


30

Continuing CalibrationVerificationstandards(CCV)

Every 12 hours.

Should be at or near the mid-point ofcalibration range for all targetcompounds, CCCs, SPCCs andsurrogates and is prepared fromstandards used for calibration. Typicallyuse 10/100 ppb for H2O and Low LevelSoils, 0.5/5.0 mg/kg for MeOH preservedsoils.

Heated purges for low-level soils..

1. RRF for SPCCs Chloromethane, 1, 1-Dichloroethane, and Bromoform >0.10 and forSPCCs Chlorobenzene and 1,1,2,2-Tetrachloroethane ≥0.30.

2. % Deviation for RRFs of each CCC <20%.

3. Non-CCCs - <20% Deviation for RRFs, <20 % Driftfor linear curve and non linear curves- Sporadicmarginal failure of up to 10 % of targetcompounds = 40% RSD.

4. ACOE, NELAC, or other programs/agencies mayrequire different criteria than stated here. Programand/or project specific criteria should be follow asstated in their documents.


IF % RSD >20%, then system must be inspectedand problem corrected before sample analyses.

If >20% RSD correct problem if determinable thenreanalyze, and/or determine if it’s a sporadicproblem involving compounds that are typicallypoor performers. In any case sample results reported that have %D failures must be qualified(A).

ACOE allows no tolerance for % D. Problemcompounds need to be addressed on a project toproject basis

Internal Standards (ISTD) Added to all blanks, standards, andsamples.

1. Peak area within -50% to +100% of area inassociated CCV standard.

2. Retention time (RT) within 30 sec of RT forassociated CCV standard.

3. ACOE, NELAC, or other programs/agencies mayrequire different criteria than stated here. Programand/or project specific criteria should be follow asstated in their documents.

Inspect instrument for malfunctions; correctidentified malfunctions, then reanalyze samples. If no instrument malfunction identified proceed asfollows:* Reanalyze sample.* If reanalysis is outside limits the data should be qualified (S). Follow specified criteria as stated in Shell or otherdocumentation.

Method Blank (MB) One per medium/20 samples per matrix. The MB is used to documentcontamination resulting in the analyticalprocess and should be carried throughthe complete sample preparation andanalytical procedure.

1. Concentration of analytes of concern should beless than the highest of either :

*Method Detection Limit

*Five percent of the regulatory limit for that analyte or.

*Five percent of the measured concentration in the sample.

2. ACOE ≤ ½ MRL

3. Follow criteria according to specificprogram/agency.

Reanalyze to determine if instrument or laboratorybackground contamination was the cause. If themethod blank is still non-compliant, re-prepare andreanalyze blank and samples.*

For ACOE data if less than ½ MRL no actionrequired.*

*If reanalysis of blank still contains contaminationabove specified limits, affected data should beflagged (B).


31

Laboratory ControlSample (LCS)

One per medium/per 20 samples/matrix. Must undergo all sample preparationprocedures. Should be from a secondsource and contain target compoundswith concentrations at or near the mid-point of the calibration range.

1. % Recoveries (and RPDs, if applicable) within in-house generated limits. Default 70-130% (20% RPD). Sporadic marginal failure(SMF) of up to 10 % of target compounds = 60-140 % rec.

2. ACOE Limits: H2O 80-120 % rec., Soils- 75-125%rec. Sporadic Marginal Failures (five percent oftarget compounds) = 60-140%.

3. Use Project Specific/Client limits whenapplicable.

If LCS recoveries are within control limits or withinSMF frequency and limits then no action isrequired. If the LCS exceeds control limits, as wellas SMF criteria the reanalyze the LCS to confirmproper preparation procedure.If still exceeding limits then reanalyze associatedsamples with a new LCS..If sample data is reported with LCS failures thenthat data must be qualified (Q). Exception: If theLCS recoveries are high with no associatedpositives then no further action is taken.

Matrix Spike/Matrix SpikeDuplicate

One per set of 20 samples per matrix. Must undergo all sample preparationprocedures. Must be spiked with targetcompounds with concentrations at ornear the mid-point of the calibrationrange.

1. % Recoveries and RPDs within in-housegenerated limits. Default 70-130 / 20%RPD.

2. ACOE limits = 70-130% rec. RPD = 30% for water.No limits for soils. Sporadic Marginal Failures(five percent of target compounds) = 60-140%rec. 40% RPD for water.

3. Use Project Specific/Client limits when applicable.

If LCS is acceptable, then report probable matrixinterference.Qualify data if the recoveries are low (M) and/or ifdetects in samples are less than 25% of theamount spiked.If recoveries are high and there are no detects inthe unspiked sample then that data does notrequire flagging.Qualify data for RPD failures (Y) when there is adetect for the failing compounds (non-detectedcompounds are not qualified). Exception: If acompound is already qualified for a LCS failurethen no RPD qualifier is applied.

Qualitative/QuantitativeIssues

1. If detection level of any compound in asample exceeds the detection level ofthat compound in the highest levelstandard, the sample must be diluted toapproximately mid-level of thecalibration range and reanalyzed.

2. If the concentration of the targetanalyte (that exceeded the calibrationrange) is present in the samplefollowing the high level sample and isgreater than the RL but <5x RL, thenthat sample must be reanalyzed todetermine if carryover occurred.

1. The instrument level of all compounds must bewithin the calibration range for all samples.

2. The sample analyzed immediately after a high-level sample must display concentrations of thehigh level target compounds less than the RL orgreater than 5x RL.

Dilute the sample to bring the level of the highestconcentration of target compounds within thecalibration range. If any data is reported with anyresults over range then those results should beflagged (X).

A sample displaying concentrations of targetcompounds between the RL and 5x the RL thatwas analyzed immediately after a high-levelsample must be reanalyzed. If the results do notagree within the RL, report only the secondanalysis.


32

Surrogate 1. Calibrated as target compounds.

2. Added to all blanks, samples, and QCsamples, as a part of the internalstandard-surrogate spiking mixture.

1. All % Recoveries within in-house generated limits. Default 70-130%.

2. ACOE: Interference free matrix = 80-120% forwater, 75-125% for solids. Project sample matrix= 70-130%

3. Use Project Specific/Client limits whenapplicable.

If recoveries are not within limits:

Check to be sure that there are no errors incalculations, surrogate solutions, or internalstandards. Also, check instrument performance.If no problem is found, re-prepare and reanalyzethe sample.If the reanalysis is within limits, report only thereanalysis.If the reanalysis is still out of limits the sampleshould be qualified (S).Due to matrix affect, no reanalysis is required ifthe MS and/or MSD are outside limits.


33

Table 3.Characteristic ions

Analyte Primary Ion

SecondaryIon(s)

Analyte PrimaryIon

SecondaryIon(s)

AcetoneBenzeneBromobenzeneBromochloromethaneBromodichloromethaneBromoformBromomethane2-Butanonen-Butylbenzenesec-Butylbenzenetert-ButylbenzeneCarbon disulfideCarbon tetrachlorideChlorobenzeneChloroethane2-Chloroethylvinyl etherChloroformChloromethane2-Chlorotoluene4-ChlorotolueneDibromochloromethane1,2-Dibromo-3-chloropropane1,2-DibromoethaneDibromomethane1,2-Dichlorobenzene1,3-Dichlorobenzene1,4-DichlorobenzeneDichlorodifluoromethane1,1-Dichloroethane1,2-Dichloroethane1,1-Dichloroethenecis-1,2-Dichloroethenetrans-1,2-Dichloroethene1,2-Dichloropropane1,3-Dichloropropane

ISTD

FluorobenzeneChlorobenzene-d51,4-Dichlorobenzene-d4

43 78 156128 8317394 43 9110511976 11911264638350 91 91 129 157 107 93 146 146 146 85 63 62 96 96 96 63 76

96 117 152

58 51,77 77,158 49,130 85,129175,171 96 72,57 92,13413491,13478 12177,114 6665,1068552126 126 127,131 155 109 95,174 111,148 111,148 111,148 87 65,83 98,6461,63 61,9861,9876,112 78

77

2,2-Dichloropropane1,1-Dichloropropenecis-1,3-Dichlropropenetrans-1,3-DichloropropeneDiisopropyl etherEthylbenzeneHexachlorobutadiene2-HexanoneIsopropylbenzenep-IsopropyltolueneMethylene chloride4-Methyl-2-pentanoneMethyl tert butyl etherNaphthalenen-PropylbenzeneStyrene1,1,1,2-Tetrachloroethane1,1,2,2-TetrachloroethaneTetrachloroetheneTetrahydrofuranToluene1,2,3-Trichlorobenzene1,2,4-Trichlorobenzene1,1,1-Trichloroethane1,1,2-TrichloroethaneTrichloroetheneTrichlorofluoromethane1,2,3-Trichloropropane1,2,4-Trimethylbenzene1,3,5-TrimethylbenzeneVinyl chlorideVinyl acetateo-Xylenem/p-Xylene

SSTD

Dibromofluoromethane1,2-Dichloroethane-d4Toluene-d84-Bromofluorobenzene

77 110 75 75 45 91 225 43 105 119 84 43 73 128 91 104 131 83 166 42 92 180 180 97 83 95101 75 105 105 62 43106106

113 102 98 95

97,79 77,75 110 77,110 87,43 106223,22758,57 120 134,91 86,4958,57 57,43 51,129 120 78133,119 85 168,12972,71 91 182,145 182,145 99,6197,85,99 130,132 103,105 110 120 1206486 91 91

111,192 104 100 174,176


34

Page left Blank:


35

Table 4.

INDEPENDENT DATA REVIEW CHECKLIST Method: GCMS (EPA SW-846 8260)

Analysis Date Analyst/Data Interpreter Independent Reviewer Date or Review Approved?

Yes No

Instructions: Complete one checklist per analytical run. Enter the appropriate response for each question. Each "No" response requires anexplanation in the Comments section and may require the initiation of a Nonconformance Report.

Requirement: AcceptanceCriteria

AnalystReview


Yes No Yes No I. BFB Tune Check

BFB tune check analyzed? Relative abundancecriteria met?

II. Initial CalibrationWas initial calibration performed using aminimum of five standard concentratrion levels?

Lowest standardat or near MDL/LOD?

Were SPCC compounds acceptable? Avg. RRF> 0.1; 0.3?

Were CCC RF's less than 15% ? (Or alternatively no greater than30% if generating results using linear regression?)

Was Initial Calibration Blank analyzed?

III. Continuing Calibration Verification (CCV)Was a BFB tune check run at the beginning of every twelve hour shift?

Relative abundancecriteria met?

Was a CCV analyzed after every 12 hourtune check?

Were SPCC compounds acceptable? Avg. RRF> 0.1; 0.3?

Were CCC compounds acceptable? %D < 20%

Were all other compounds acceptable?If yes, then continue run. %D < 20%

If No, did number of failures exceed sporatic marginal failure limits? <10% failing or seeprogram limits

If yes, samples reanalyzed

Were detects for outlying compounds qualified?


36

Requirement: AcceptanceCriteria AnalystReview IndependentReview Comments:

Yes No Yes No IV. Blanks

Was method blank (MB) analyzed prior to analysis of samples? Were the MB results for all target analytes less than reporting limits(RL)? See program or client RL If not, were there any detects in the samples <20x the amount in theblank? If yes, were those detects flagged? (If detect >20x, no actionrequired.)

V. Laboratory Control Spike (LCS)Was a LCS analyzed at a frequency of one per 20 samples (orprogram specified frequency)?

Were the LCS recoveries for all analytes within acceptance criteria?Default 70-130%, or see

internally generated limits, orclient/program specified limits.

If no, were detects (and non-detects for low recoveries) qualified?

Was the LCS a second source to the initial calibration standards? VI. Laboratory Control Spike Duplicate (LCSD). This section applies only to runs without MS/MSD

Was a LCSD analyzed at a frequency of one per 20 samples (orprogram specified frequency)?

Were the LCSD recoveries for all analytes within acceptance criteria?Default 70-130%, or see

internally generated limits, orclient/program specified limits.

If no, were detects (and non-detects for low recoveries) flagged "Q"?

Is the relative percent difference (RPD) for each analyte betweenduplicate samples acceptable?

Default 20%, or see internallygenerated limits, or

client/program specified limits.

If No, were detects in samples flagged "Y"? VII. Matrix Spike/Matrix Spike Duplicate (MS/MSD)

Was a MS and a MSD analyzed at a frequency of one each per 20samples (or program specified frequency)?

Were the MS/MSD recoveries for all analytes within acceptancecriteria?

Default 70-130%, or seeinternally generated program

limits, or client specified limits.


37

Requirement: Acceptance Criteria AnalystReview IndependentReview Comments:

VII. MS/MSD continuedYes No Yes No

If No, were nondetects for analytes with low MS/MSD recoveriesand detects < 25% spiked amount flagged “M”?

Is the relative percent difference (RPD) for each analyte betweenduplicate samples acceptable?

Default 20%, or see internallygenerated limits, or client

specific limits.

If No, were detects in samples <25% spiked amount flagged “Y”?

VIII. Sample AnalysesAre chromatogram characteristics, including peak shapes and areas,consistent with those of the CCV?

Were surrogate recoveries for all samples and QC within acceptancecriteria?

Default 70-130%, or seeinternally generated program

limits, or client specified limits.

If no, was the sample reanalyzed and/or flagged "S"?

Were all samples having analytes detected in amounts exceeding thecalibration range diluted and reanalyzed? Target upper middle range of

calibration curve.

Did all samples meet hold time and preservation criteria as defined bymethod/program.

Was a sample with detects between LOD and 5x LOD reanalyzed iffollowing a sample with high level detects exceeding calibration range?

Detects are not attributed tocarryover

Were all samples and QC injected within 12 hours of BFB tunecheck?

Were internal standard recoveries acceptable relevant to associatedCCV?

Response = -50 to +200%;Ret. time = +/- 30 sec.

IX. Records and Reporting

Is sequence file / injection log present in the data package? Were all data, calculations, and values verified in LIMS uponcompletion of data capture? Were reported results with amounts exceeding acceptance criteriaflagged with appropriate qualifier and, if needed, a NCR completed? Was the integrity of the sample kept intact? If not, was a NCRcompleted?

CT Laboratories SOP NO: FO-8 Rev. 4Quality Assurance Section Page 1 of 8 2/14/03

1

CT Laboratories.Baraboo Laboratory Division

Title Laboratory Waste Disposal

SOP Number: FO-8

Prepared by: ______________________________________Date





2

Laboratory Waste Disposal

1.0 Introduction

CT Laboratories generates waste while performing the tasks normally associated with the business of testing. Allof the wastes we generate are regulated in some form or another. Wastes that can be managed by municipalservices are done so following guidelines issued by that provider. Other waste must be handled in a differentmanner by CT Laboratories personnel or their contractors. These other waste can be divided into two groups,hazardous and nonhazardous. Due to the variability of nonhazardous waste, these are not fully addressed in thisprocedure. Below are outlined procedures addressing the handling of mainly hazardous and other lab waste.

2.0 Scope

As noted in the Introduction, this procedure focuses on manageable wastes generated CT Laboratories at 1230Lange Ct., Baraboo WI. Municipal waste handling is addressed in a municipal pamphlet and is under thedirection of lab management. Hazardous waste management from CT Laboratories lab operations areaddressed below.

3.0 Definitions and Explanations

Municipal Waste -For the purposes of this procedure the term municipal waste is any waste handled by the City of Baraboo. TheGarbage Recycling Guidelines, issued by the city, identifies the wastes the city will handle. It includes recyclingpaper, plastic and glass as well as general garbage. It does not include “household hazardous wastes” or anyother program designed specifically for normal residential homeowners.

Hazardous Waste -A hazardous waste is defined two ways: either it is specifically listed or it is not listed but exhibits ahazardous characteristic. Listed hazardous waste can be found in Wisconsin Administrative Code NR605.08 or .09. Wastes not specifically listed may be hazardous if they exhibit a hazardous characteristic,such as ignitability, corrosive, reactive or EP Toxic.

Nonhazardous / Non-municipal Waste -This term is used to describe wastes that the city will not dispose of and are not hazardous by definition.Although these types of waste arise occasionally, they are not covered in this policy. These types ofwaste are the responsibility of CT Laboratories to properly dispose of. They may include such things asbuilding materials, drums and office furniture.

4.0 Procedures

4.1 Municipal waste

4.1.1. Non-hazardous waste that can be disposed of or recycled by the municipal program ishandled under the direction of the laboratory office manager. Procedures involving CTLaboratories’s municipal waste removal are referred to the office manager.

4.1.2. A current guide provided by the city of Baraboo describes their program. Every effort shouldbe made to recycle or dispose of waste through this program. The laboratory office manager


3

has a copy of the municipal program and its requirements.

4.1.3. Materials and containers that were considered hazardous and are made non-hazardous byacceptable means are allowed into this program.

4.2 Hazardous Waste

4.2.1 Reduction

The most important portion of hazardous waste management is the prevention and reduction ofwastes that would be considered hazardous. The type and amount of hazardous wastegenerated by our laboratory operations can be minimized through daily attention to thechemicals we use. Outlined below are some steps to be taken but they may not be the onlyones. Through constant awareness of this potential or real problem all employees may findadditional ways to reduce the wastes we generate.

4.2.2 If testing allows for choices in the methods or chemicals used try to select the one that generatesthe least acute, quantity or additional category of hazardous waste. Check with the supervisoror Safety Officer for assistance.

4.2.3 Purchase only the quantity of chemical that can be used within its’shelf life. Excessive quantityand outdated chemicals are both costly and may be dangerous to dispose of.

4.2.4 Containers that held hazardous chemicals are themselves considered hazardous waste if they arenot cleaned before disposal. Listed below are two methods of disposal for containers that heldchemicals, one for acutely hazardous and one for containers that did not contain acutelyhazardous chemicals. If it is unclear if the chemical that was in the container was acutelyhazardous or not then it should be treated as hazardous.

4.2.5 Containers that held hazardous waste can be disposed of with the municipal waste if they arecompletely empty and triple rinsed.

4.2.6 Containers that held non-acute chemicals can be directly disposed of if ;

4.2.6.1 no more material can be removed from the container by normal means (pouring orpumping).

4.2.6.2 containers have no more than one inch of waste remaining.4.2.6.3 containers have no more than 3 % by weight of waste remaining.

4.2.7 Labels on containers are altered so as not to misidentify contents (example: methanol solvent can,emptied and triple rinsed with tap water should have the labels covered or scratched out, thenput into the dumpster).

5.0 Determination of Hazardous Wastes

5.1 Determine if the material waste is hazardous according to NR 605.09. The MSDS may be useful in thisdetermination. The Safety Officer has a copy of this rule.


4

5.2 If the material is listed, then the material and the container the material is directly contained in are considereda HAZARDOUS MATERIAL. Contact the Safety officer for proper disposal. Provide the name, typehazard (number and/or class) and quantity of material to be disposed of in writing to the Safety Officer.

5.3 If it is not clear if the material is hazardous, contact the Safety Officer and/or the area supervisor for furtherinvestigation. The material can be tested for hazardous characteristics (NR 605.08) at CT Laboratories orsubcontracted to another lab.

5.4 If the chemical is not listed as a hazardous waste it may be disposed of by other means. Reference bookssuch as Flinn Chemical Catalog & Reference, Aldrich Chemical or Baker Chemical are sourcesproviding guidance on disposal.

6.0 Known Wastes and Established Procedures

6.1 Samples, Solvents and Solutions

6.1.1 Water samples may contain known and suspected hazards in them such as acid preservatives,bacteria and industrial contaminants. To date, all of the waters CT Laboratories receives can bedisposed of through the municipal sewer system. When water samples are released from samplestorage, they can be directly disposed of by discharge into the sink drain, never a storm waterdrain. Samples from some sources may emit noxious odors and therefore dictate a sink drain in ahood. The bottles should be rinsed and disposed of in the municipal recycling program

6.1.2 Wastes containing potential pathogens (i.e., spent media, bacteria solutions, culture plates, etc.)Are autoclaved for a minimum of 30 minutes at 121° C/15 PSI prior to placement in theMunicipal waste.

6.1.3 Pretreatment - Solid samples vary in disposal process depending on the type of solid and theeffects of testing on the sample. We split solid samples into two groups, sludge and soils Sludge isdisposed of in the same manner as water samples due to their origin from wastewater treatmentfacilities. Soils are all disposed of in different waste streams, and may be pretreated to reduce theeffects from testing. Listed below are the pretreatments performed.

6.1.3.1 Non-RCRA soil samples, not used in testing or never come in contact with testingchemicals do not require pretreatment. The soil may be removed from the sample container,placed in the soil disposal drum and the sample container recycled with the municipal wastes, orthe sample and container placed in the disposal drum. Other sample containers that did notcontain acutely toxic chemicals and can be recycled with the municipal waste.

6.1.3.2 RCRA soils, and sample containers with solvent and soil, are disposed of into theappropriate hazardous (RCRA) soil waste stream, either PCB containing or reagent exposed.

6.1.3.3 Instrumental testing byproducts, such as extracts and eluents, require special attention insome instances. Wastes from the Lachat Autoanalyzer and the AA Spectrometers arediscarded to the municipal wastewater system. Extracts from organic testing are disposed of byremoving the liquid extracts from the containers and adding them to the flammable waste stream.The current exceptions to this are extracts that contain carbon disulfide, an acutely hazardous


5

chemical. The small quantity of carbon disulfide used in testing (< 50 mL a month) is exemptfrom current laboratory emissions. The carbon disulfide is decanted from the vials into a beakerin a hood and allowed to evaporate.

6.1.3.4 Waste solvents not recycled are presently split into three hazardous waste streams.These are listed below along with a general description of the hazard. Any waste not listed mustnot be added to these waste streams without prior authorization of the Safety Officer. To do somay change the waste stream into a different classification and make CT Laboratoriesnoncompliant under regulations. Before transferring these wastes into the storage barrels checkand wear proper personal protection equipment.

6.1.3.4.1 Flammable Liquid waste, such as hexane from testing, extracts and recyclingare combined into one stream. A drum properly marked is used to combine these typesof wastes.

6.1.3.4.2 Halogenated Liquid wastes, such as methylene chloride and freon mixturesfrom testing, extracts and recycling are combined into another waste stream. A drumproperly marked is used to combine these types of wastes.

6.1.3.4.3 Corrosive - Oxidizer Liquid wastes from COD, Phosphorus and TKN testingcomprise the last of the liquid waste streams we have. A drum properly marked is usedto combine these wastes. Special care must be exercised when transferring these wastesinto the storage drum as not to mistakenly add these to the flammable waste. This couldproduce a potentially explosive mixture.


6

6.2 Disposal (Hazardous waste)

6.2.1 Waste Disposed of Off-site

CT Laboratories contracts with licensed hazardous waste handlers to dispose of the laboratory wastestreams. The current hazardous waste (RCRA) contract is held by Safety Kleen. The contractedhazardous waste hauler must be contacted for a pick-up every 180 days or less. There are a total offive waste streams that are approved for disposal at Safety Kleen. These waste streams include thefollowing; 1) 6950299-Flammable solvents, this waste stream consists of the solvent waste from varioustesting, 2) 6950303-Reagent soils, this waste stream is made up of soil samples brought to thelaboratory preserved or come into contact with extraction solvents during the testing process, 3)6950301-COD/TKN/Metals Standards waste, this waste stream consists of digested COD solution ,digested and undigested TKN solution along with old standard from the metals group, 4) 6950302-Halogenated solvents, this waste stream consists of Methylene chloride from PAH testing, 5)(Unassigned number)- PCB liquids, this waste streams consists of all liquid wastes that are known tocontain PCBs. 5) (Unassigned number)- PCB solids, this waste streams consists of all solid wastes thatare known to contain PCBs. The current special soil waste (NON-RCRA) contract is held by LeachEnvironmental Services.

The following table describes the disposal methods used for each particular waste stream:

Profile No. Waste Stream Name Disposal Method

6950299 Flammable solvents Incineration

6950303 Reagent Soils Incineration

6950301 COD/TKN Chemical Fixation orIncineration

6950302 Halogenated solvents Resource RecoveryUnassigned PCB Incineration

Non-RCRA Soils Special soils License Landfill


7

The following table describes the proper containers for each specific waste stream:

Waste Stream Name Container Description Container Size

Flammable Solvents Black Steel Drum 30 or 55 gallon

Reagent Soils Black Open Head Steel Drum 55 gallon

COD/TKN WasteMetal Standards

Poly (Plastic) Closed HeadDrum

30 or 55 gallon

Halogenated Solvents Black Steel Drum 30 or 55 gallon

PCB Black Steel Drum 30 gallon

Non-RCRA Soils Black Steel Drum 55 gallon

6.2.2 The hazardous waste storage area is located in the brown shed on the west side of the building. This storage is for hazardous waste only and any hazardous waste supplies such as extra drums,vermiculite, etc,.

6.2.3 All bulking of laboratory waste receptacles into the proper labeled drums must be done inthe storage shed and over the safety pallets to ensure that nothing is spilled onto the concrete pad or theground. Each time a new drum is starting to be filled the accumulation start date is noted on the drum. This notation can be marked on the side of the drum or a hazardous waste label can be used and theaccumulation start date area filled in.

The following is a table which describes the packing and labeling requirements for each waste stream:

Waste Steam Name Packing Requirements Labeling Requirements

Flammable Solvents Fill with liquid only, leave last 4inches free of liquid.

Requires Flammable Liquid label

RCRA Solids Fill with RCRA solids only. Leave 3inches of headspace.

Hazardous Waste Label

COD/TKN Fill with liquid only. Leave last 3inches free of liquid.

Corrosive Liquid label

Halogenated Solvent Fill only with liquids. Leave last 3inches free of liquid.

Hazardous Waste Liquid Label

PCB Fill with liquid and solids. Leave last3 inches free.

PCB & Hazardous Waste LiquidLabel

Non-RCRA Soils Fill with special soils only. Leave 3inches of headspace.

NON-RCRA Blue Label


8

6.2.4 All of the above waste streams require a waste label. The pacing requirementsare straight forward and follow common sense practices. Never combine two wastestreams into one drum. This could lead to a serious reaction inside the drum. Also, thewaste streams are accepted by the waste disposal company as they are nowcategorized. If a mutual change is made by both CT Laboratories and the wastedisposal company the new agreement would supersede the current agreement.

6.2.5 The non-RCRA waste stream requires a blue NON-RCRA waste label.

Appendix B Chain-of-Custody and Sample Tag

Field Sampling Plan (FSP)

DRAFT FIELD SAMPLING PLAN



June 2005

MKE\050770002 III

Contents

Acronyms and Abbreviations ..........................................................................................................v

1. Introduction ...............................................................................................................................1-1 1.1 Site Setting.........................................................................................................................1-1 1.2 Plant History and Operations.........................................................................................1-2 1.3 Previous Investigations and Remediation....................................................................1-2 1.4 Geologic and Hydrogeologic Settings...........................................................................1-4

1.4.1 Geology.................................................................................................................1-4 1.4.2 Hydrogeology......................................................................................................1-4

1.5 Potential Receptors...........................................................................................................1-5 1.6 Recent Chemical Characteristics ....................................................................................1-6 1.7 Project Approach and Objectives...................................................................................1-6

2. Groundwater Monitoring Methodology ..............................................................................2-1 2.1 Sample Locations..............................................................................................................2-1

2.1.1 Compliance Monitoring .....................................................................................2-1 2.1.2 Natural Attenuation............................................................................................2-5

2.2 Analytical Program and Sampling Frequency.............................................................2-5 2.2.1 Compliance Monitoring .....................................................................................2-5 2.2.2 Natural Attenuation Monitoring ......................................................................2-5 2.2.3 Sampling Approach ............................................................................................2-6

3. Field Investigation Program ...................................................................................................3-1 3.1 Objectives ..........................................................................................................................3-1 3.2 Tasks...................................................................................................................................3-1 3.3 Field Operations and Procedures ..................................................................................3-1

3.3.1 Site Reconnaissance ............................................................................................3-2 3.3.2 Mobilization .........................................................................................................3-2 3.3.3 Groundwater/Surface Water Investigation ....................................................3-2 3.3.4 Demobilization ....................................................................................................3-4

4. General Field Operations ........................................................................................................4-1 4.1 Sample Management .......................................................................................................4-1

4.1.1 Sample Identification..........................................................................................4-1 4.1.2 Sample Containers ..............................................................................................4-1 4.1.3 Sample Preservation and Holding Times ........................................................4-2 4.1.4 Sample Handling, Packaging and Shipment...................................................4-3

4.2 Field Activity Documentation and Logbook................................................................4-3 4.2.1 Field Logbook ......................................................................................................4-3 4.2.2 Sample Chain-of-Custody..................................................................................4-3

4.3 Field Parameter Documentation ....................................................................................4-4 4.4 Quality Control Sample Procedures..............................................................................4-4

4.4.1 Decontamination .................................................................................................4-4 4.4.2 Field Duplicates...................................................................................................4-4

FIELD SAMPLING PLAN

IV MKE\050770002

4.4.3 Equipment Blanks............................................................................................... 4-5 4.4.4 Trip Blanks........................................................................................................... 4-5 4.4.5 Matrix Spike/Matrix Spike Duplicate ............................................................. 4-5 4.4.6 Temperature Blanks ........................................................................................... 4-5

4.5 Disposal of Investigation Derived Wastes ................................................................... 4-6 4.6 Field Monitoring Instrumentation ................................................................................ 4-6 4.7 Additional Field Operations .......................................................................................... 4-6

5. References .................................................................................................................................. 5-1

Appendix

A Field Operating Procedures

Tables

1 Monitoring Program Locations......................................................................................... 2-3 2 Site Analytes and Field Parameters—Natural Attenuation Monitoring..................... 2-6 3 Sample Containers, Preservations, and Holding Times................................................ 4-2 Figures

1 Existing Conditions Map 2 Conceptual Depiction of Site Aquifer Units and Well Placement 3 Compliance Monitoring Locations 4 Natural Attenuation Monitoring Locations

MKE\050770002 V

Acronyms and Abbreviations

1,1-DCA 1,1-dichloroethane 1,1-DCE 1,1-dichloroethene 1,1,1-TCA 1,1,1-trichloroethane

ARAR applicable or relevant and appropriate requirements

cis-1,2-DCE cis-1,2-dichloroethene COC chain-of-custody CRL Central Regional Laboratory CVOC chlorinated volatile organic compound

DE Disposable equipment DO dissolved oxygen DQO data quality objective

FOP Field Operating Procedure FORMS Field Operations Reporting Management System FSP Field Sampling Plan FTL Field Team Leader

HASP Health and Safety Plan

IDW investigation derived waste

LOD limit of detection

MNA monitored natural attenuation MS/MSD matrix spike/matrix spike duplicate MTBE methyl tert butyl ether

NAPL nonaqueous phase liquid NEIC National Enforcement Investigations Center NPL National Priorities List

OEP Oconomowoc Electroplating ORP oxidation-reduction potential OU operable unit

PAL Preventative Action Limit PID photoionization detector PPE personal protective equipment

QA/QC quality assurance/quality control

RI/FS Remedial Investigation/Feasibility Study ROD Record of Decision

SMO Sample Management Office

FIELD SAMPLING PLAN

VI MKE\050770002

TCE trichloroethene

USACE United States Army Corps of Engineers

VOC volatile organic compound

WDNR Wisconsin Department of Natural Resources WGNHS Wisconsin Geologic and Natural History Survey

MKE\050770002 1-1

SECTION 1

Introduction

This Field Sampling Plan (FSP) defines the procedures that will be used to complete groundwater sampling at the former Oconomowoc Electroplating (OEP) site in accordance with the Statement of Work dated May 17, 2004 for Work Assignment No. 236-RALR-05M8, Contract No. 68-W6-0025.

For 8 years, a groundwater extraction system operated at the OEP site located in Oconomowoc, Wisconsin. This extraction system substantially lowered the concentration of metals and chlorinated volatile organic compounds (CVOCs) in groundwater. In the summer of 2002, metals were at low enough concentrations that the WDNR and USEPA agreed to discontinue active groundwater metals treatment. The extraction system was shut down in July 2004 because groundwater CVOC concentrations from the extraction wells were no longer decreasing with continued operation or were decreasing at a very small rate. Other source reduction activities performed previously at the site included the removal of the former lagoon sediment and sludge, contaminated soil, and contaminated sediment in the wetlands around Davy Creek.

For the remaining groundwater concentrations of CVOCs, natural attenuation (NA) processes are being monitored and evaluated at the site and at downgradient locations. In October 2004, groundwater samples were collected from a subset of existing wells at OEP. The data support that NA of CVOCs is occurring at downgradient portions of the plume. In spite of the groundwater treatment system shutdown, October 2004 data indicate that concentrations similar to those measured in the previous sampling round of April 2003, when the system was in operation, are present. This suggests that the CVOC plume is currently stable.

The purpose of the groundwater and surface water sampling presented in this FSP is two-fold, including the collection of groundwater samples (1) for the evaluation of natural attenuation as a stand alone remedy and (2) for compliance with state and federal drinking water regulations. Also presented in this FSP is a brief discussion of the installation of a nested pair of “sentinel wells” and the replacement of two staff gauges in Davy Creek. The sentinel wells will be installed further downgradient than any existing monitoring wells. These wells, once installed, will serve as downgradient monitoring points. The staff gauge replacement will aid in the monitoring of levels along Davy Creek, allowing for greater understanding of surface water/groundwater interaction.

1.1 Site Setting The 10-acre study area comprises the former 4-acre OEP site (bounded by Elm, Oak, and Eva Streets, and Town of Ashippun buildings) located at 2572 Oak Street in Ashippun, Wisconsin, and 6 acres of a wet, low-lying area located adjacent to the southwest portion of the former site (Figure 1). This low-lying area is referred to in this plan as a wetland area similar to previous project documents.

FIELD SAMPLING PLAN

1-2 MKE\050770002

Due to the proximity of Ashippun to Oconomowoc, Wisconsin, the names of the township and the city are often interchanged. This document will refer to the project location as Oconomowoc, Wisconsin.

The site is in southeastern Wisconsin in Dodge County, roughly 40 miles west-northwest of Milwaukee. The site is located in the northwest quarter of the southeast quarter of Section 30 Township 9 North, Range 17 East. Nearby surface water bodies include Davy Creek, located a few hundred feet to the southwest of the site, and Rock River, located about 1 mile west of the site. The site slopes gently toward Davy Creek to the southwest. Landscaped linear berms bound the site at its northwestern, northeastern, and southeastern perimeters, with rough heights above the surrounding ground surface that generally range from 3 to 4 feet. The former OEP buildings have been demolished at the site. The groundwater treatment plant building is present in the northeast portion of the site.

1.2 Plant History and Operations Various onsite metal cleaning and electroplating processes that used chlorinated solvents, cyanide, chromium, cadmium, copper, nickel, tin, and zinc were performed at OEP since operation began in 1957. Chromate conversion, coating, and anodizing were also used as part of the finishing processes. Degreasing operations were performed at the site, however the constituents used in these operations were not documented (Ebasco 1990).

Wastes generated as a byproduct of these processes were discharged into low areas on the east side of the site, wastewater lagoons on the southwest side of the site, and the wetland area and Davy Creek to the south of the site (Figure 1). These waste disposal practices led to the widespread contamination of soil, sediment, and groundwater across the site (RMT 2004).

OEP ceased operation in 1990 due to financial hardship. Buildings at the site were demolished and removed in May 1992.

1.3 Previous Investigations and Remediation A USEPA Field Investigation Team (FIT) performed a preliminary assessment of the OEP site in 1983. As a result of this preliminary assessment, the site was placed on the National Priorities List (NPL) (Ebasco 1990). The Wisconsin Department of Natural Resources (WDNR) and Wisconsin Geologic and Natural History Survey (WGNHS) conducted preliminary groundwater sampling efforts at the site from 1983 to 1987. The results of this sampling showed that chlorinated solvents (primarily trichloroethene [TCE] and 1,1,1-trichloroethane and their associated degradation products) and metals were detected in groundwater (RMT 2004).

USEPA, in consultation with the WDNR, conducted a Remedial Investigation and Feasibility Study (RI/FS) at the site from April 1987 to September 1990. The RI determined that, as a result of hazardous waste disposal at the electroplating site, various chemical contaminants had leached into the shallow groundwater, which in turn flows mostly toward Davy Creek. Soils were contaminated with organic chemicals and metals. The concentrations of chemicals found in the groundwater and soils were found to present

1—INTRODUCTION

MKE\050770002 1-3

unacceptable potential risk levels to human and/or environmental receptors based on a baseline risk assessment (Ebasco 1990). For the purposes of the FS, the site was divided into the following four operable units (OUs): OU-1—the lagoons, OU-2—the contaminated soil, OU-3—the contaminated groundwater, and OU-4—the Davy Creek wetland area sediment.

USEPA issued a Record of Decision (ROD) in 1990 that declared remedies for each OU. These remedies include:

• OU-1—the excavation and disposal of lagoon sludge and surrounding soils

• OU-2—the excavation and disposal of nonlagoon contaminated soils and debris (including an abandoned electroplating building)

• OU-3—the extraction and treatment of groundwater to state groundwater quality standards

• OU-4—the excavation and disposal of metals-contaminated sediments offsite from the wetland area adjacent to Davy Creek

Remedial actions for OU-1 (removal of 650 cubic yards [cy] of lagoon sludge/soil), OU-2 (removal of 700 cy of soil), and OU-4 (removal of 6,000 cy of creek sediment) have been completed in accordance with the approved remedial design. In 1996, USEPA constructed a treatment system to treat groundwater extracted by five wells (Figure 1). This system is operated on behalf of the USEPA by the U.S. Army Corps of Engineers (USACE). Although pumping and treating the groundwater has substantially lowered the concentration of contaminants, the rate of concentration decrease has leveled off. The extraction system was shut down in July 2004 because groundwater concentrations from the extraction wells were no longer decreasing with continued operation or were decreasing at a very small rate.

A subsequent study conducted by RMT Inc. of Madison, Wisconsin, (on behalf of the WDNR) utilized both ground/surface water sampling and three-dimensional groundwater flow and contaminant transport modeling to evaluate the effectiveness of the groundwater treatment system. The results of the study were documented by RMT (RMT 2004) and are not included in this report. Groundwater sampling was performed in April 2003 during apparent groundwater extraction system operation. However, the system was temporarily turned off in July 2003 to collect water level measurements.

RMT (RMT 2004) evaluated historical trends of several monitoring and extraction wells and noted decreasing concentrations of TCE and vinyl chloride. Modeling, performed by RMT to evaluate the effectiveness of the pump and treat system, suggested that a possible reason for the stabilized concentrations in groundwater was the presence of nonaqueous phase liquids (NAPLs) that remained sorbed to the organic material deposited within soil. Additional modeling indicated that further extraction of groundwater would not reduce the time to reach the regulatory target concentrations. As a result, the treatment plant was shut down in July 2004. Shutdown details are found in the Groundwater Treatment Facility Shutdown Plan (CH2M HILL 2004).

FIELD SAMPLING PLAN

1-4 MKE\050770002

1.4 Geologic and Hydrogeologic Settings The geologic and hydrogeologic settings summarized below are discussed both in terms of regional conditions and those encountered during investigations for the site as documented in previous reports (RMT 2004).

1.4.1 Geology The OEP site is located in Dodge County in southeastern Wisconsin. The regional geology beneath the site is comprised of unconsolidated Quaternary- and/or Holocene-aged deposits underlain by a succession of Precambrian and Paleozoic bedrock units. Precambrian crystalline basement rock is overlain by Cambrian sandstone and Ordovician dolomite, sandstone, and shale. Silurian dolomite is present in some locations of Dodge County, but not beneath the OEP site. The Paleozoic units (Cambrian, Ordovician, and Silurian) are all sedimentary in their origins, and they generally dip to the east and southeast. Due to the thickness and great depth of the Precambrian and Cambrian units, only the uppermost bedrock (Ordovician-aged) and unconsolidated deposits are discussed in greater detail.

The Ordovician bedrock units, from oldest to youngest, are composed of the Prairie du Chien Group, St. Peter Sandstone, Galena-Platteville Unit, and Maquoketa Shale. The Prairie du Chien Group and the Galena-Platteville Unit primarily consist of dolomite, but they also contain some sandstone, sandy dolomite, and shaly dolomite. The St. Peter Sandstone is predominantly a fine– to medium-grained sandstone, but it is dolomitic and shaly in some locations. The Maquoketa Shale is primarily dolomitic shale, but it is dolomite in some locations. A dolomite portion of the Maquoketa Shale lies directly beneath the site. Rock cores collected from the Maquoketa shale that underlie the site indicated both distinct zones with heavy amounts of fracturing and zones with little fracturing. A preglacial and glacial erosional surface unconformity separates the Ordovician bedrock surface from the overlying unconsolidated deposits.

The unconsolidated deposits beneath the site range in thickness from 28 feet beneath the former OEP site to 55 feet at the southwestern edge of the site (RMT 2004). Silt and clay fill is sporadically present in the upper 4 to 10 feet of unconsolidated material at several locations at and in the vicinity of the former OEP site.

The unconsolidated glacial material consists of gray-brown and yellow-brown sand, silty sand, and clay. The silt content in the glacial material varies from trace amounts to greater than 50 percent. Discontinuous lenses of silt and clay were observed to be present within the sands in several borings across the study area. Compacted clay up to 8 feet thick is present directly above the top of bedrock in some locations (RMT 2004).

1.4.2 Hydrogeology Dodge County has four major aquifers named here in order from shallowest to deepest: 1) the unconsolidated sand and gravel, 2) the Silurian dolomite, 3) the Galena-Plateville dolomite, and 4) the St. Peter Sandstone aquifers (Devaul, Harr, and Schiller 1983). Only two of these aquifers are present beneath the OEP site: the Galena-Platteville dolomite and the St. Peter Sandstone aquifers. Maquoketa shale, which sits above these bedrock aquifers and

1—INTRODUCTION

MKE\050770002 1-5

is the uppermost bedrock encountered at the site, is considered to be an aquitard unit on a regional basis. However, it does contain some dolomite layers that are capable of yielding sufficient quantities of water for residential use.

Groundwater is present in the unconsolidated silty sand that sits above the Maquoketa shale at the site, although it is not considered to be part of the regional sand and gravel aquifer due to its higher silt content. The water table in this unconfined water-bearing unit roughly parallels the ground surface topography (the groundwater is assumed to be under atmospheric pressure [Devaul, Harr, and Schiller 1983]).

Groundwater monitoring wells are installed at the site study area in the unconsolidated zone and in the upper bedrock. Nested wells are installed in the unconsolidated zone, with the shallow wells monitoring the upper portion of this unit and the deep wells monitoring the lower portion of this unit (Figure 2).

Groundwater levels were measured in the unconsolidated zone October 2004, over two months after the extraction system was shutdown. Because of the length of time that elapsed between system shutdown and the water level measurements, the data is believed to represent current natural flow conditions (that is, no influences from previous pumping at the site). The water table surface (shallow unconsolidated groundwater) measured in October 2004 indicates groundwater flow from the site is generally to the south toward the wetland area and Davy Creek, similar to previous investigations (RMT 2004). The depth to shallow groundwater ranges from 4 feet in wells closest to Davy Creek, and up to 10 feet at the west side of the site. Based on October 2004 data, groundwater in the deeper portions of the unconsolidated aquifer radiates to the southeast and southwest from the site.

Bedrock wells penetrate into areas of the water-bearing dolomite portions of the Maquoketa shale. In October 2004, bedrock well groundwater levels showed groundwater flow to be variable and may reflect the monitoring of discontinuous dolomite beds within the Maquoketa shale.

In general, vertical gradient calculations suggest downward groundwater flow near the site reversing to upward groundwater flow near Davy Creek between the shallow and deep portions of the unconsolidated aquifer. Measurements between the unconsolidated aquifer and bedrock aquifer suggest overall similar trends, however the magnitude of upward groundwater flow near Davy Creek and the wetlands appears to be less. This suggests that unconsolidated zone groundwater may discharge to Davy Creek.

1.5 Potential Receptors Potential human and ecological receptors for the OEP site’s groundwater include Davy Creek and its associated wetland area, private water supply wells, and residential structures. Davy Creek and its associated wetland area are likely connected to unconsolidated groundwater in the area.

Several water supply wells associated with private residences are located to the west and northwest of the site (Figure 1). These wells are screened in the Maquoketa shale and upper portions of the Galena-Platteville dolomite, and previous investigation has shown no detection of site contaminants (RMT 2004).

FIELD SAMPLING PLAN

1-6 MKE\050770002

1.6 Recent Chemical Characteristics The most recent investigation of groundwater quality at the OEP site was performed by CH2M HILL in October 2004 to evaluate natural attenuation processes occurring in unconsolidated zone groundwater at and downgradient of the site. During this investigation, groundwater samples were collected from 12 monitoring wells. Each sampling point was analyzed for volatile organic compounds (VOCs), natural attenuation parameters, and field parameters. Detailed field and analytical results for this sampling event are presented in the Groundwater Management Plan dated March 2005.

In general, the distribution of parent products, TCE and 1,1,1-trichloroethane (1,1,1-TCA), in the shallow aquifer extends from the southern portion of the site generally south of Elm Street toward the wetland area, corresponding with the groundwater flow direction. The highest concentrations of TCE (240-2200 μg/L) were detected in the deep wells at MW-105D and MW-103D, respectively. The highest concentrations of degradation products (cis-1,2-chloroethene, vinyl chloride, 1,1-dichloroethane, 1,1-dichloroethene, and chloroethane) were observed near the apparent source area (MW-103 well nest) and at downgradient locations. In general, degradation products were detected further downgradient toward Davy Creek than parent products including those sampled wells (MW-13D and MW-16S) closest to Davy Creek. In spite of the groundwater treatment system shutdown, October 2004 data show similar concentrations as the previous sampling round in April 2003, when the system was in operation. This suggests that the CVOC plume is currently stable.

Based upon groundwater monitoring data for the shallow and deep unconsolidated zones performed in October 2004, parent products in groundwater (TCE and 1,1,1-TCA) are being degraded to degradation products by anaerobic reductive dehalogenation and other NA processes. Additionally, final and nontoxic degradation byproducts, ethene and ethane, were also detected at the site in October 2004.

For the October 2004 sampling event, federal Maximum Concentration Limits (MCLs) and Wisconsin Administrative Code (WAC) NR 140 Enforcement Standard (ES) exceedances were generally observed in the near source well nest (MW-103) or at generally downgradient well nests (shallow and deep locations) in the wetland adjacent to Davy Creek (MW-12, MW-13, MW-15, MW-16, and MW-105). The following compounds were detected at or above their respective ES: chloride, iron, manganese, sulfate, 1,1,1-TCA, 1,1-dichloroethene, cis-1,2-dichloroethene, TCE, and vinyl chloride.

1.7 Project Approach and Objectives There are two intended purposes to groundwater sampling for the project. The first purpose is to gather groundwater data at residential wells, monitoring wells located in the downgradient portions of the plume, and surface water samples to evaluate impacts to potential receptors and compliance with state and federal groundwater and surface water standards (that is, Compliance Monitoring). The second purpose is to collect groundwater data throughout the CVOC plume to assess natural attenuation as a sole remedy for the site (that is, Natural Attenuation Monitoring).

1—INTRODUCTION

MKE\050770002 1-7

Due to the different objectives of Compliance and Natural Attenuation monitoring, they are discussed separately in many of the following sections of this FSP.

The installation of a nested pair of sentinel wells will provide additional downgradient groundwater monitoring beyond Davy Creek. The replacement of two staff gauges along Davy Creek is intended to provide additional surface water elevation data, aiding in the improved understanding of groundwater/surface water interactions along Davy Creek.

MKE\050770002 2-1

SECTION 2

Groundwater Monitoring Methodology

This section presents sample locations, sample analysis, and frequency of sampling for groundwater monitoring for the project. The approach of groundwater monitoring for the project was based on the overall objective to gather data to evaluate impacts to potential receptors (Compliance Monitoring) and to evaluate natural attenuation as a stand-alone remedy (Natural Attenuation Monitoring).

The methodology for groundwater monitoring will provide data to:

• Verify current groundwater flow patterns and gradients (vertical and horizontal) in the shallow, deep, and bedrock portions

• Obtain surface water data to evaluate compliance with state standards (NR 105)

• Obtain private water supply data to evaluate compliance with federal and state standards (MCLs and NR 140)

• Obtain groundwater monitoring well data to evaluate the stability of the plume and compliance with federal and state standards (MCLs and NR 140)

• Obtain groundwater field parameter data useful in the assessment of natural attenuation capabilities

• Obtain analytical groundwater data for VOCs and geochemical parameters useful in the assessment of natural attenuation capabilities

2.1 Sample Locations Available sample locations for the project include private water supply wells, extraction wells, groundwater monitoring wells, drive point piezometers, and surface water (wetland and Davy Creek) (Figure 1). Sample locations for compliance and natural attenuation monitoring are discussed separately.

2.1.1 Compliance Monitoring For compliance sampling, sample locations were chosen to include 11 private water supply wells (within 250 feet of the site), 20 groundwater monitoring wells in the downgradient portions of the plume, and 3 staff gauges for the collection of surface water samples (Table 1 and Figure 3). Available well construction information (RMT 2004) in the vicinity of the site generally indicates completion within 15 feet of the bedrock surface. Well construction information for the 2550 Oak Street well indicates it is cased through the upper 68 feet of the bedrock. Because this well is cased through the upper portions of the bedrock and obtains its groundwater from greater depths, it is not recommended for sampling. Furthermore, VOCs were not detected in this well during sampling in April 2003. However, if chlorinated

FIELD SAMPLING PLAN

2-2 MKE\050770002

VOCs are detected in bedrock monitoring wells or adjacent water supply wells, it should be added to the sampling program.

Groundwater samples will also be collected from five bedrock monitoring wells, eight deep monitoring wells, and seven shallow monitoring wells. The compliance monitoring locations will monitor private water supplies and surface water for compliance with state and federal drinking water and surface water standards, respectively. Furthermore, monitoring of the downgradient monitoring wells will provide information on the stability of the CVOC plume.

TABLE 1Monitoring Program LocationsOconomowoc Electroplating, Oconomowoc, Wisconsin

Well Name/Location Monitoring ZoneWater Level

MeasurementCompliance Sampling (1)

Natural Attenuation Sampling (2) Comments

Water Supply WellsPW-01 GW-Upper bedrock X 2551 Oak Street, Town of AshippunPW-02 GW-Upper bedrock X 2580 Oak Street, KrierPW-03 GW-Upper bedrock X 2601 Oak Street, McMullenPW-04 GW-Upper bedrock X 2605 Oak Street, OttoPW-05 GW-Upper bedrock X 2611 Oak Street, PeirickPW-06 GW-Upper bedrock X 547 Eva Street, Krier (rental property owner)PW-07 GW-Upper bedrock X 2602 Elm Street, KrierPW-08 GW-Upper bedrock X 2603 Elm Street, KehlPW-09 GW-Upper bedrock X 2606 Elm Street, OttoPW-10 GW-Upper bedrock X 2607 Elm Street, BurrowPW-11 GW-Upper bedrock X 2612 Elm Street, Fortlage

SUBTOTAL 11Monitoring WellsMW-1S GW-Shallow unconsolidated X X UpgradientMW-1D GW-Upper bedrock XMW-2D GW-Upper bedrock XMW-3S GW-Shallow unconsolidated XMW-3D GW-Upper bedrock XMW-4S GW-Shallow unconsolidated XMW-4D GW-Upper bedrock X X DowngradientMW-5 GW-Shallow unconsolidated XMW-5D GW-Deep unconsolidated X X DowngradientMW-9S GW-Shallow unconsolidated XMW-12S GW-Shallow unconsolidated X X X DowngradientMW-12D GW-Deep unconsolidated X X X DowngradientMW-12B GW-Upper bedrock X X DowngradientMW-13S GW-Shallow unconsolidated X X DowngradientMW-13D GW-Deep unconsolidated X X X DowngradientMW-14D GW-Deep unconsolidated X X UpgradientMW-15S GW-Shallow unconsolidated X X X DowngradientMW-15D GW-Deep unconsolidated X X X DowngradientMW-15B GW-Upper bedrock X X DowngradientMW-16S GW-Shallow unconsolidated X X X DowngradientMW-101S GW-Shallow unconsolidated XMW-101B GW-Upper bedrock X X Downgradient - sentinel wellMW-102S GW-Shallow unconsolidated X

TABLE 1Monitoring Program LocationsOconomowoc Electroplating, Oconomowoc, Wisconsin

Well Name/Location Monitoring ZoneWater Level

MeasurementCompliance Sampling (1)

Natural Attenuation Sampling (2) Comments

Monitoring Wells ContinuedMW-102D GW-Deep unconsolidated X X Downgradient - sentinel wellMW-103S GW-Shallow unconsolidated X X Near source areaMW-103D GW-Deep unconsolidated X X Near source areaMW-104S GW-Shallow unconsolidated XMW-104D GW-Deep unconsolidated XMW-105S GW-Shallow unconsolidated X X X DowngradientMW-105D GW-Deep unconsolidated X X X DowngradientMW-105B GW-Upper bedrock X X DowngradientMW-106S GW-Shallow unconsolidated X X Downgradient - sentinel wellMW-106D GW-Deep unconsolidated X X Downgradient - sentinel wellMW-107S (4) GW-Shallow unconsolidated X X X Downgradient - sentinel wellMW-107D (4) GW-Deep unconsolidated X X X Downgradient - sentinel wellOW-6 GW-Upper bedrock X

SUBTOTAL 36 20 14Drive Point PiezometersP-1 SW XP-2 SW XP-3 SW X

SUBTOTAL 3Staff GaugesSG-1 SW X X XSG-2 SW X X XSG-3 SW X X X

SUBTOTAL 3 3 3TOTAL 42 34 17

GW-Groundwater

SW-Surface water

(1) Compliance sampling includes the analysis of VOCs. Water levels would be taken at all accessible monitoring wells, drive point piezometers, and staff gauges. Semi-annual sampling will be performed.

(2) Natural Attenuation sampling includes the analysis of VOCs and natural attenuation parameters (nitrate, diss. Managnese, total and diss. Iron, sulfate, sulfide, methane, ethene, ethane, chloride, alkalinity and soluble organic carbon) and the measurement of field parameters (temperature, pH, specific conductivity, dissolved oxygen, and oxidation reduction potential). Water levels would be taken at all accessible monitoring wells, drive point piezometers, and staff gauges. Quarterly sampling will be performed to evaluate seasonal trends in natural attenuation parameters for a two year period.

(3) Surface water monitoring will be performed for the same analysis and frequency as NA groundwater sampling. In addition, Orthophosphate and ammonia will be performed on surface water samples.

(4) Proposed groundwater monitoring well nest on the south side of Davy Creek.

2—GROUNDWATER MONITORING METHODOLOGY

MKE\050770002 2-5

2.1.2 Natural Attenuation For natural attenuation sampling, 2 upgradient locations, 2 near source, and 10 downgradient monitoring wells were chosen for monitoring (Table 1 and Figure 4). In addition, surface water samples will be collected from the three staff gauge locations. Seven of the wells are screened in the shallow unconsolidated aquifer, and seven are screened in the deep unconsolidated aquifer. The locations of the sampling points will monitor natural attenuation processes throughout the plume.

2.2 Analytical Program and Sampling Frequency In developing the sampling program for the OEP site, the project objectives and the following elements were considered:

• Identification of target compounds with respect to the results of previous investigations.

• Obtain quality and meaningful data useful for the assessment of natural attenuation and compliance with state and federal water quality and state surface water quality standards.

• Determine the appropriate and acceptable analytical methodology that meets the data quality objectives (DQOs), including any site-specific applicable or relevant and appropriate requirements (ARARs).

• Determine an effective analytical program with appropriate QA/QC requirements, such that site sampling location and frequency may be optimized.

Analytical methodology for compliance and natural attenuation monitoring are discussed separately.

2.2.1 Compliance Monitoring Samples collected from compliance locations will be analyzed for VOCs using method SW 846 8260 (see QAPP for listing of VOCs). An offsite laboratory subcontracted by CH2M HILL will analyze the groundwater compliance samples for VOCs using the appropriate analytical methods to reach the project-specific analytical requirements.

Semiannual compliance groundwater samples will be collected initially from 11 private water wells, 20 groundwater monitoring wells, and 3 surface water locations. Subsequent compliance sampling events will include a group of eight private water wells composed of residential wells primarily located near the corner of Eva Street and Elm Street.

2.2.2 Natural Attenuation Monitoring Samples collected from natural attenuation monitoring well locations will be analyzed for NA parameters (nitrate, dissolved manganese, total and dissolved iron, sulfate, sulfide, methane, ethane, ethane, chloride, alkalinity, and soluble organic carbon), VOCs, and field parameters (water level, temperature, pH, specific conductance, dissolved oxygen, and oxidation reduction potential) (Table 2). Surface water samples will be analyzed for the same parameters, however, ortho-phosphate and ammonia will also be performed. Because NA data is being collected to evaluate a potential remedy for the site and thus serves as

FIELD SAMPLING PLAN

2-6 MKE\050770002

engineering data, an offsite laboratory subcontracted by CH2M HILL will analyze the natural attenuation samples using the appropriate analytical methods to reach the project-specific analytical requirements.

Natural attenuation groundwater samples will be collected on a quarterly basis for a 2-year period, with an optional year of monitoring to be conducted at the discretion of the WAM, to evaluate seasonal variability. The natural attenuation sampling frequency will be reevaluated and modified, if necessary, after the initial 2-year period. For natural attenuation monitoring locations (MW-12S, MW-12D, MW-13D, MW-15S, MW-15D, MW-16S, MW-105S, MW-105D, and the proposed new sentinel well nest) that correspond to compliance sample locations, VOC analysis shall be performed in accordance with those methods described for compliance monitoring. For efficiency and data comparability, compliance and natural attenuation sampling events will be coordinated.

TABLE 2 Site Analytes and Field Parameters—Natural Attenuation Monitoring Oconomowoc Electroplating, Oconomowoc, Wisconsin

Analytes Field Parameters

Alkalinity DO Chloride ORP

Dissolved Iron pH Dissolved Manganese Specific Conductance

Ethane Temperature Ethene

Methane Nitrate Sulfate Sulfide

Total Iron Total Organic Carbon

Ortho-phosphate (surface water samples only) Ammonia (surface water samples only)

VOCs Note: A listing of individual VOCs can be found in the Quality Assurance Project Plan (QAPP).

2.2.3 Sampling Approach Water levels will be measured from all accessible groundwater monitoring wells, drive point piezometers, and staff gauges during the first day of each sampling event (Table 1, Figure 1).

Sampling at monitoring wells will be conducted using low-flow purging and sampling techniques (see Field Operating Procedure (FOP) No. 1—Low-Flow Groundwater Sampling Procedures). Groundwater field parameters will be monitored with a multimeter and flow-through cell while the wells are purged. The wells will be purged continuously until monitored field parameters stabilize within the limits specified in FOP No. 1—Low-Flow Groundwater Sampling Procedures. Samples will be collected immediately following the

2—GROUNDWATER MONITORING METHODOLOGY

MKE\050770002 2-7

stabilization of groundwater field parameters. The samples will be processed, packaged, and shipped on the day of collection.

Private water supply wells will be sampled only after opening the tap wide open for 15 minutes and after any holding or storage tanks have been drained. An attempt will be made to collect the sample at a tap nearest the wellhead and prior to any treatment. The specific equipment to be used and detailed procedures for private well sampling are presented in FOP No. 10—Private Residential Well Groundwater Sampling Procedures.

Surface water sampling will be performed by collecting water in a beaker while standing on a nearby bank. This water will be immediately transferred into sample containers. The specific equipment to be used and detailed procedures for surface water sampling are presented in FOP No. 9—Surface Water Sampling Procedures.

MKE\050770002 3-1

SECTION 3

Field Investigation Program

The specific objectives of the field investigation program are developed based on observations made during previous site visits, current site conditions, available information pertaining to past activities, and available soil and groundwater analytical data.

3.1 Objectives The general objectives of the field investigation are as follows:

• Measure groundwater elevations at the wells listed in Table 1 and verify the previous groundwater flow patterns in the bedrock aquifer and the shallow and deep unconsolidated aquifers.

• Collect analytical and field groundwater chemistry data to assess natural attenuation capacity.

3.2 Tasks The following tasks will be performed to complete the field investigation objectives:

• Site Reconnaissance—Information regarding site access and well information will be used to refine the locations selected for the groundwater sampling event. Groundwater elevation levels will be collected from the wells listed in Table 1, provided they are accessible.

• Mobilization—This task consists of assembling and mobilizing the necessary equipment to the site prior to the groundwater sampling event.

• Groundwater Sampling—Samples will be collected from compliance and natural attenuation monitoring points.

• Demobilization—At the completion of fieldwork, personnel, equipment, and supplies will be demobilized from the site. Investigation derived waste (IDW) will be collected onsite in 55-gallon drums and stored until they may be disposed of at a later date.

3.3 Field Operations and Procedures This section provides an overview of the equipment, operations, and procedures that will be performed during groundwater sampling events. It also references specific FOPs in Appendix A that provide step-by-step procedures for conducting the field tasks. For instances in which FOPs are not referenced, the text of that particular section will act as the FOP.

FIELD SAMPLING PLAN

3-2 MKE\050770002

3.3.1 Site Reconnaissance Site reconnaissance tasks will be completed prior to the start of sampling activities. These tasks will include:

• Confirming health and safety information, including the route and travel time to the hospital specified in the Health and Safety Plan (HASP) and the addresses of local fire and police departments.

• Coordinating with USEPA staff for sampling dates and access.

• Locating the Federal Express office nearest to the site and noting its hours of operation, and determining whether the office will provide sample pick-up service.

• Locating and measuring groundwater levels at accessible monitoring wells, as indicated in Table 1. Groundwater levels will be measured using FOP No. 2—Groundwater Level Measurements. All observations and measurements will be documented in the field notebook using FOP No. 3—Field Logbook.

• Inspecting proposed sampling locations (site wells are listed in Table 1) to determine if modifications are necessary based on access issues, broken or dry wells, or any other unspecified difficulties. Any modifications necessary will be recorded along with the reason for the modification.

3.3.2 Mobilization Prior to initiating any field work, the following preparatory activities will be completed:

• The necessary field equipment and supplies (sample bottles, coolers, water level indicator, tubing, etc.) must be assembled.

• Identified field supplies (for example, personal protective equipment [PPE], sample containers, preservatives, sample forms, and other related items) and field monitoring equipment must be obtained and transported to the site.

• Analyses must be confirmed to be scheduled through an independent laboratory

• It must be confirmed that field equipment is in proper working order and has received the appropriate quality control checks

During mobilization activities, the Field Team Leader (FTL) will perform a walk-through inspection of the site and will inspect and generate field sampling maps. The level of health and safety protection during the mobilization activities will be Level D.

3.3.3 Groundwater/Surface Water Investigation

3.3.3.1 Monitoring Well Purging and Sampling

The water level and well depth measured during Site Reconnaissance (described in FOP No. 2—Groundwater Level Measurements will be used to calculate a purge volume and assess the amount of solids collecting in a well. Wells will be purged as described in FOP No. 1—Low-Flow Groundwater Sampling Procedures. While purging the wells, field parameters of the

3—FIELD INVESTIGATION PROGRAM

MKE\050770002 3-3

groundwater will be monitored with a multimeter and flow-through cell. The multimeter will be calibrated using FOP No. 4—Equipment Calibration.

Groundwater samples collected from compliance sample points will be analyzed for VOCs. Groundwater samples collected from natural attenuation sample points will be analyzed for VOCs, natural attenuation parameters, and field parameters (pH, specific conductance, DO, ORP, and temperature; Table 2).

Groundwater samples are to be collected from existing monitoring wells using low-flow sampling techniques. The specific equipment to be used and the procedures for low-flow groundwater sampling are presented in FOP No. 1—Low-Flow Groundwater Sampling Procedures. Procedures for field filtering all groundwater samples are provided in FOP No. 5—Field Filtering Samples.

Non-dedicated sampling equipment will be decontaminated between locations using FOP No. 6—Field Sampling Equipment Decontamination. Dedicated sampling equipment will be disposed of in on-site 55-gallon drums.

3.3.3.2 Private Well Purging and Sampling

All property owners will be notified of the need to access their property before sampling of any private residential wells. Notification shall include a letter issued to the owner at least 1 month prior to sampling. This letter will detail the preferred sampling dates and ask for permission to utilize the outdoor faucet/spigot closest to the wellhead for sampling. The notification letter will be followed by a phone call, placed at least 1 week prior to sampling, requesting confirmation of permission to access the owner’s property and utilize their preferred sampling point.

Groundwater samples to be collected from private residential wells will be taken from an outdoor sample point deemed appropriate by the property owner. The faucet/spigot should be run wide open for at least 15 minutes, or until any storage tanks are drained. Field parameters (pH, specific conductance, DO, ORP, and temperature; Table 2) will be collected at all private well locations following well purging and prior to collecting groundwater samples. The specific equipment to be used and detailed procedures for private well field parameter collection and groundwater sampling are presented in FOP No. 10—Private Residential Well Groundwater Sampling Procedures. For any samples that would require field filtering, procedures are provided in FOP No. 5—Field Filtering Samples.

3.3.3.3 Surface Water Sampling Surface water samples will be collected at each of the three staff gauge locations along Davy Creek and its’ associated wetlands. Access to and depth of the water will dictate how the samples will be taken. The water will first be collected in a beaker made of inert materials and then transferred to specific sample containers. This beaker will be decontaminated between each sampling location. Field parameters will be collected by immersing a multi-meter probe in the creek, and recording the parameters once the readings have stabilized. The specific equipment to be used and detailed procedures for surface water sampling and field parameter collection are presented in FOP No. 9—Surface Water Sampling Procedures. For any samples that would require field filtering, procedures are provided in FOP No. 5—Field Filtering Samples.

FIELD SAMPLING PLAN

3-4 MKE\050770002

3.3.4 Demobilization Upon conclusion of the field activities, equipment from the site will be demobilized. Equipment and tools will be properly decontaminated before they are demobilized from the area using FOP No. 6—Field Sampling Equipment Decontamination. IDW will be collected onsite in 55-gallon drums and stored until they may be disposed of at a later date.

MKE\050770002 4-1

SECTION 4

General Field Operations

4.1 Sample Management The section describes the procedures to be implemented to ensure that representative environmental samples are properly containerized, preserved, shipped, and otherwise handled in a manner that will maintain sample integrity once they are obtained. The use of these techniques will provide representative samples and will reduce the possibility of sample contamination from external sources.

4.1.1 Sample Identification CH2M HILL has devised a sample-numbering system that will be used to identify each sample, including duplicates and blanks. A Sample Management Office (SMO) number and a Central Regional Laboratory (CRL) number will be assigned to each sample to be analyzed by an offsite laboratory. (Refer to the User’s Guide to the Contract Laboratory Program for an explanation of the SMO numbers. Refer to the CRL Sample Handling Manual for an explanation of the CRL number.) The Field Activity Manager will maintain a listing of sample IDs in the sampling logbook. Each CH2M HILL sample number will consist of three components.

Each sample will have a three-digit project identification code (identifying the Oconomowoc Electroplating site as “OEP”), followed by an alphanumeric code corresponding to the medium and a three-digit sequential number. Sample numbers will be reserved for the different media being sampled. They will not be repeated within a sample station, medium, or among differing media. Duplicate samples will not be distinguished within the sample numbers, but they will be distinguished through the subsample identification within the sample tracking and data management systems. This is done so that no bias may be given to the samples during analysis. The media codes are:

• MW—Monitoring well groundwater sample • FB—Field blank QC sample • FD—Field duplicate QC sample

The following is an example of a sample number:

• OEPMW01S001—Groundwater sample collected from OEP sample location MW01S, sample number 001.

4.1.2 Sample Containers The contaminant-free sample containers (bottles) used in this sampling effort will be purchased from an approved vendor or prepared by the subcontracted laboratory. Sample containers for laboratory analyses will meet or exceed the USEPA requirements specified in OSWER Directive #9240-05A, Specifications and Guidance for Obtaining Contaminant-Free Containers (USEPA 1990). Bottles used for the sampling activity will not contain target organic and inorganic contaminants exceeding the level specified in USEPA’s guidance.

FIELD SAMPLING PLAN

4-2 MKE\050770002

Specifications for the bottles will be verified by checking the supplier’s certified statement and analytical results for each bottle lot.

Equipment (field) blanks, trip blanks, etc., will be used to monitor for contamination. Corrective action will be taken as soon as a problem is identified. Such action may include:

• Discontinuing the use of a specific bottle lot • Contacting the bottle supplier(s) for retesting the representative bottle from a suspect lot • Assessing decontamination procedures • Re-sampling the suspected samples • Validating the data

Table 3 presents a summary of the sample containers needed for the various field investigations to be performed for groundwater sampling events.

TABLE 3 Sample Containers, Preservations, and Holding Times Oconomowoc Electroplating, Oconomowoc, Wisconsin

Parameter Container Preservation/Storage Maximum Holding Time

Water

VOCs Three 40-mL glass vials HCl to pH <2, 4°C 14 days to analysis

Metals (Total Fe, Dissolved Mn & Fe)

One 500-mL poly HN03 to pH <2, 4°C 180 days

Alkalinity One 1-L poly 4°C 14 days

Chloride, Sulfate One 1-L poly 4°C 28 days

Sulfide One 1-L amber glass NaOH to pH>9, Zn acetate, 4°C

7 days

Methane, Ethane, Ethene

Three 40-mL glass vials 4°C 14 days

Total Organic Carbon One 250-mL poly HCl to pH <2, 4°C 28 days

Ammonia (surface water sample only)

One 250-mL poly H2SO4 to pH < 2, 4°C 28 days

Ortho-phosphate (surface water sample only)

One 1-L poly 4°C 48 hours

Nitrate One 1-L poly 4°C 48 hours

4.1.3 Sample Preservation and Holding Times Sample containers, preservations, and sample holding times will meet the requirements set forth by the USEPA. Sample containers will be certified by the laboratories or vendors as pre-cleaned. Chemical preservatives will be added to certain aqueous samples in accordance with USEPA guidelines to retard sample degradation during storage and shipment prior to laboratory analysis. Sample bottles received from the CH2M HILL subcontracted laboratory will be pre-preserved by the laboratory before shipment to the field team. In addition to chemical

4—GENERAL FIELD OPERATIONS

MKE\050770002 4-3

preservatives, samples for chemical analysis will be transported to the laboratory in temperature-controlled coolers. Ice will be used to maintain the internal cooler temperature at 4 + 2°C during sample collection and shipment to the laboratory. A summary of preservation/storage requirements and holding times for the analyses to be performed are provided in Table 3.

Filtered groundwater may be submitted for metals analyses if turbidity levels cannot be reduced during purging. Filtering will occur in the field during sample collection. Samples will be filtered through a 0.45 micron filter following the procedures listed in FOP No. 5—Field Filtering Samples.

4.1.4 Sample Handling, Packaging and Shipment Sample packaging and shipping procedures are designed to ensure that the samples will arrive at the laboratory intact with their chain-of-custody (COC) forms. Sample tags and COC forms will be produced using Forms II Lite software. Sample handling, packaging, and shipping procedures are described in FOP No. 7—Sample Handling, Packaging, and Shipping.

Sample coolers will be shipped such that they will arrive at the independent laboratory the morning after sampling (priority overnight) or they will be sent through a courier to arrive on the same day. For non-CLP samples analyzed at an independent laboratory, the laboratory will be notified of the sample shipment and the estimated date of arrival of the samples being delivered.

4.2 Field Activity Documentation and Logbook Several procedures will be implemented by CH2M HILL to document the time, field conditions, well/sample locations, and parameters of the samples collected in the field. These procedures include a bound field logbook, which will be maintained to record the acquisition of each sample, parameters for laboratory analysis, and specific problems or issues at any sampling point. A binder will contain a complete record of COC forms for environmental samples and the field QC samples be completed. The following sections describe the sample documentation methods that will be used at the OEP site.

4.2.1 Field Logbook A field sampling logbook will be initiated at the start of the first onsite activity and maintained to document field activities throughout the field effort in accordance with FOP No. 3—Field Logbook.

4.2.2 Sample Chain-of-Custody For samples collected for analysis, USEPA’s COC protocols will be followed as described in the National Enforcement Investigations Center (NEIC) Policies and Procedures, EPA-330/9-78-DDI-R, Rev. June 1985. COC forms will be completed using USEPA’s Field Operations Reporting Management System (FORMS) II Lite software program. Custody procedures are described in Section 2.3.2 of the QAPP. The protocol for filling out the COC forms is provided in FOP No. 8—Documentation/Chain-of-Custody Procedures.

FIELD SAMPLING PLAN

4-4 MKE\050770002

4.3 Field Parameter Documentation Information collected in the field through visual observations, manual measurement, and/or field instrumentation will be recorded on field notebooks, data sheets, and/or forms and then entered into an electronic data log. Data will be reviewed by the FTL for adherence to the QAPP/SAP and consistency. Any concerns identified will be corrected and incorporated into the data evaluation process.

Field data calculations, transfers, and interpretations conducted by the field team will also be reviewed by the FTL. Field data logs and documents will be checked for the following:

• General completeness • Legibility/readability • Use of appropriate procedures and modifications to sampling procedures are clearly stated • Appropriate instrument calibration and maintenance records (as appropriate) • Reasonability of data collected • Correctness of sample locations • Correctness of reporting units, calculations, and interpretations

Where appropriate, field data forms and calculations will be processed and included in the appendixes to the appropriate report. Original field logs, documents, and data reductions will be kept in the project file.

4.4 Quality Control Sample Procedures Each of the offsite laboratories identified in the QAPP will have a QC program to ensure the reliability and validity of the analyses being performed. QC procedures for photoionization detector (PID), pH, DO, ORP, specific conductance, and temperature measurements include calibrating the instruments (see FOP No. 4—Equipment Calibration), measuring duplicate samples, and checking the reproducibility of the measurements by taking multiple readings from a single sample. Field sampling precision and bias will be evaluated by collecting field duplicate and equipment (field) blanks for laboratory analysis.

4.4.1 Decontamination A solution of de-ionized water, Liquinox, and 10 percent methanol will be used to decontaminate the water level indicator probe after each use. Other sampling equipment is dedicated to a specific well and will not be re-used. The multimeter and flow-through cell will be decontaminated between each well location. Decontamination water will be collected in 5-gallon pails and stored onsite in 55-gallon drums to be disposed of at a later date.

4.4.2 Field Duplicates Field duplicate samples will be used to measure the heterogeneity of the sample matrix and the precision of the field sampling and analytical process. Duplicate samples will be collected at a frequency of one duplicate per 10 samples collected.

Groundwater field duplicate samples will be collected by alternately filling first the sample bottle for one analysis and then the duplicate bottle for one analysis. This procedure will be followed


MKE\050770002 4-5

until the bottles for analyses are filled. For dissolved metals samples, a separate inline filter will be used to fill the sample and duplicate containers before shipping them to the laboratory.

The sample bottles will be labeled as described in this FSP. The samples will be preserved and stored in the same manner as the field samples. The frequency of collection will be at least 10 percent.

4.4.3 Equipment Blanks Equipment (field) blanks will be collected and analyzed to determine whether the decontamination procedure has been adequately performed and that no cross-contamination of samples is occurring due to the equipment or residual decontamination solutions. Equipment blanks will be collected for the matrices to be sampled. A consistent volume of demonstrated analyte-free distilled and deionized water will be poured directly into or over the decontaminated sampling equipment and then collected in a sample container. The sample bottles will be labeled as described in this FSP. The samples will be preserved and handled in the same manner as the groundwater samples. The frequency of collection will be at least 5 percent.

4.4.4 Trip Blanks Trip blanks will be used to determine if any onsite atmospheric contaminants are seeping into the sample bottles, or if any cross-contamination of samples is occurring during the shipment or storage of sample containers. Aqueous trip blanks will be included with groundwater samples.

Aqueous trip blanks will consist of demonstrated analyte-free distilled and deionized water preserved with 1:1 HCl to a pH of less than or equal to 2 standard units in 40 mL Teflon-lined septum vials. One set of trip blanks will accompany each sample cooler containing one or more VOC samples. The sample bottles will be labeled as described this FSP. The samples will be stored in the same manner as the groundwater samples.

4.4.5 Matrix Spike/Matrix Spike Duplicate Matrix spike/matrix spike duplicate (MS/MSD) samples will be used by the laboratories to assess the precision and accuracy of sample analysis. The MS/MSD samples will be fortified by the laboratories in accordance with the specifications of the analytical methods. Two extra volumes of sample are required for each combination of MS/MSD samples. Sample containers will be filled and stored in the same manner as field duplicate samples. The frequency for collection of MS/MSD samples will be at least 5 percent.

4.4.6 Temperature Blanks A temperature blank will be included in each cooler to allow the laboratory receiving the shipment of samples to determine if the samples have been maintained at the proper temperature. Temperature blanks will consist of an unpreserved sample container filled with distilled water. One temperature blank will accompany each sample cooler being shipped to the laboratory.

FIELD SAMPLING PLAN

4-6 MKE\050770002

4.5 Disposal of Investigation Derived Wastes The waste materials generated during a field investigation are known as IDW. Materials which may become IDW requiring proper treatment, storage, and disposal are:

• PPE, including disposable gloves, booties, etc.

• Disposable equipment (DE), including sampling tubing, used filters, broken or unused sample containers, sample container boxes, paper toweling, tape, etc.

• Groundwater obtained through well development or well purging

• Decontamination water

Management of IDW and materials (including personal protective equipment) will be performed in accordance with the USEPA guidance Guide to Management of Investigation-Derived Wastes, 9345.3-03FS, dated January 1992. DE will be containerized and appropriately labeled during the sampling events, and will be disposed of accordingly. Purged groundwater and water generated during equipment decontamination will be containerized and staged onsite in 55-gallon drums. The drums will be stored onsite until they may be disposed of at a later date. Equipment will be decontaminated as appropriate, as discussed in FOP No. 6—Field Sampling Equipment Decontamination.

4.6 Field Monitoring Instrumentation Three field monitoring instruments will be used during groundwater sampling events. These include the following:

• A water quality multimeter, which measure pH, specific conductance, temperature, DO, and ORP

• A PID

• An electronic water level indicator

Each device will be calibrated according to the manufacturer’s operating manual prior to each day’s use, as specified in FOP No. 4—Equipment Calibration.

Calibration of the equipment will be documented in the field logbook or in an equipment calibration log. During calibration, an appropriate maintenance check will be performed on each piece of equipment. If damaged or failed parts are identified during the daily maintenance check and it is determined that the damage could impact the instrument‘s performance, the instrument will be removed from service and replaced until the identified parts may be repaired or replaced.

4.7 Additional Field Operations Three additional field tasks are to be completed to support compliance and NA monitoring. These include the following:

• Installation of a nested pair of downgradient monitoring wells


MKE\050770002 4-7

• Replacement of two staff gauges along Davy Creek and its’ associated wetlands • Completion of a survey of the elevation and position of newly installed monitoring wells

and staff gauges

The two nested monitoring wells will be installed near the south bank of Davy Creek (Figure 1). One well will be screened as a water table observation well in the shallow unconsolidated aquifer, and the other well will be screened within the deep unconsolidated aquifer. This nested pair of wells will be installed using hollow-stem auger drilling methods and logged using continuous split-spoon soil sample collection as specified in FOP No. 11—Hollow-Stem Auger Drilling and Soil Sample Logging. Monitoring well construction and development will be performed as specified in FOP No. 12—Monitoring Well Installation and Development. Both wells will be constructed using 2-inch polyvinyl chloride.

The two staff gauges to be replaced will be located at about the same location as former staff gauges SG-1 and SG-2 (Figure 1). These gauges will be anchored to the substrata in a location that is accessible for elevation readings. The staff gauges will be set so that the actual elevation of the water surface can be read clearly from a distance.

Surveying work will consist of tying all newly installed wells and staff gauges into the coordinate system used for the site. At the monitoring wells, the elevation of the ground surface and top of the inner casing will be determined. For the two staff gauges, the elevation of the top of the each gauge will be determined. The northing and easting (X-Y coordinates) of each location will also be determined for each new well and staff gauge.

MKE\050770002 5-1

SECTION 5

References

CH2M HILL. 2004. Groundwater Treatment Facility Shutdown Plan.

Devaul, R.W., C.A. Harr, and J.J. Schiller. 1983. Ground-water Resources and Geology of Dodge County, Wisconsin. University of Wisconsin-Extension, Geological and Natural History Survey.

Ebasco Services Inc. 1990. Final Remediation Investigation Report at Oconomowoc Electroplating Site, Ashippun, WI.

United States Environmental Protection Agency (USEPA). 1990. Specifications and Guidance for Obtaining Contaminant-Free Containers. OSWER Directive #9240-05A.

RMT Integrated Environmental Solutions. 2004. Hydrogeologic Investigation and Groundwater Extraction System Evaluation—Former Oconomowoc Electroplating Company, Inc. Ashippun, Wisconsin.

United States Environmental Protection Agency. 1992. Guide to Management of Investigation-Derived Wastes. 9345.3-03FS.

Figures

Figure 2Conceptual Depiction of Site Aquifer

Units and Well PlacementOconomowoc Electroplating Company

Oconomowoc, WI

E012005008MK

E

Former OEP Facility

Davy CreekWetland

Area

≈ 55 ft.

SW NE

- NOT TO SCALE -

Galena - Plateville Dolomite

Maquoketa Shale with Dolomite Lenses

Erosional Surface

“Deep”Monitoring

Wells “Bedrock”Monitoring

Wells

“Shallow”Monitoring

Wells

Sand and Silty Sand ≈ 28 ft.

Clay

Clay

Bedrock Surface

Appendix A Field Operating Procedures

Low - Flow Well Sampling: Field Data Sheet

Well Number: Site:Field Crew: Date: Project #:Well Depth (ft) Purge Diameter Gal. Per foot Diameter Gal. Per footDTW (ft.) Methodology: 2" 0.163 5" 1.02Water Column (ft):Well Diameter (in): 3" 0.367 6" 1.469Gal. Per ft.:Well Volume (gal): 4" 0.653 8" 2.611Depth of Screen (ft):

TimeDTW (toc)

Flow Rate(ml/min)

TotalVolume

(gal)

pH(Std. Units) Temp (C)

Cond.(mS/cm)

ORP(mV)

D.O.(Surface)

(mg/L)Turbidity

(NTU) Color/OdorINT. Stabilization <0.3' 300-500 0.1 1 oC 3% 10 mV 10% 10%

1 VOL.2 VOL.3 VOL.4 VOL.5 VOL.6 VOL.7 VOL.8 VOL.9 VOL.

10 VOL.11 VOL.12 VOL.13 VOL.14 VOL.15 VOL.16 VOL.17 VOL.18 VOL.19 VOL.

Remarks:

Depth to Water before SamplingSample Methodology:Sample Date/Time:Signed Sampler:Filtered Metals Collected: Y / N Filter Size:Sample Ovservations:Parameters:

Field Parameters

Sampling

1

Field Operating Procedure No. 1—Low-Flow Groundwater Sampling Procedures

Purpose The following describes the procedures for the collection of groundwater samples using the low-stress (low-flow) method. Methods were developed in accordance with procedures presented in USEPA publications.

Scope This procedure is applicable for monitoring wells that are 1 inch in diameter or greater, and is considered to be appropriate for collections of VOCs, SVOCs, PCBs, and metals. This procedure is not appropriate for the collection of LNAPLs or DNAPLs. Operations manuals should be consulted for specific calibration and operating procedures.

Equipment/Materials The following list presents the equipment needed for low-flow groundwater sampling of organic site-related constituents, as specified in the FSP.

• Electronic water level indicator with an accuracy of 0.01 foot.

• Electronic oil/water interface probe with an accuracy of 0.01 foot.

• Sampling pump with adjustable flow rate. Must be either gear driven, helical driven, air-activated piston, or low-flow centrifugal. An adjustable-rate peristaltic pump can be used when the depth to water is 20 feet or less if the other pump types are not readily available.

• Teflon® or Teflon®-lined polyethylene tubing.

• An appropriate power source for the sampling pump being used.

• A graduated container to determine volume and a watch to monitor flow rate and time.

• YSI Model 6920 (or comparable) multi-parameter meter with flow-through cell. At a minimum, the meter must be capable of measuring pH, ORP, DO, turbidity, specific conductance, and temperature.

• Calibration solutions for the multi-parameter meter.

• Decontamination supplies including 10 percent methanol rinse, non-phosphate soap, and distilled water, paper towels, and plastic sheeting.

• Sample bottles and coolers for submittal to the laboratory.

FIELD OPERATING PROCEDURE NO. 1—LOW-FLOW GROUNDWATER SAMPLING PROCEDURES

2

• Peristaltic pump, disposable Teflon® tubing, and 0.45μ cellulose acetate filters for filtering dissolved metals samples

• Field notebook, sample data sheets, chain-of-custody forms, and custody seals.

• Ice for sample coolers.

• Appropriate PPE.

• PID, explosimeter, and oxygen meter (LEL/O2) and calibration gases, as appropriate.

• Tool box.

• 55-gallon drum or 5-gallon buckets, with covers, to contain purge water.

During the preparation for the field event, the list should be reviewed and modified, as appropriate, to accommodate sample collection of additional analytes or other site-related activities.

Procedures/Guidelines The following activities shall be completed before the start of purging and sampling:

1. Calibrate the multi-parameter meter, PID, and LEL/O2 meter. Record all calibration information in the field notebook.

2. Begin sampling at the monitoring well with the lowest concentrations of site-related constituents based on the results of the previous sampling event. Exceptions may be necessary to accommodate site-specific conditions. If no previous groundwater data are available, results of a MIP investigation may be used to determine areas of higher VOCs.

3. Inspect the protective well cover, concrete pad, inner well casing, and locking cap of the monitoring well and record observations in the field notebook. Polyethylene sheeting should be placed on the ground to minimize the potential for sampling equipment to contact the soil. Monitoring, purging, and sampling equipment should be placed on the sheeting.

4. Monitor the headspace of the well with the PID and LEL/O2 meters immediately after removing the inner casing cap. Readings should be noted in the field notebook. Refer to the site-specific HSP for required actions based on PID and LEL/O2 readings.

5. Measure the depth to water in the well. Also check the well for nonaqueous-phase liquids using the oil/water interface probe. Total well depth measurement using the oil/water interface probe should not be collected until all samples have been collected to minimize turbidity generated in the well. Measurements will be recorded on sample data sheets and in the field notebook.

Purging and Sampling Activities Procedures for purging and sampling are as follows:


3

1. Slowly lower the pump and tubing into the monitoring well until the pump intake is set near the midpoint of the screened interval. Record the depth of the pump intake (feet below top of inner well casing) in the field notebook.

2. Re-measure the depth to water and record the information on the sample data sheets. Leave the water level indicator in the well.

3. Place the multi-parameter meter into the flow-through cell. Connect the discharge end of the tubing from the pump to the flow-through cell of the multi-parameter probe. Place the flow-through cell discharge tubing into the 55-gallon drum or a 5-gallon bucket for collection of purge water.

4. Set the flow rate on the pump to the lowest setting, turn the pump on, and slowly increase the flow rate until water begins to flow. Using a graduated cylinder to monitor the flow rate, adjust the pump until a rate of 50 to 500 mL per minute is reached. Maintain a steady flow rate while keeping drawdown to less than 0.33 foot. If drawdown is greater than 0.33 foot, reduce the pumping rate. If a drawdown of less than 0.33 foot cannot be achieved, continue purging and record the groundwater levels and flow rate every 5 minutes.

5. Provided the drawdown does not exceed 0.33 foot (see above), record the discharge rates and drawdown on the sampling data sheets every 5 minutes, and continue purging at a flow rate to minimize drawdown. A minimum of one tubing volume must be purged before recording water quality parameters.

6. After a minimum of one tubing volume has been purged, record the values of the water quality parameters. After the initial measurement, record the water quality parameter readings concurrently with the discharge rate and drawdown measurements.

7. Continue purging until three successive readings of the water quality field parameters stabilize, following the criteria in Table 1, below. When the water quality parameters stabilize, collect the samples.

TABLE 1 Stabilization Criteria with References for Water-Quality-Indicator Parameters*


pH ± 0.1

Specific Electrical Conductance (SEC)

± 3%

Oxidation-Reduction Potential (ORP)

± 10 millivolts

Turbidity ± 10% (when turbidity is greater than 10 nephelometric turbidity units)

Dissolved Oxygen (DO) ± 0.3 milligrams per liter

*USEPA, 2002.


4

8. If a stabilized drawdown in the well cannot be maintained at less than 0.33 foot and the water level is approaching the top of the well screen, reduce the flow rate or turn the pump off for 15 minutes and allow for recovery. The pump should not be turned off if it does not have a check valve installed inline with the tubing to prevent water flowing out of the tubing into the well. If the pump must be turned off and no check valve is present, the discharge end of the tubing should be clamped to minimize the potential for water to flow back into the well. After 15 minutes, resume pumping, at a lower rate, if possible. If water levels again approach the top of the well screen, turn the pump off and allow another 15 minutes for recovery. If two tubing volumes have been removed (including the volume in the flow-through cell and tubing), collect a sample when the pump is turned on. Record this information in the field notebook so that adjustments can be made for the next sampling event.

9. For collection of samples, pumping rates should be maintained to minimize disturbance of the water column. The discharge tubing should be disconnected from the input of the flow-through cell and samples collected directly from the pump discharge tubing. Samples shall be collected in the following order: VOCs, dissolved gases, anions and alkalinity, ammonia, sulfide, TOC, total metals and dissolved metals last. Sample bottles for VOCs and/or dissolved gasses should always be filled first to ensure minimal release of volatiles and dissolved gasses. The dissolved metals require a filter to be attached to the discharge tubing and therefore should be the last sample collected as to avoid spreading any contamination that may have occurred during filter use.

9a. Collection of VOCs and dissolved gasses. Slowly fill one 40mL VOA vial to the top without overflowing (creating a convex meniscus on the top) and cap. Turn the vial upside down and tap to ensure the absence of air bubbles. Repeat this procedure for all the vials.

10. Upon completion of sample collection, remove the pump from the well, decontaminate the pump, and dispose of the tubing, if it is not dedicated.

Attachments • Low-Flow Well Sampling: Field Data Sheet

Key Checks/Items None.

1

Field Operating Procedure No. 2—Groundwater & Surface Water Level Measurements

Purpose The purpose of this procedure is to provide a general guideline for measurement of water levels in monitoring wells, piezometers, and surface water staff gages.

Scope Standard method of water level measurements.

Equipment/Materials • Water level indicator • Deionized water/liquinox/10% methanol solution in spray bottles • Photoionization detector • Paper towels

Procedures/Guidelines—Groundwater 1. Uncap the well and immediately place the photoionization meter at the wellhead for

readings.

2. Vent well caps and allow water levels to reach static levels for at least 15 minutes.

3. Decontaminate water level indicator with liquinox, 10% methanol, and deionized water.

4. Test battery on water level indicator.

5. Measure depth to water by:

• Adjusting gain/sensitivity (while probe is dry) to the maximum sensitivity that does not activate the audible sensor

• Lower probe into the well slowly until the audible sensor activates

• Raise and lower the probe slowly to precisely measure the top of the water

• Hold the tape (indicating depth) against the north top edge of the well casing (the designated measuring point) and read depth to water to the nearest 0.01 feet

6. Record depth to water

7. Measure total well depth by:

FIELD OPERATING PROCEDURE NO. 2—GROUNDWATER LEVEL MEASUREMENTS

2

• Turn gain/sensitivity off

• Lower probe into the well until the probe contacts the bottom

• Raise and lower the probe slowly so that the probed is vertical and not leaning across the diameter of the well

• Hold the tape (indicating depth) against the north top edge of the well casing and read depth to the nearest 0.01 feet

Key Checks/Items • Vent wells before measurement • Use the same location on the well casing to ensure comparability of readings • Decontaminate water level indicator with liquinox, 10% methanol, and deionized water

Procedures/Guidelines—Surface Water 1. Locate staff gage.

2. If possible, check to ensure that the staff gage has not been damaged or influenced by peak flow events.

3. Position self as close to the gage as safely possible, facing the staff-ruler side of the gage.

4. Read the staff gage and record the water level elevation.

Key Checks/Items • Confirm the location and identification number of the gage with the site map • Locate a safe position from which the gage can be read • Note the water current around the staff gage; if current is strong, record this in field

book since it can affect the gage elevation reading

1

Field Operating Procedure No. 3—Field Logbook

Purpose The purpose of this procedure is to delineate protocols for recording field survey and sampling information in a field logbook.

Scope Data generated from the use of this FOP may be used to support the following activities: site characterization, risk assessment, and evaluation of remedial alternatives.

Equipment/Materials • Field logbook • Indelible black ink pen

Procedures/Guidelines All information pertinent to a field survey or sampling effort will be recorded in a bound field logbook that will be initiated at the start of the first onsite activity. The field logbook will consist of a bound notebook with consecutively numbered pages that cannot be removed. The outside front cover of the logbook will contain the project (site) name and the specific activity (e.g., remedial investigation sampling). The inside front cover will include:

• Site name and USEPA Work Assignment number • Project number • Site manager’s name and mailing address • Sequential logbook number • Start date and end date of logbook

Each page will be consecutively numbered, dated, and initialed. All entries will be made in indelible black ink, and all corrections will consist of line-out deletions that are initialed and dated. If only part of a page is used, the remainder of the page should have an "X" drawn across it. At a minimum, entries in the logbook will include the following:

• Time of arrival and departure of site personnel, site visitors, and equipment

• Instrument calibration information, including the make, model, and serial number of the equipment calibrated

• Field observations (e.g., sample description, weather, unusual site conditions or observations, sources of potential contamination, etc.)

FIELD OPERATING PROCEDURE NO. 3—FIELD LOGBOOK

2

• A detailed description of the sampling location, including a sketch

• Details of the sample site (e.g., the elevation of the casing, casing diameter and depth, integrity of the casing, etc.)

• Sampling methodology and matrix, including a distinction between grab and composite samples

• Names of samplers and crew members

• Start or completion of borehole and monitoring well installation, sample collection activities

• Field measurements (e.g., PID readings, pH, water levels)

• Type of sample (e.g., groundwater, soil)

• Number, depth, and volume of sample collected

• Field sample number

• Requested analytical determinations

• Sample preservation

• QC samples

• Sample shipment information, including COC form number, carrier, date, and time

• Health and safety issues (including level of PPE)

• Signature and date by personnel responsible for observations

Sampling situations vary widely. No general rules can specify the extent of information that must be entered in a logbook. Records should, however, contain sufficient information so that someone can reconstruct the sampling activity without relying on the collector's memory. The field team leader will keep a master list of all field logbooks assigned to the sampling crew.

Attachments None.


1

Field Operating Procedure No. 4—Equipment Calibration

Field Air Monitoring (Photoionization Detector (PID) & Combustible Gas Indicator (CGI))

Purpose The purpose of this operating procedure is to provide a general guideline for the field measurement of air quality via PID or a CGI

Scope This is a general description of PID / CGI calibration procedures

Equipment/Materials Photoionization Detector (Mini-Rae 2000, OVM, or equivalent)

Combustible Gas Indicator (MSA Watchman or equivalent)

Procedures and Guidelines Because instruments used during the field investigation may be in fact several models produced by different manufacturers, it is not feasible to present instrument-specific details in this section. Instead, instrument-specific calibration will be performed in accordance with each manufacturer’s instructions in regard to both frequency and method.

Attachments None.

Key Checks and Items Make sure the manufacturer’s calibration/user manual is included with equipment.

Check to see that batteries are adequately charged.

Make sure all materials necessary for calibration are present (e.g. calibration gas/calibration standards, correct regulator and tubing, spare batteries and charging equipment.

Field Measurements of pH

Purpose The purpose of this operating procedure is to provide a general guideline for the field measurement of pH in water samples.

FIELD OPERATING PROCEDURE NO. 4—EQUIPMENT CALIBRATION

2

Scope Standard field pH determination techniques and instrument calibration for use on groundwater samples.

Equipment/Materials • pH buffer solution for pHs 4, 7, and 10 • Deionized water in squirt bottle • pH meter • Combination electrodes • Beakers • Solution of HCl • Glassware that has been washed with soap and water, rinsed twice with hot water, and

rinsed twice with deionized water

Procedures/Guidelines

Procedures 1. Before going into the field:

• Check batteries. • Do a quick calibration at pHs 7 and 4 to check electrode. • Obtain fresh standard solutions.

2. Calibrate meter using calibration procedure. 3. Pour sample into a clean beaker. 4. Rinse electrode with deionized water between samples. 5. Immerse electrode in sample solution. Record pH reading. 6. Recheck calibration with pH 7 buffer solution after every 5 samples.

Decontaminate pH meter before use at each sample location. Rinse probe with deionized water before storage each day. Check meter for battery charge and physical damage each day. Store meter and pH buffer solution in a cool, dry environment.

General 1. When calibrating meter, use pH buffers 4 and 7 for samples with a pH < 8, and buffers

7 and 10 for samples with a pH > 8. If meter will not read pH 4 or 10, something may be wrong with the electrode.

2. Measurement of pH is temperature dependent. Therefore, temperatures of buffers and samples should be within about 2°C. For refrigerated or cool samples, use refrigerated buffers to calibrate the pH meter.

3. Weak organic and inorganic salts, oil, and grease interfere with pH measurements. If oil or grease are visible, note it on the data sheet. Clean the electrode with soap and water, rinse it with a 10 percent solution of HCl, and recalibrate the meter.

4. Following field measurements:

• Report any problems • Compare with previous data


3

• Clean all dirt off of the meter and from inside the case • Store the electrode in a pH 4 buffer solution

5. Accuracy and precision are dependent on the instrument used. Refer to manufacturer’s manual. Expected accuracy and precision are ± 0.1 pH unit.

Attachments None.

Key Checks/Items • Check batteries • Calibrate

Preventive Maintenance • Refer to operation manuals for recommended maintenance. • Check batteries. Have a replacement set on hand.

Field Measurements of Conductivity and Temperature

Purpose The purpose of this operating procedure is to provide a general guideline for the field measurement of conductivity and temperature.

Scope Field instruments must be calibrated daily before beginning sampling activities. The methods and frequencies of calibration for the instruments used for each field activity are described below.

Equipment/Materials • Reagents—deionized water in squirt bottle and standard potassium chloride solution • Reagent preparation:

− Stock potassium chloride (KCl) solution (1.00 N): Dissolve 74.555 g KCl in deionized water and dilute to 1,000 mL in a volumetric flask.

− Standard potassium chloride solution (0.01 N): Dilute 10.0 mL of stock 1.00 N KCl solution to 1,000 mL with deionized water using a volumetric pipet and flask.

• Conductivity meter and electrodes • Beakers or jars, plastic or glass • Spare size D alkaline batteries


Groundwater

Detection limit = 1 μmho/cm @ 25°C; range = 0.1 to 100,000 μmho/cm


4

10 μmhos/cm = 1 mS/m

Calibration Check Check instrument calibration before initial daily use and at least once every 4 hours or every 5 samples, whichever is less. Check instrument with standard solution. Deviations should be noted in the field log book.

1. Turn on the instrument.

2. Hit mode key until “°C” symbol is flashing to indicate temperature corrected results (conductivity units should be μmhos).

3. Read the standard and note the results.

4. Rinse the probe with deionized water.

5. Run the sample and record the results

6. Rinse with deionized water when finished.

Decontaminate the conductivity meter before use at each sample location. Rinse the probe with deionized water before storage each day. Check the meter for battery charge and physical damage each day. Store the meter and conductivity standard in a cool, dry environment.

Operating Procedures 1. Perform calibration at beginning and end of each day.

2. Switch mode to Temperature. Allow time for the probe temperature to come to an equilibrium with the water before reading. Read the temperature on the bottom scale of the meter in degrees Celsius.

3. Switch mode to X100. If the reading is below 50 on the 0 to 500 range (5.0 on the 0 to 50 mS/m range), switch to X10. If the reading is still below 50 (5.0 mS/m), switch to the X1 scale. Read the meter scale and multiply the reading by the mode factor. The answer is expressed in μmhos/cm. Measurements are not temperature compensated.

4. When measuring on the X100 and X10 scales, depress the CELL TEST button. The meter reading should fall less than 2 percent; if greater, the probe is fouled and the measurement is in error. Clean the probe and remeasure.

Operating Suggestions

• Obstructions near the probe can disturb readings.

• When the calibration test indicates low readings, the probable cause is dirty electrodes. Hard water deposits, oil, and organic matter are the most likely contaminants.

• Caution: Do not touch the electrodes inside the probe. The plating material is soft and it can be scraped off easily.

• If cleaning does not restore probe performance, replatinizing may be required. Always rinse the probe thoroughly in tap water, then in deionized water after cleaning and


5

before storage. Note that it is best to store conductivity cells in deionized water. Collect rinsate water for storage pursuant to the Waste Management Plan.

• Most problems in obtaining good records with monitoring equipment are related to electrode fouling and inadequate sample circulation.

• Decontaminate the conductivity meter before use at each sample location. Rinse probe with deionized water before storage each day. Check meter for battery charge and physical damage each day. Store the meter and conductivity standard in a cool, dry environment.

• Water temperature readings can be taken using the conductivity meter. Switch from conductivity mode to temperature mode and record the reading in the field notebook.

Attachments None.

Key Checks/Items • Document any deviations from above procedure • Check battery • Check calibration • Clean probe with deionized water when finished • When reading results, note sensitivity settings


Field Measurements of Dissolved Oxygen

Purpose The purpose of this operating procedure is to provide a general guideline for the field measurement of dissolved oxygen in water samples.

Scope This procedure provides information regarding the equipment, materials, and procedures used for standard field dissolved oxygen determination in water samples.

Equipment/Materials • Dissolved oxygen meter • Dissolved oxygen probe • Potassium chloride (KCl) probe refill solution • Spare probe membranes • Spray bottle with deionized water


6



• Check batteries • Perform calibration • Check probe membrane

2. Record instrument make, model, and serial number in the log book or data form.

3. Calibrate the meter using the manufacturer’s recommended calibration procedure and take a duplicate reading every 10 samples.

4. Pour the collected water sample into a clean beaker.

5. Rinse probe with deionized water.

6. Immerse the probe in the sample. Record the dissolved oxygen reading in the log book or data form, and record the results once the readings have stabilized.

7. Decontaminate the probe and the beaker and cover them to guard against contamination.

General

• Measurement of dissolved oxygen is temperature dependent. Therefore, temperature correction must be accurate when calibrating.

• Following field measurements:

− Record any problems − Compare with previous data and note any large variances − Clean all dirt off of the meter and from inside the case − Store probe in calibration container with wet towel/sponge

• Accuracy and precision are dependent on the instrument used. Refer to manufacturer’s manual. Expected accuracy and precision are ± 0.1 mg/L.

Key Checks/Items • Check batteries • Check the membrane • Calibrate • Decontaminate and cover the probe

Field Measurements of Oxidation-Reduction Potential

Purpose The purpose of this operating procedure is to provide a general guideline for the field measurement of oxidative-reductive potential (ORP) in water samples.


7

Scope Standard field ORP determination techniques for use on groundwater samples.

Equipment/Materials • 0.1 M potassium ferrocyanide • 0.05 M potassium ferricyanide • Hach cat. no. 50280-05 filling solution • Distilled water in a squirt bottle • ORP meter • 2 x 100ml volumetric flasks • Beakers • Glassware that has been washed with soap and water, rinsed twice with hot water, and

rinsed twice with de-ionized water



• Check batteries.

• Obtain fresh standard solutions.

2. Calibrate the meter using the following calibration procedure:

• Transfer 100 ml of 0.1 M potassium ferrocyanide to a 150 ml beaker. Place the electrode in the solution and wait until the reading stabilizes. The potential should be about 234 mV.

• Rinse the electrode with deionized water and repeat with 0.05 M potassium ferricyanide. The potential should read about 300 mV.

3. Pour the sample into a clean beaker.

4. Rinse electrode with distilled water between samples.

5. Immerse the electrode in the sample solution. Record the ORP reading.

6. Recheck the calibration with the iron solutions after every 10 samples.

Decontaminate the ORP meter before use at each sample location. When not in use, the electrode may be stored dry, in air. Remove salt crystals on the outside of the electrode sleeve by rinsing it with distilled water and draining the filling solution from the chamber. Flush the chamber with distilled water and store it dry. Check the meter for a battery charge and physical damage each day. Store the meter and ORP calibration solution in a cool, dry environment.

General 1. The filling solution is Hach cat. No 50280-05


8

2. Following field measurements:

• Report any problems

• Compare with previous data

• Clean all dirt off of the meter and from inside the case

• Store the electrode in a pH 4 buffer solution

3. Accuracy and precision are dependent on the instrument used. Refer to manufacturer’s manual. Expected accuracy and precision are ± 10 mV.

Attachments None.

Key Checks/Items • Check batteries • Calibrate


1

Field Operating Procedure No. 5—Field Filtering Samples

Purpose The purpose of this procedure is to provide a general guideline for the field filtering of water samples for dissolved organic carbon and dissolved metals analysis.

Scope Standard method of field filtering techniques.

Equipment/Materials • Pre-preserved sample container with HNO3 • Deionized water • Peristaltic pump • 0.45 micron cellulose acetate filter • Disposable teflon tubing


Procedures 1. Place approximately 1.5 feet of disposable Teflon tubing into the peristaltic pump.

2. With the peristaltic pump running, purge the inlet and outer tubing with deionized water. Make sure all of the deionized water is out of the tubing before filtering the sample.

3. Submerge the inlet tube from the peristaltic pump into the sample to be filtered.

4. Attach a new in-line filter to the outlet tube of the peristaltic pump making sure the sample flow is in the same direction as the arrow on the filter housing.

5. Turn on the peristaltic pump and discard a small amount of the initial sample that flows out of the filter. Pump the remainder of the filtered sample into a clean sample bottle.

6. Add the required preservative to the filtered sample.

7. Discard the filter.

8. Repeat step for each sample.

FIELD OPERATING PROCEDURE NO. 5—FIELD FILTERING SAMPLES

2

Note: Any other pumps and filtering devices (pressure filtration, self-contained filtering devices, etc.) utilized for field filtering of samples will be in compliance with the WDNR PUBL-DG-038 96 Groundwater Sampling Field Manual.

Attachments None.

Key Checks/Items • All purge/rinse water must be deionized

• Preserve samples when done

1

Field Operating Procedure No. 6—Field Sampling Equipment Decontamination

Purpose The purpose of this procedure is to provide general guidelines for the decontamination of groundwater monitoring equipment, sampling equipment, and sample containers used in potentially contaminated environments.

Scope This is a general description of decontamination procedures. For specific deviations, see the unit-specific field sampling plans.

Equipment / Materials • Deionized water

• Alconox (or other phosphate free detergent) and water solution

• 10% methanol solution

• Large plastic pails or tubs for detergent and water, spray bottles for detergent, methanol and water, plastic bags and sheets

• DOT-approved 55-gallon drum for disposal of waste

Procedures / Guidelines

Monitoring/Sampling Equipment Decontamination 1. Cover ground surface with plastic sheet and position equipment over a 5-gallon bucket

and a plastic sheet.

2. Spray down the equipment with liquinox, then methanol solution, and rinse thoroughly with deionized water.

3. Collect all rinsate water in the 5-gallon bucket.

Sample Container Decontamination The outer surface of sample containers filled in the field must be decontaminated before being packed for shipment or handled by personnel without dermal hand protection.

1. Wipe the container with a paper towel dampened with detergent solution after the it has been sealed.

FIELD OPERATING PROCEDURE NO. 6—FIELD SAMPLING EQUIPMENT DECONTAMINATION

2

2. Next, wipe the container with a paper towel dampened with potable water.

3. Dispose of all used paper towels in a DOT-approved 55-gallon drum.

Key Checks/Items • Clean with solutions of detergent, methanol (or isopropanol), and deionized water • Do not use acetone for decontamination • Collect/drum all contaminated rinsate and materials • Document any deviations from the above procedure

1

Field Operating Procedure No. 7—Sample Handling, Packaging, and Shipping

Purpose The purpose of this procedure is to delineate protocols for the packing and shipping of samples to the laboratory for analysis.

Scope This FOP is applicable for all samples collected and prepared for analysis at an offsite laboratory.

Equipment/Materials • Waterproof hard plastic coolers • Plastic zipper bags • Plastic garbage bags • Absorbent packing material (not vermiculite) • Inert cushioning material (not vermiculite) • Ice • USEPA Region 5 sample tags • Chain-of-custody forms (generated by Forms II Lite software) • USEPA Region 5 custody seals • Airbills and shipping pouches (e.g., FedEx) • Clear tape • Strapping tape • Mailing labels


Prepare Bottles for Shipment 1. Arrange decontaminated sample containers into groups according to sample number.

2. Check that sample container lids are tightly secured.

3. Secure appropriate USEPA Region 5 sample tags around container lids using string or wire.

4. Arrange containers in front of assigned coolers.

5. Affix appropriate adhesive labels to each container. Protect each label with clear tape.

FIELD OPERATING PROCEDURE NO. 7—SAMPLE HANDLING, PACKAGING, AND SHIPPING

2

6. Enclose each sample in a clear, resealable, zipper bag, making sure that sample labels are visible.

Prepare Coolers for Shipment

1. Tape drains shut, inside and out.

2. Affix “This Side UP” labels on all four sides of each cooler and “Fragile” labels on at least two sides of each cooler.

3. Place mailing labels stating the laboratory address on top of the coolers.

4. Place inert cushioning material (e.g., bubble wrap, preformed poly-foam liner) into the bottom of the cooler. Do not use vermiculite.

5. Place appropriate chain-of-custody records with corresponding custody seals on top of each cooler.

6. Place all the samples inside a garbage bag and tie the bag shut.

7. Double bag and seal loose ice in resealable, plastic zipper bags to prevent melting ice from leaking and soaking the packing material. Place the ice outside the garbage bags containing the samples. Place sufficient ice in each cooler to maintain an internal temperature at 4 ± 2°C during transport.

8. Fill each cooler with enough absorbent material (e.g., Perlite, kitty litter, etc.) and packing material to prevent breakage of the sample bottles and to absorb the entire volume of the liquid being shipped (offsite sample shipment only).

9. Sign each chain-of-custody form (or obtain signature) and indicate the time and date that each cooler was custody sealed. Record the USEPA Region 5 custody seals on each chain-of-custody form.

10. Seal the laboratory copies of the chain-of-custody forms in a large resealable plastic zipper bag and tape it to the inside of the lid of each cooler. Retain the Region copies of each chain-of-custody form for return to USEPA. Each cooler must contain a chain-of-custody form (or forms) that corresponds to its contents.

11. Close lid and latch.

12. Carefully peel custody seals from backings and place intact over lid openings (right front and left back). Cover the seals with clear protection tape.

13. Tape each cooler shut on both ends, making several complete revolutions with strapping tape. Do not cover the custody seals with the strapping tape.

14. Relinquish the coolers to the carrier (e.g., FedEx). Place airbill receipts inside a mailing envelope and send it to the sample documentation coordinator along with the other documentation.

FIELD OPERATING PROCEDURE NO. 7—SAMPLE HANDLING, PACKAGING, AND SHIPPING

3

Attachments None.


1

Field Operating Procedure No. 8—Documentation/Chain-of-Custody Procedures

Purpose The purpose of this procedure is to provide a definition of “custody” and to describe protocols for documenting the transfer of custody from one party to the next (e.g., from the site to the laboratory). A documented custody trail is established through the use of sample tags and a USEPA chain-of-custody form that uniquely identifies each sample container and the identity of the individual who has possession of the sample from the its origin to its final destination. The chain-of-custody form also describes the sampling point, date, time, and analysis parameters.

Scope Sample personnel should be aware that a sample is considered to be in a person’s custody if the sample meets the following conditions:

• It is in a person’s actual possession • It is in view after being in a person’s possession • It is locked up so that no one can tamper with it after having been in a person’s physical

custody

When samples leave the custody of the sampler, the cooler must be custody-sealed and its possession must be documented.

Data generated from the use of this FOP may be used to support the following activities: site characterization, risk assessment, and evaluation of remedial alternatives.

Equipment/Materials • Computer with Forms II Lite software loaded • Printer with paper (8.5- × 11-inch) and an ink cartridge (black or color) • USEPA Region 5 Sample Tag • Forms II Lite generated tag label (encouraged, but not mandatory) • Indelible black ink pen

Procedures/Guidelines Chain-of-Custody Forms The chain of custody form must contain the following information:

• CASE NUMBER/CLIENT NUMBER: If a CLP laboratory is used, enter the case number provided by EPA’s RSCC. If the CLP is not used, enter the SAS number provided by CH2M HILL’s Sample & Analytical Coordinator.

FIELD OPERATING PROCEDURE NO. 8—DOCUMENTATION/CHAIN-OF-CUSTODY PROCEDURES

2

• EPA REGION: Enter Region “5”.

• PROJECT CODE: For OEP, choose “TFA-102”.

• CERCLIS ID: For OEP, use “WID006100275”.

• SPILL ID: For OEP, use “05M8”.

• SITE NAME/STATE: For OEP, this will be “Oconomowoc Electroplating”, “WI”.

• PROJECT LEADER: “Bill Andrae”.

• ACTION: For OEP, choose “Long Term Remedial Action”.

• SAMPLING CO.: “CH2M HILL”.

• SAMPLE NO.: This is the unique number that will be used for sample tracking. For CLP, this number is taken from a block of numbers assigned by the EPA RSCC. For non-CLP, the CH2M HILL Sample & Analytical Coordinator will assign this number.

• MATRIX: Describes the sample media (e.g. Groundwater, Soil, Wipe, etc.).

• SAMPLER NAME: The name of the sampler or sample team leader.

• CONCENTRATION: Low (L), Low/Medium (M), or High (H).

• SAMPLE TYPE: “Grab” or “Composite”.

• ANALYSIS: This indicates the analyses required for each sample.

• TAG NO.: This number appears on the bottom of the sample tag and includes a prefix (“5”) followed by a series of numbers. The entire number must appear on the chain-of-custody form.

• PRESERVATIVE: Document what preservative has been added to the sample (e.g. “HCl”, “Ice Only”, “None”).

• STATION LOCATION: This is the CH2M HILL Station Location Identifier.

• SAMPLE COLLECT DATE/TIME: Use military time.

• QC TYPE: This is for field QC only, and includes field duplicates, field blanks, equipment blanks, and trip blanks.

• DATE SHIPPED: The date that samples are relinquished to the shipping carrier.

• CARRIER NAME: The name of the shipping carrier (e.g., “FedEx”).

• AIRBILL: Airbill number used for shipping (if samples are hand-delivered to their destination, “Hand Delivered” should appear in this field).

• SHIPPED TO: This is the laboratory name and full address, including the laboratory contact. If the contact is not known, use “Sample Custodian”.

• CHAIN OF CUSTODY RECORD fields: The sampler’s signature must appear in the “Sampler Signature” and the “Relinquished By” fields. The date and time (military time) must also be included. If additional personnel were involved in sampling, their signatures should appear in the “Additional Sampler Signature(s)” field.

FIELD OPERATING PROCEDURE NO. 8—DOCUMENTATION/CHAIN-OF-CUSTODY PROCEDURES

3

Although the samples are “relinquished” to the shipping carrier, the shipping carrier does not have access to the samples as long as the shipping cooler is custody sealed. Consequently, the shipping carrier does not sign the chain-of-custody form.

• SAMPLE(S) TO BE USED FOR LABORATORY QC: This identifies which samples are to be used for matrix spike/matrix spike duplicate analyses.

• Indicate if shipment for case is complete: Use “Y” or “N”.

• CHAIN-OF-CUSTODY SEAL NUMBER: Record the custody seal numbers that appear on the Region 5 custody seals that can be found on the shipping container. There is usually a minimum of two per shipping container.

Sample Tags

Each sample container will be identified with a uniquely-numbered sample tag issued by USEPA Region 5. Each tag will contain the following information:

• Case/SAS number • The unique sample number for sample tracking • CH2M HILL station location (i.e., the sample identifier) • Date of sampling • Time the sample was collected (in military time) • All parameters for which the sample will be analyzed • Preservative used (if any) • Sample type (grab or composite) • Sample concentration (low, medium, high) • Sample matrix (groundwater, soil, air, etc.) • The signature of sample team leader • Identification stating when the sample is intended to be used by the lab for a matrix

spike/matrix spike duplicate

Attachments • Attachment 1: Forms II Lite Quick Reference Guide • Attachment 2: Example Chain-of-Custody Form, Sample Tag, Custody Seal

Key Checks/Items • All sample containers must be properly tagged.

• Each cooler must have a chain-of-custody form and the samples in the cooler (as identified by the sample tags) must match what is listed on the chain-of-custody form.

• Each chain-of-custody form must be properly relinquished (signature, date, time).

• The custody seal numbers must be written on each chain-of-custody form.

• The shipping cooler must be custody sealed in at least two places.

1

FOP-8, Attachment 1 Forms II Lite Quick Reference Guide

Getting Started (a) Click on the Start button on the Windows Desktop and select Programs. Select Forms II

Lite and click on the FORMS II Lite item. The FORMS II Lite application will begin. (b) Click File on the Main Menu bar. Click on the New Site item. The first data entry screen

will appear.

Step 1 - Enter Site Information

a) Enter all relevant information necessary for Chain-of-Custody paperwork (in accordance with Regional guidance). For CLP Traffic Reports (TRs) this includes: • Site Name • State • EPA Region Number • CLP Case Number • Lead Sampler

b) Click the Next button to proceed to Step 2.

Step 2 - Select Sampling Team a) Select sampling team members from the Unassigned Team Members window by

clicking on each name. b) Click the > button. The selected name will move to the SelectedTeam window. Repeat

until all team members for this sampling event are selected. c) Click the Add/Edit Team Members button to add any remaining sampling team

members' names that do not appear in the Unassigned Team Members window. d) Enter the first and last name of each sampler. If you would like to add the sampler to the

permanent list, click the Add to Permanent List box. After you have entered the samplers’ names, click the OK button. These samplers will appear in the Selected Team Members window on the Select Sampling Team screen.

e) Click the Next button to proceed to Step 3.

Step 3 - Select Analysis

a) Select an analysis from the Available Analyses window by clicking on the analysis. b) Click the > button. The selected analysis will move to the Selected Analyses window.

Repeat until all analyses to be performed on samples collected for this sampling event are selected.

c) To edit Turnaround Time, click the Edit Turnaround Days button. The Edit Project and Turnaround screen will appear.

d) Click on the Turnaround Time drop down menu to select the number of days or type in a value. Click Close to close screen.

e) Click the Next button to proceed to Step 4.

2

Step 4 - Enter Station

a) Enter all relevant information necessary for Chain-of-Custody paperwork (in accordance with Regional guidance). For CLP TRs this includes: • Station Name and Location • Sample Matrix • Sample Date/Time • Sample Type • Sampler Name

b) The Sample Date/Time field is strictly military time. You may click on the System Date/Time checkbox to populate the current system date/time value into the sample date/time.

c) Click the Add Station button to enter the name of a new station and continue with the station locations. To enter a new station location associated with a previously entered station, click on the station name, then click the Add Location button, and enter the name of the new station location.

d) Click the Next button to proceed to Step 5.

Step 5 - Assign Bottles and Samples

a) Select the Station Location from the Station/Location window. b) Select the analyses associated with the containers from the Analysis window. If more

than one analysis is associated with a container, select the additional analysis(es) by holding down the control key, and clicking on the additional analysis(es).

c) Enter the number of bottles that will be assigned a specific analysis or set of analyses. d) Enter the sample tag prefix and starting tag number. Click Auto Increment Tag Number

if you wish to assign sequential tag numbers for your sampling event. Sample numbers are automatically and sequentially assigned for your sampling event and are unique per Station Location.

e) By default CLP sample numbers are automatically used for CLP analyses. Note that FORMS II Lite generates CLP sample numbers using a BASE 32 system which differs from the CLASS generated CLP sample numbers.

f) Edit the sample number and other pertinent information for these samples in the space provided. After you have confirmed your entries, click the down arrow.

g) Repeat steps 5b through 5f until all desired analyses have been assigned to bottles. h) Click the Next button to proceed to Step 6.

Generate Labels

a) Click the Generate Labels button in Step 5. The application automatically displays samples for the current Station Location. These are the samples for which labels will be generated. Click the appropriate checkbox at the bottom of the screen to select all samples for the station or site. Enter the number of labels to print next to each record if you need more than one.

b) Click the Generate Labels button and select the appropriate label template to view, then click OK. Edit an existing template by clicking the Edit Label button. If you wish to add a new label template, click the Add New Label button and follow the wizard to create a

3

new template. Enter the number of blank labels to control printing on a label other than the first one on the page.

c) View the labels at the end of the edit label or new label process. If labels are not acceptable, close the view and edit the label template. If the labels are acceptable, print the labels.

d) Select File and then Print from the Main Menu bar. Select the desired number of copies to be printed and click the OK button to print the labels. Click Close to return to Step 5.

Step 6 - Select Samples and Assign Lab

a) Select a laboratory from the Lab Code drop down menu. If the laboratory where samples will be shipped does not appear in the list, click the Add Lab button and add the lab information.

b) Select samples from the Unassigned Samples window by holding down the [Ctrl] key and clicking on each sample that will be shipped to this laboratory. After you have selected all the samples for the laboratory, click the down arrow.

c) Repeat steps 6a and 6b until all samples have been assigned to laboratories. d) Click the Next button to proceed to Step 7.

Step 7 - Select Labs and Assign Shipping

a) Enter the carrier, date of shipment and airbill number. b) Select samples from the Unassigned window by holding down the [Ctrl] key and

clicking on each sample that will be shipped using this airbill. After you have selected the samples to be shipped, click the down arrow.

c) Repeat steps 7a and 7b until all samples have been assigned airbill numbers. d) Click the Finish button for system generated TRs. FORMS II Lite will then display a

screen that enables you to view and print TRs for the site. e) Click Next and proceed to Step 8 to customize TRs for specific sets of samples.

Step 8 - Customize Traffic Report a) Confirm the last four digits of the TR number. (The first two digits represent the Region

number, the next nine digits are a random number and the next six digits are the date the TR was created, and the last four digits are automatically incremented by the system but may be edited by the user.)

b) Select a shipment from the Shipping window. Select the samples from the Samples window that will be assigned to this TR. After you have selected the samples, click the down arrow. (NOTE: samples must be of the same program type and must have the same project code to be assigned to a single TR.)

c) Repeat steps 8a and 8b until all samples have been assigned. d) Click the Finish button. FORMS II Lite will display a screen that will enable you to view,

print, archive and export TRs. Follow the directions to print the TRs.

Quick Edit a) On the View/Print TR screen displayed after completion of Step 8, click the Quick Edit

button.

4

b) The user may edit most data fields, except those in red, prior to printing a TR. Also able to sort and filter any column and print a report.

Helpful Hints to Use FORMS II Lite 4.0

This Quick Reference Guide is designed to help FORMS II Lite users enter information for their sampling events and generate bottle labels and Chain-of-Custody paperwork. FORMS II Lite provides users the flexibility to enter most of their information ahead of the sampling event.

FORMS II Lite allows users to:

• Add values that are not included in the “list and pick” menus: Select Admin from the Main Menu bar, enter the password to log in. Admin now shows the user as being (logged in). Select Reference Tables, and choose the table that requires editing.

• Customize screens and disable non-key fields: While logged into Admin on the Main Menu Bar, select Custom Features and click on Field Names. Field names and non-key fields can be renamed or hidden on the screen.

• Review the data entered throughout the data entry process by clicking on the Quick View button in Steps 4 through 8.

• Select multiple items by highlighting the first item, then hold down the [Ctrl] key and click on the additional items. Or simply click and drag to highlight multiple items.

• Sort data displayed in windows by clicking on the column label. Click on a second column label for a secondary sort.

• Specify more than one sampler’s name for samples collected at a

• specific station location. In Step 4, select a sampler’s name, then click within the data entry field after the name. Type a comma and type in the second name.

• Export Site information as either a text or (.dbf) file.

• Note: FORMS II Lite will not allow information that has been typed over to be saved as a separate file. Once a value in a field has been replaced (edited) with a new value, the original value is lost.

User Preferences

• The following features are maintained in User Preferences under Admin on the Main Menu bar and can be turned on or off.

• Select Copy Station to make the button available in Step 4 to duplicate the current station and its station location information. Copy Location duplicates station locations.

• Select the option Use Default Number of Bottles, set in the Analysis Reference Tables, to populate the number of containers for each analysis in Step 5.

5

• Select Assign All to make the button available in Step 5 to assign each of the analyses to a separate container. Set the number of containers for each analysis in the bottles field or define through User Preferences.

• Select One-Step Printing to make this button available in Step 5 to print labels or tags with a single click. Label template, and number of copies are defined in User Preferences.

1

FOP-8, Attachment 2 Chain-of-Custody Form, Sample Tag, Custody Seal

1

Field Operating Procedure No. 9—Surface Water Sampling Procedures

Purpose The following describes the procedures for the collection of surface water samples. Methods were developed in accordance with procedures presented in previous USEPA publications.

Scope This procedure is applicable for collecting surface water samples that can be collected directly from the surface water body by direct submersion of a sample container or by using a glass or stainless steel beaker to collect a sample for filling sample bottles. This must be performed in a safe manner from the water’s edge. Wading to collect the sample is not normally acceptable, as this will agitate sediment into the water column. Wading is only considered to be part of acceptable sampling procedure if the current is significant enough that the sample will not be impacted by recently agitated sediment.

Equipment/Materials The following list presents the equipment needed for surface water sampling of organic site-related constituents, as specified in the FSP.

• Sample bottles and coolers for submittal to the laboratory. • A calibrated multi-meter • A clean glass or stainless steel beaker/container. • Field notebook, sample data sheets, chain-of-custody forms, and custody seals. • Ice for sample coolers. • Appropriate PPE.

During the preparation for the field event, the list should be reviewed and modified, as appropriate, to accommodate sample collection of additional analytes or other site-related activities.

Procedures/Guidelines The following activities shall be completed in order to collect a viable sample:

1. Sample collector should position themselves safely along the edge of the water body.

2. Immerse multi-meter probe in water body and record field parameters values once they have stabilized.

3. Rinse glass or stainless steel beaker in water body several times.

FIELD OPERATING PROCEDURE NO. 9—SURFACE WATER SAMPLING PROCEDURES

2

4. Immerse glass or stainless steel beaker in water body and fill.

5. Transfer water in beaker to sample container. Any sample containers containing chemical preservative should not be overfilled.

6. Repeat until adequate sample volume is collected.

7. Place all samples in designated sample cooler(s).

Attachments None.

Key Checks/Items Make sure glass or stainless steel beaker is rinsed several times in sample water before sampling.

1

Field Operating Procedure No. 10—Private Residential Well Groundwater Sampling Procedures

Purpose The following describes the procedures for the collection of groundwater samples from private residential wells. Methods were developed in accordance with procedures presented in previous USEPA publications.

Scope This procedure is applicable for residential wells that are functioning within their designed specifications, and is considered to be appropriate for collections of VOCs, SVOCs, PCBs, and metals. This procedure is not appropriate for the collection of LNAPLs or DNAPLs. The well owner should be consulted for any specific well operating procedures.

Equipment/Materials The following list presents the equipment needed for groundwater sampling of organic site-related constituents, as specified in the FSP.

• Sample bottles and coolers for submittal to the laboratory • A calibrated multi-meter • Field notebook, sample data sheets, chain-of-custody forms, and custody seals • A clean section of garden hose • A clean 5-gallon bucket • Ice for sample coolers • Appropriate PPE • Tool box

During the preparation for the field event, this list should be reviewed and modified, as appropriate, to accommodate the needs of the well owner and/or the collection of additional analytes.


Pre-sampling Activities (Purging) The following activities shall be completed before the start of sampling:

FIELD OPERATING PROCEDURE NO. 10—PRIVATE RESIDENTIAL WELL GROUNDWATER SAMPLING PROCEDURES

2

1. If possible, locate a tap/faucet/spigot that will allow samples to be collected upstream of any water treatment/conditioning, such as softeners, filters, or chlorination systems.

2. Confirm that the tap/faucet/spigot selected is deemed acceptable for sampling to the well owner.

3. If present, remove aerator on tap/faucet/spigot.

4. Connect garden hose to tap/faucet/spigot, if necessary, and run water through the plumbing system to keep the well running continuously for at least 15 minutes, and also allow any storage/pressure tanks to be drained.

5. Make sure any water being purged is properly collected/diverted out of or away from the Owner’s buildings using the garden hose.

Sampling Activities Procedures for sampling are as follows:

1. Fill the 5-gallon bucket from the selected collection point, and immerse the multi-meter probe in the water. Record field parameter values once they have stabilized.

2. Fill all sample containers directly at selected tap/faucet/spigot. Any sample containers containing chemical preservative should not be overfilled.

3. Place all samples in designated sample cooler(s).

4. Make sure sampling point is shut off before leaving private property.

Note: Sample bottles for VOCs and/or dissolved gasses will be filled first to ensure minimal release of volatiles and dissolved gases. The 40 mL VOA vial will be sampled directly from the tap/faucet/spigot at a low flow rate. The vial should be filled to the top without overflowing (creating a convex meniscus on the top) and cap and should be turned upside down and tapped to ensure the absence of air bubbles. This procedure should be repeated for all VOA vials.

Attachments None.

Key Checks/Items • System purge. • Water softner/filter. • Sample tap aerator. • Sources of contamination.

1

Field Operating Procedure No. 11—Hollow-Stem Auger Drilling and Soil Sample Logging

Purpose The purpose of this field operating procedure is to provide guidance for logging soil samples using hollow-stem auger drilling methods.

Scope The method described for hollow-stem auger soil sampling is applicable for soil sampling below the ground surface. Specific equipment and the responsibilities of drilling subcontractors are described in the project specific work plan and/or contracting documentation.

Equipment/Materials • As specified in ASTM Method D-1586-99 • Photoionization Detector (PID) & Combustible Gas Indicator (CGI) • Soil/Rock logging sheets • Personal Protective Equipment

Procedures/Guidelines 1. Ensure that augers, split-barrel samplers (split spoons), and other non-dedicated

downhole equipment and sampling equipment are decontaminated.

2. Wear appropriate personal protective equipment (PPE), as required by the H&S plan.

3. While drilling, subsurface soil samples will be collected continuously from the ground surface to the bottom of the boring using 2-foot–long, split-barrel samplers advanced in accordance with the ASTM Method D-1586-99. Between sampling intervals, the samplers will be decontaminated in accordance with the procedures outlined in Field Operating Procedure No. 6—Field Sampling Equipment Decontamination.

4. Drill rig operators will open the sampler and present it to the field staff for logging and/or sampling. PID screening of each sampler interval will be performed by the field geologist/field technician, and will be recorded on the borehole log sheet. Samples will be logged according to the visual methods outlined in ASTM Method D-2487-98.

5. After an interval is logged, the hollow stem augers will be advanced to the next sampling interval. During auger advancement, a bottom plug or drill bit will be inserted into the auger to prevent soils from collecting within the auger annulus. Prior to collection of the next soil sample, the bottom plug or drill bit will be temporarily

FIELD OPERATING PROCEDURE NO. 11—HOLLOW-STEM AUGER DRILLING AND SOIL SAMPLE LOGGING

2

removed from the auger. This procedure of sampling, auger advancement, and sampling will continue to planned depth of the boring, or until refusal.

6. The drilling subcontractor will be responsible for notifying the field geologist/field technician of changes in drilling conditions, and keeping a separate general log of the soils encountered and blow counts (the number of hammer blows required to advance the sampler 6 inches into the ground).

7. Excess drill cuttings will be contained in designated 55-gallon drums.

Key Checks/Items 1. Verify that the drill rig is clean and in proper working order.

2. Ensure that the drilling subcontractor collects and contains all soil cuttings, IDW (investigation-derived waste), and decontamination rinse water.

1

Field Operating Procedure No. 12—Monitoring Well Installation and Development

Purpose To provide site personnel with a review of the well installation procedures that will be performed. These procedures are to be considered general guidelines only, and are in no way intended to supplement or replace the contractual specifications of the driller’s subcontract.

Scope The methods describe the procedure for monitoring well installation following hollow-stem auger drilling in unconsolidated sediment/soil. Specific equipment and the responsibilities of drilling subcontractors are described in the project specific work plan and/or contracting documentation. All well construction and development shall meet the requirements of Wisconsin Department of Natural Resources regulations (NR 141).

Equipment/Materials • Personal Protective Equipment (PPE) • Photoionization Detector (PID) • Combustible Gas Indicator (CGI) • Monitoring well construction form


Unconsolidated Sediment/Soil Well Installation (HSA Drilling Methods) 1. Monitoring wells will be installed using hollow-stem auger drilling methods described

in Field Operating Procedure No. 11— Hollow-Stem Auger Drilling and Soil Sample Logging. For the purposes of installing a 2-inch diameter monitoring well, augers with at least 4.25 inch inner diameter will be used. The monitoring well shall be sufficiently plumb and straight such that there is no interference with the utilization of sampling equipment.

2. While drilling, subsurface soil samples will be collected continuously from ground surface to the bottom of the boring using a 2 ft long split-barrel samplers advanced in accordance with ASTM Method D-1586-99.

3. After augers have been advanced to the required depth and soil sampling/logging is complete as specified by the on-site field geologist/field technician, the monitoring well materials will be installed through the augers as specified in ASTM Method D-5784-95.

FIELD OPERATING PROCEDURE NO. 12—MONITORING WELL INSTALLATION AND DEVELOPMENT

2

The monitoring well will consist of a length of 2-inch diameter schedule 40 PVC flush threaded casing (meeting ASTM D-1785 specifications) to a 0.010-inch machine slotted well screen (appropriate for the surrounding material and well function). When screening a water table well, the screen may not exceed 15 feet in length. Piezometer screens may not exceed 5 feet.

4. A sand filter pack, consisting of a washed and graded silica sand with at least 90% of the retained grain size greater than 0.010 inches, will be placed between the outside of the well screen and the borehole wall. A downhole tape measure will be used to assess the proper emplacement of the sand filter pack. The sand filter pack will extend from 6 inches below the bottom of the well screen to a minimum of 2 feet above the top of the well screen.

5. A bentonite seal, consisting of a bentonite slurry or bentonite chips, will be placed on top of the sand filter pack and will be a minimum thickness of 2 feet. If the seal extends above the groundwater table and bentonite chips were used, potable water will be used to hydrate the bentonite.

6. Following the installation of the bentonite seal, the remaining annular space between the outside of the riser casing and the borehole wall will be filled with a cement/bentonite grout mixture.

7. A locking compressive plug will be inserted into the top of the riser casing. An above-grade protective casing will be installed over the top of the riser casing and cemented in place. A lock will also be installed to add protection for the well.

8. Monitoring well specifications will be recorded on a monitoring well construction form.

9. Excess drill cuttings will be contained in designated 55-gallon drums.

Well Development Following installation, the monitoring wells will be developed to remove any fine-grained materials that may have settled in and around the well screen during installation. This helps to ensure that the well is transmitting groundwater representative of the surrounding aquifer. Well development activities will be conducted a minimum of 24 hours after completion of well construction. This allows time for the bentonite and cement to cure.

Well development will be completed using an appropriate method, such as a low-yield submersible pump, air jetting, or bailing. Development will be accomplished by surging the well screen followed by purging the suspended sediments. Water quality parameters such as pH, temperature, and specific conductance may be periodically monitored to assess stabilization of formation water within the well screen. Well development will continue until the well yields relatively sediment-free water and/or monitored water parameters have stabilized. These parameters can be considered stabilized when pH measurements are within 0.5 units, temperature variation within 0.1 degrees C, and specific conductance within 10 percent.

A well development record will be maintained by the on-site field geologist/field technician. This record should include documentation of well development methods used, the estimated volume of water purged, and results of water quality parameters monitored.

FIELD OPERATING PROCEDURE NO. 12—MONITORING WELL INSTALLATION AND DEVELOPMENT

3

Specific NR 141 rules regarding monitoring well development are dependant upon whether or not the well can be purged dry or not. If the well cannot be purged dry, development of the well should consist of 30 minutes of surge and purge cycling. Following the 30 minutes of surge/purge cycling, the well should be pumped or bailed until “10 well volumes of water are removed or until the well produced sediment free water”. For wells that can be purged dry, development should be performed in such a way as to limit agitation by slowly purging the well. No water should be added to the well and surging should not be performed.

Fluids generated during well development activities will be contained in on-site 55-gallon drums. Equipment used during well development will be decontaminated in accordance with Field Operating Procedure No. 6—Field Sampling Equipment Decontamination.

Key Checks/Items 1. Verify that the PVC materials are new, clean, undamaged, and threaded properly.

2. Ensure that the drilling subcontractor collects and contains all development purge water, IDW (investigation-derived waste), and decontamination rinse water.

3. Verify that all NR 141 requirements are being met with regards to well construction and development.