anaconda smelter npl site soils operable...

ANACONDA SMELTER NPL SITE ANACONDA REGIONAL WATER, WASTE & SOILS OPERABLE UNIT

Draft Final Long-Term Groundwater Monitoring Program Quality Assurance Project Plan (QAPP)

Atlantic Richfield Company March 5, 2015

ANACONDA SMELTER NPL SITE ANACONDA REGIONAL WATER, WASTE & SOILS OPERABLE UNIT

Draft Final Long-Term Groundwater Monitoring Program Quality Assurance Project Plan (QAPP) Prepared for:

Atlantic Richfield Company 317 Anaconda Road Butte, Montana 59701

Prepared by:

Pioneer Technical Services, Inc. 307 East Park Street, Suite 421 Anaconda, Montana 59711

March 5, 2015

APPROVAL PAGE

Quality Assurance Project Plan for Long-Term Groundwater Monitoring

Anaconda Smelter NPL Site Approved: Date: Charles Coleman, Site Project Manager, EPA, Region 8 Approved: Date: Joel Chavez, Project Officer, Montana DEQ Approved: Date: Shannon Dunlap, Operations Project Manager

Atlantic Richfield Company

Plan is effective on date of approval.

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DISTRIBUTION LIST Anaconda Smelter NPL Site

Quality Assurance Project Plan (QAPP) Anaconda-Deer Lodge County, Montana

QAPP Recipients Title Organization Telephone Number E-mail Address Charles Coleman Remedial Project Manager EPA (406) 457-5038 [email protected] Julie DalSoglio Director EPA Region 8 EPA (406) 457-5025 [email protected]

Joe Vranka Superfund Branch Chief EPA (406) 457-5021 [email protected] Andy Lensink Senior Attorney for Mining EPA (303) 312-6908 [email protected]

Katherine Haque-Hausrath Attorney DEQ (406) 841-5019 [email protected] Joel Chavez State Project Officer DEQ (406) 444-2251 [email protected]

Gunnar Emilsson EPA Contractor CDM Smith (406) 441-1422 [email protected] Connie Ternes-Daniels Chief Executive ADLC (406) 563-4000 [email protected]

Shannon Dunlap Operations Project Manager Atlantic Richfield (406) 782-9964 [email protected] Jenni Harris Associate Project Manager Atlantic Richfield (406) 782-9964 [email protected] Cord Harris Life Cycle Manager Atlantic Richfield (714) 670-3903 [email protected] Terry Moore Senior Technologist Atlantic Richfield (214) 505-3992 [email protected] Tim Hilmo Atlantic Richfield Contractor Atlantic Richfield (406) 782-9964 [email protected] Jill Kelley Atlantic Richfield Legal Contractor Kelley Services (630) 580-9575 [email protected] Don Booth Atlantic Richfield Contractor Booth Consulting (406) 579-5455 [email protected] John Davis Atlantic Richfield Legal Contractor Poore, Roth and Robinson (406) 497-1200 [email protected] Bill Duffy Atlantic Richfield Legal Contractor Davis, Graham & Stubbs, LLP (303) 892-7372 [email protected]

Duane Logan Atlantic Richfield Contractor Pioneer Technical Services, Inc. (406) 563-9371 [email protected] Nicole Hockaday Atlantic Richfield Contractor Pioneer Technical Services, Inc. (406) 563-9371 [email protected]

Kevin Bethke Atlantic Richfield Contractor TREC, Inc. (406) 586-8364 [email protected]

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TABLE OF CONTENTS Page

APPROVAL PAGE ......................................................................................................................... i

DISTRIBUTION LIST ................................................................................................................... ii

LIST OF FIGURES ........................................................................................................................ v

LIST OF TABLES .......................................................................................................................... v

LIST OF APPENDICES ................................................................................................................. v

1.0 INTRODUCTION .............................................................................................................. 1

2.0 PROJECT MANAGEMENT .............................................................................................. 1 2.1 Project Organization and Responsibilities .............................................................. 1 2.2 Problem Definition and Background ...................................................................... 2 2.3 Project Description and Schedule ........................................................................... 3 2.4 Quality Objectives and Criteria .............................................................................. 4

2.4.1 Data Quality Objectives .............................................................................. 4 2.5 Special Training .................................................................................................... 10 2.6 Documents and Records ....................................................................................... 10

2.6.1 Property Access Agreements .................................................................... 10 2.6.2 Field Logbooks/Data Sheets ..................................................................... 10 2.6.3 Field Photographs ..................................................................................... 12 2.6.4 Transducer Data ........................................................................................ 12 2.6.5 Chain of Custody Records ........................................................................ 12 2.6.6 Analytical Laboratory Records ................................................................. 12 2.6.7 Project Data Reports ................................................................................. 13 2.6.8 Quality Records ........................................................................................ 13

3.0 MEASUREMENT AND DATA ACQUISTITION ......................................................... 13 3.1 Sampling Process and Design ............................................................................... 14

3.1.1 Monitoring Well Designation and Sample Frequency .............................. 14 3.1.2 Groundwater Sampling from Monitoring Wells ....................................... 16

3.1.2.1 Sample Analysis and Procedures .................................................. 17 3.1.3 Groundwater Expression Sampling .......................................................... 17

3.1.3.1 Sample Analysis and Procedures .................................................. 18 3.1.4 Sample Disposal........................................................................................ 18 3.1.5 Sample Labeling and Identification .......................................................... 18 3.1.6 Field Documentation ................................................................................. 19 3.1.7 Sample Handling, Chain of Custody and Shipping .................................. 19 3.1.8 Laboratory Sample Handling and Storage ................................................ 20

3.2 Laboratory Methods .............................................................................................. 20 3.2.1 Sample Preparation Methods .................................................................... 21

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Anaconda Smelter NPL Site

3.2.2 Sample Analysis Methods......................................................................... 21 3.3 Quality Assurance/Quality Control....................................................................... 21

3.3.1 Field Quality Control Samples.................................................................. 21 3.3.2 Laboratory Quality Control Samples ........................................................ 22

3.4 Instrument/Equipment Testing, Inspection and Maintenance .............................. 24 3.4.1 Field Equipment ........................................................................................ 24 3.4.2 Laboratory Equipment .............................................................................. 25

3.5 Inspection/Acceptance of Supplies and Consumables .......................................... 25 3.6 Data Management Procedures .............................................................................. 25

4.0 ASSESSMENT AND OVERSIGHT ................................................................................ 26 4.1 Corrective Actions ................................................................................................ 27 4.2 Corrective Action during Data Assessment .......................................................... 28 4.3 Quality Assurance Reports to Management ......................................................... 28

5.0 DATA REVIEW AND USABILITY ............................................................................... 28 5.1 Data Review and Verification ............................................................................... 28

5.1.1 Field Data Review..................................................................................... 29 5.1.2 Laboratory Data Review ........................................................................... 29 5.1.3 Laboratory Data Reporting Requirements ................................................ 29 5.1.4 Laboratory Electronic Data Deliverable ................................................... 30 5.1.5 Specific Quality Control/Assessment Procedures .................................... 30

5.2 Internal Data Review ............................................................................................ 30 5.2.1 Field Quality Control Data........................................................................ 30 5.2.2 Laboratory Chemistry Data....................................................................... 30

6.0 REFERENCES ................................................................................................................. 33

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LIST OF FIGURES Figure 1 Project Organization Chart Figure 2 ARWW&S OU Long-Term Groundwater Monitoring Plan

LIST OF TABLES Table 1 Anaconda Smelter NPL Site Groundwater Monitoring Plan Table 2 Work Schedule Table 3 Water Quality Performance Standards Table 4 Precision, Accuracy and Completeness Calculation Equations Table 5 Summary of Laboratory Quality Assurance/Quality Control Checks Table 6 Summary of Sampling and Monitoring activities Table 7 Engineered Cover Wells Sampling Schedule Table 8 Monitoring Well Sample Summary Table 9 Spring Sample Summary Table 10 Sample Identification Table 11 Summary of Sample Analyses and Preparations Table 12 Method Detection Limits and Reporting Limits Table 13 Project Sampling Field SOP References Table 14 Laboratory SOPs

LIST OF APPENDICES Appendix A Standard Operating Procedures Appendix A1 Field Standard Operating Procedures Appendix A2 Laboratory Standard Operating Procedures Appendix B Corrective Action Report Appendix C Data Validation Checklists

REVISION SUMMARY

Revision No.

Author Version Description Date

Rev 1 Nicole Hockaday Draft Issued for Internal Atlantic

Richfield Company Review 02/2015

Rev 2 Nicole Hockaday

Draft Final Issued for Agency Review 03/5/2015

Draft Final Long-Term Groundwater Monitoring Program QAPP Page v of viii


LIST OF ACRONYMS AND ABBREVIATIONS amsl above mean sea level Atlantic Richfield Atlantic Richfield Company Atlantic Richfield PM Atlantic Richfield Project Manager ARWW&S Anaconda Regional Water, Waste and Soils CAR Corrective Action Report CCB Continuing Calibration Blank CCV Continuing Calibration Verification CFRSSI Clark Fork River Superfund Site Investigations CLP Contract Laboratory Program COC Constituent of Concern CPM Contractor Project Manager DEQ Montana Department of Environmental Quality DI Deionized DO Dissolved Oxygen DQA Data Quality Assessment DQO Data Quality Objectives DSR Data Summary Report EDD Electronic Data Deliverable EDW Event Driven Well EPA U.S. Environmental Protection Agency FS Feasibility Study GPS Global Positioning System GWIC Ground-Water Information Center HDPE High Density Polyethylene HSSE Health Safety Security and Environment ICB Initial Calibration Blank ICP-MS Inducted Coupled Plasma-Mass Spectrometry ICV Initial Calibration Verification IM Integrity Management LCS Laboratory Control Sample LCSD Laboratory Control Sample Duplicate MB Method Blank MBMG Montana Bureau of Mines and Geology MDL Method Detection Limit MS Matrix Spike Sample MSD Matrix Spike Sample Duplicate MW Monitoring Well NPL National Priorities List ORP Oxidation-Reduction Potential OU Operable Unit

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PARCCS precision, accuracy, representativeness, completeness, comparability and sensitivity

PDS Post Digestion Spike POC Point of Compliance ppb parts per billion PPE Personal Protective Equipment PRP Potentially Responsible Party QA Quality Assurance QA/QC Quality Assurance/Quality Control QAPP Quality Assurance Project Plan QC Quality Control RA Remedial Action RAWP Remedial Action Work Plan RI Remedial Investigation RL Reporting Limit ROD Record of Decision RPD Relative Percent Difference RSD Relative Standard Deviation SAP Sampling Analysis Plan SC Specific Conductance SOP Standard Operating Procedure SSHASP Site-Specific Health and Safety Plan TDS Total Dissolved Solids TI Technical Impracticability WMA Waste Management Area µm Micron ºC degrees Celsius

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1.0 INTRODUCTION The purpose of this Quality Assurance Project Plan (QAPP) is to provide guidance for groundwater sampling and monitoring activities for the Anaconda Regional Water, Waste and Soils (ARWW&S) Operable Unit (OU) of the Anaconda Smelter National Priorities List (NPL) Site and to reference the documents necessary to describe the Quality Assurance/Quality Control (QA/QC) policies and procedures to be used during data collection and analyses. This QAPP was prepared in a manner consistent with the Uniform Federal Policy for Quality Assurance Project Plans: Evaluating, Assessing, and Documenting Environmental Data Collection and Use Programs (EPA, 2005) and the forthcoming Anaconda Smelter NPL Site Quality Management Plan (QMP). This QAPP includes the following four basic element groups: • Project management and objectives; • Measurement and data acquisition; • Assessment and oversight; and • Data review. The sections below provide the project elements and include the appropriate content needed for planning, sampling, monitoring and analyses within the site. The sections in this QAPP expand or reference information in other site-wide documents to comply with the Uniform Federal Policy for Quality Assurance Project Plans: Evaluating, Assessing, and Documenting Environmental Data Collection and Use Programs (EPA, 2005) and to present project-specific requirements. 2.0 PROJECT MANAGEMENT This section addresses project administrative functions and project concerns, goals and approaches to be followed during sampling and monitoring activities on the site. 2.1 Project Organization and Responsibilities An organizational chart showing the overall organization of the project team is provided as Figure 1. Responsibilities of key individuals comprising the project team and their detailed responsibilities are listed below. Atlantic Richfield Project Manager (Atlantic Richfield PM) The Atlantic Richfield PM monitors the performance of the contractor(s), consults with the Contractor Project Manager and Contractor QA Officer on deficiencies, and aids in finalizing resolution actions. Atlantic Richfield Quality Assurance Manager (Atlantic Richfield QA Manager) The Atlantic Richfield QA Manager is responsible for maintaining the official, approved QAPP and documenting and distributing changes. Contractor Project Manager (CPM) The CPM is responsible for scheduling all sampling work to be completed and ensures that the work is performed in accordance with the requirements contained herein. The CPM is also

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responsible for consulting with the Contractor QA Officer regarding any project deficiencies and resolutions. Contractor Quality Assurance Officer The Contractor QA Officer is responsible for reviewing field and laboratory data and evaluating data quality. Field Team Leader The Field Team Leader ensures that the QAPP has been reviewed by all members of the field team and is properly followed during field activities. The Field Team Leader will conduct daily safety meetings, assist in field activities, and document activities in the field logbook. The Field Team Leader is responsible for facilitating field activities, managing equipment, and problem solving and decision making in the field. The Field Team Leader is responsible for technical aspects of the project and provides “on-the-ground” overview of project implementation by observing site activities to ensure compliance with technical project requirements, and the Site-Specific Health and Safety Plan (SSHASP). The Field Team Leader is responsible for identifying potential Integrity Management (IM) issues during field activities and reporting any and all issues to the Contractor QA Officer. Safety and Health Manager The Safety and Health Manager is responsible for developing and reviewing the SSHASP with all members of the field team. In addition, the Safety and Health Manager will lead applicable Task Risk Assessments and conduct the initial safety meeting prior to starting fieldwork. The Safety and Health Manager will ensure that work crews comply with all site health and safety requirements and will revise the SSHASP, if necessary. Contract Laboratory Contract Laboratory QA personnel are familiar with the approved QAPP and are available to perform the work as specified. Contract Laboratory personnel are responsible for reviewing final analytical reports produced by the laboratory, coordinating the laboratory analyses schedule and supervising in-house chain of custody procedures described in Section 3.1.8. 2.2 Problem Definition and Background The ARWW&S OU is located in southwest Montana. It consists of approximately 300 square miles in Anaconda-Deer Lodge County (Figure 2). Mining and smelting activities were conducted for nearly 100 years in Anaconda and the surrounding areas, resulting in the contamination of soils, surface water and groundwater. This contamination was spread primarily through airborne emissions and waste disposal practices from smelting operations. The Anaconda Smelter site was placed on the NPL in September 1983. Atlantic Richfield Company (Atlantic Richfield) was identified as the Potentially Responsible Party (PRP) and has been actively involved with the U.S. Environmental Protection Agency (EPA) and the Montana Department of Environmental Quality (DEQ) in conducting numerous investigations to determine the extent of contamination from historic smelting activities and associated processes. Numerous response actions were undertaken, including three Remedial Investigations (RIs) and five


Feasibility Studies (FSs), followed by the subsequent Anaconda Smelter NPL Site, Anaconda Regional Water, Waste and Soils Operable Unit Record of Decision (ROD) (ARWW&S ROD) (EPA, 1998). The ARWW&S OU Short-Term Groundwater Monitoring Sampling and Analysis Plan (SAP) (AERL, 2000) was implemented in 2000 and was subsequently modified in 2009 with the ARWW&S OU Short-Term Groundwater Monitoring Sampling and Analysis Plan (SAP) Addendum No. 1 (Atlantic Richfield Company, 2009). The EPA in consultation with DEQ issued the Anaconda Smelter NPL Site, Anaconda Regional Water, Waste and Soils Operable Unit, Record of Decision (ROD) Amendment (2011 ROD Amendment) (EPA and DEQ, 2011) in 2011. The 2011 ROD Amendment redefined the Domestic Well Area of Concern and brought site water quality Constituents of Concern (COCs) standards into compliance with Montana Numeric Water Quality Standards – Circular DEQ-7 (DEQ, 2010) issued in 2010, refer to the Draft Anaconda Smelter NPL Site Long-Term Ground Water Monitoring Plan (CDM, 2013a). A SAP detailing long-term sampling and monitoring activities complying with updated Montana DEQ standards has not previously existed; therefore, this QAPP will function as the SAP for the ARWW&S long-term groundwater monitoring activities. 2.3 Project Description and Schedule The purpose of this QAPP is to determine compliance with performance standards and assess the effectiveness and protectiveness of remedies at the Anaconda Smelter NPL Site. Based on the results of sampling completed under this QAPP, additional remedial action (RA) can be applied, as appropriate. The objectives of the QAPP are as follows: 1. Establish the groundwater monitoring network, monitoring schedule, and analysis parameters

for long-term groundwater monitoring; 2. Provide a sampling and analysis program for monitoring Point of Compliance (POC)

boundaries and determine compliance with performance standards; and 3. Provide data to monitor the effectiveness and protectiveness of the Remedies. This QAPP will consist of measuring water levels and collecting water quality samples from approximately 97 groundwater monitoring wells and 27 non-well sampling points (26 springs and one of the Opportunity drain tile line discharges) identified in Table 1 and shown on Figure 2. The monitoring network is specifically targeting the following groundwater areas of concern: • Anaconda Ponds/Smelter Hill/Opportunity Ponds Waste Management Area (WMA); • Old Works WMA/Area of Concern; • South Opportunity Alluvial Technical Impracticability (TI) Zone; • Blue Lagoon Area of Concern; • North Opportunity Alluvial TI Zone; • Town of Opportunity Area of Concern; and • Bedrock Aquifer TI Zones. Below is a summary of project tasks that are to be completed under the QAPP at the identified monitoring locations. Sampling activities, including types of monitoring locations, sampling frequencies, and COC lists are provided in greater detail in Table 1.


• Conduct semi-annual sampling at POC groundwater monitoring wells as shown in Table 1. • Conduct one annual 5-year review sampling (every five years) during high water at springs

and seeps as shown in Table 1. • Conduct semi-annual 5-year review sampling (every five years) at groundwater monitoring

wells as shown in Table 1. • Conduct one round of groundwater sampling at the event driven wells identified in Table 1 if

the water levels reach the trigger elevation of 5,165.5 feet in monitoring well (MW)-213 located within the Old Works WMA.

• Conduct semi-annual sampling at the Town of Opportunity well (MW-9) as shown in Table 1. • Conduct semi-annual sampling at the Engineered Cover Wells for 5 years following cover

installation, then annually once every 5 years as shown in Table 1. Data management, QA, and reporting tasks will be performed in accordance with the standards outlined in the Standard Operating Procedures (SOPs) provided in Appendix A. The field SOPs (Appendix A1) are updated versions of the standards outlined in the Clark Fork River Superfund Site Investigations (CFRSSI) Standard Operating Procedures (SOPs) (ARCO, 1992). An annual Data Summary Report (DSR) documenting the results of the fieldwork for low and high groundwater conditions will be submitted to the Agencies by the end of the first quarter of the following year. The field effort described herein will include the work schedule provided in Table 2. 2.4 Quality Objectives and Criteria Developing Data Quality Objectives (DQOs) was completed following the EPA’s Guidance on Systematic Planning Using the Data Quality Objectives Process (EPA, 2006). The DQOs are statements that define the type, quality, quantity, purpose, and use of data to be collected. The EPA has developed a seven-step process for establishing DQOs to help ensure that data collected during a field sampling program will be adequate to support reliable site-specific decision making (EPA, 2001 and 2006). The following section outlines and establishes the QAPP DQOs.

2.4.1 Data Quality Objectives The DQO process is intended to clarify the study objectives, define the most appropriate types of data to collect, and specify acceptable levels of decision errors that will be used as the basis for establishing the quantity and quality of data needed to support design objectives. The output from each step of the DQO seven-step process will influence the choices that will be made later in the process. The EPA DQO process consists of the following seven steps: • Step 1: State the Problem; • Step 2: Identify the Decisions; • Step 3: Identify the Inputs to the Decision; • Step 4: Define the Boundaries; • Step 5: Develop a Decision Rule;


• Step 6: Specify Tolerable Limits on Decision Errors; and • Step 7: Optimize the Design. The following DQO steps will be used to guide the data collection and analyses activities: Step 1: State the Problem. The purpose of this step is describe the problem to be studied so that the focus of the investigation will not be ambiguous. Various studies have collected groundwater and surface water samples at the site over the last three decades, resulting in the conclusion that mining activities have impacted groundwater and surface water/springs/seeps throughout the ARWW&S site. These studies have led to identifying seven geographic areas where remediation has taken place or is in the process of being remediated. Groundwater and surface expressions of groundwater (springs and seeps) monitoring is required to ensure the chosen remedies are working and performance standards are being met at the POC sites. Step 2: Identify the Decisions. This step identifies the principal questions that the QAPP will attempt to resolve and what actions may result. The key questions may be stated as follows: • Are performance standards being met for the 5 COCs at the 25 established POC groundwater

monitoring wells?

• Are RA activities, including reclamation, covering, and natural attenuation being effective?

• Are current groundwater conditions in plume areas being monitored and assessed sufficiently to identify trends?

Resulting alternative actions addressing the principal questions include: • If acceptable levels of COCs are met, continue monitoring as necessary for long-term

management.

• If exceedance of acceptable levels of COCs, perform contingency remedy measures per the Draft Anaconda Smelter NPL Site Groundwater Management Plan (GWMP) (CDM, 2013b).

Step 3: Identify the Inputs to the Decision. The purpose of this step is to identify the variables required to resolve the decision statements and determine which variables require environmental measurements.


The following data will be collected to supplement existing data: • Groundwater (monitoring wells and springs/seeps).

o Screening quality laboratory analyses for COC metals. o Field measurements of pH, specific conductance (SC), dissolved oxygen (DO), oxidation-

reduction potential (ORP), and temperature. o Field measurements of depth-to-groundwater (wells) and flow rate (where possible from

springs/seeps).

• All Samples. o Geospatial data will be collected for all samples, as well as descriptive data about the

samples (e.g., color, visual presence of waste, etc.). Data will be obtained from sampling as described in Section 3.0: Measurement and Data Acquisition. The data will be used with previously collected data to assess water quality trends in POC wells, and evaluate the effectiveness of cover material and completed reclamation activities at the site, as necessary. The media to be sampled, sampling procedures, analytical parameters, EPA developed risk-based screening levels for COCs, and laboratory methods outlined for this QAPP are generally consistent with samples previously collected within the ARWW&S site. Specific SOPs will be employed during the QAPP investigations to ensure integrity of the sample results. Specific parameters, detection limits, holding times, etc. are provided in Section 3.0. Step 4: Define the Boundaries. The purpose of this step is to define the spatial and temporal boundaries of the QAPP. The study area is limited to the groundwater monitoring network within the Anaconda Smelter NPL Site shown on Figure 2. Project activities are expected to occur annually, and will comply with the SSHASP. Sampling at monitoring wells and springs is expected to occur from February through September. Potential constraints that could delay fieldwork include adverse weather conditions, fires, closed roads, and the inability to obtain property access for sampling. Major project delays resulting from these constraints will be reported, and recorded in the field logbooks. Step 5: Develop a Decision Rule. The purpose of this step is to define the parameters of interest, specify action levels, and integrate any previous DQO inputs into a single statement. Arsenic, cadmium, copper, lead and zinc are the primary COCs throughout the ARWW&S site. Action levels will be based on COC standards for the ARWW&S site released in the 2011 ROD Amendment (EPA and DEQ, 2011). The 2011 ROD Amendment includes changes to water quality standards within the ARWW&S site from the ARWW&S ROD (EPA, 1998). The 2011 Rod Amendment brought the ARWW&S site COC standards in compliance with the then current


2.5 Special Training All field personnel will review and be trained in the requirements of this QAPP in a project meeting held prior to fieldwork. A review of sampling and monitoring procedures and requirements will be reviewed prior to field activities to ensure collecting and handling methods are according to QAPP requirements. Field personnel will be trained in proper use of field equipment and procedures according to field data collection SOPs. One hard copy of the current approved version of this QAPP will be maintained for ready reference purposes in the field vehicle and/or field office. All field team personnel will have access to PDF format files of the complete QAPP. A review of the SSHASP will be conducted with all field personnel prior to fieldwork to assess the site’s specific hazards and the control measurements that have been put in place to mitigate these hazards. The SSHASP review will cover all other safety aspects of the site including, site personnel responsibilities and contact information, additional site-specific safety requirements and procedures, and the emergency response plan. Training for calibrating field measurement instruments is the responsibility of the individual Field Team Leaders. Each of these individuals is experienced in the use and calibration of the equipment that will be used, and it is their responsibility to train and oversee the support staff. Laboratories providing analytical services will have a documented QC program that complies with EPA Requirements for Quality Management Plans (QA/R-5) (EPA, 2001). The Contractor QA Officer will be responsible for ensuring that all personnel have been properly trained and are qualified to perform assigned tasks. 2.6 Documents and Records This section describes procedures for documentation management and record keeping for this QAPP from initial record generation through final data formatting and storage.

2.6.1 Property Access Agreements Atlantic Richfield will request that all private property owners grant access to their properties for all RA-related activities, including sampling and monitoring. The Field Team Leader will manage requests for access, track the status of access requests and maintain copies of completed agreements received from property owners. Completed agreements will be photocopied and scanned with the electronic version stored on a hard drive. Photocopied access agreements will also be copied to the project record files.

2.6.2 Field Logbooks/Data Sheets Documentation in field logbooks provides a description of site conditions during sampling and monitoring activities, and provides a permanent record of all field activities. A field logbook and/or appropriate field data sheets (refer to field SOPs) will be used for field activities. When field logbooks are used, each logbook will have a unique document control number, and will be


bound and have consecutively numbered pages. The information recorded in these logbooks/field data sheets will be written in ink. Whenever a sample is collected or a measurement is made, a detailed description of the sample location and any additional observations will be recorded. Global positioning system (GPS) coordinates will be recorded when appropriate. Field logbooks/field data sheets will include the information listed below, at a minimum: • A description of the field task; • Time and date fieldwork started; • Location and description of the work area, including sketches if possible, map references and

references to photographs collected; • Names and titles of field personnel; • Name, address and phone number of any field contacts or site visitors (e.g., Agency

representatives, auditors, etc.); • Meteorological conditions at the beginning of fieldwork and any ensuing changes in the

weather conditions; • Details of the fieldwork performed and the field data sheets used with special attention to any

deviation from the QAPP or applicable field SOPs; • All field measurements made; • Any field analyses results; and • Personnel and equipment decontamination procedures. For any field sampling work the following entries will be made: • Sample location and ID number; • Sample type collected; • Date and time of sample collection; • Split samples taken by other parties (note the type of sample, sample location, time/date, name

of person, person’s company and any other pertinent information); • Sampling method, particularly any deviations from the field SOPs; • Documentation or reference of preparation procedures for reagents or supplies that will

become an integral part of the sample (if any used in the field), specifically if sample bottles/preservatives are not provided by the laboratory and certified as cleaned; and

• Sample preservation (if used). Changes in the field logbook or on the field data sheets will be recorded with a single strike mark through the changed entry, with the sampler’s initials and the date recording the new entry. All entries must remain legible. Sufficient information should be recorded to allow the sampling event to be reconstructed without having to rely on the sampler’s memory. Completed field data sheets and logbooks will be photocopied and scanned with the electronic version stored on a hard drive. Photocopied field records will also be copied to the project record files (refer to Section 3.6). No bound field logbooks will be destroyed or thrown away even if they are illegible or contain inaccuracies that require a replacement document.


2.6.3 Field Photographs

Photographs may be taken of sampling locations and field activities using a digital camera. Photographs should include a scale in the picture when practical. Additional photographs documenting site conditions will be taken, as necessary. Documentation of all photographs taken during sampling activities will be recorded in the bound field logbook or appropriate field data sheets (refer to field SOPs), and will specifically include the following for each photograph taken: • The photographer’s name, date, time, and the general direction faced; • A brief description of the subject and the fieldwork portrayed in the picture; and • Sequential number of the photograph. The digital files will be placed in project files with copies of supporting documentation from the bound field logbooks.

2.6.4 Transducer Data

A telemetry system will be used to upload data collected from continuous transducer monitoring at MW-213. Continuous monitoring using a data logger will be set to collect 1 measurement per hour, and the telemetry system will upload the data once per day to the STS Gold Com Agent software on the contractor home station computer. Data will be saved as a Microsoft Access database file (.mbd). After the data have been uploaded to the contractor home station computer, the database file will be automatically saved daily to both a central server system and an external hard drive. As a backup, the data will also be stored locally on the level logger. For additional transducer details refer to Section 3.1.1.

2.6.5 Chain of Custody Records After samples have been collected, they will be maintained under strict chain-of-custody protocols in accordance with SOP-SA-04: Chain of Custody Forms for Environmental Samples. A copy of each as-transmitted chain of custody form will be scanned and stored on a hard drive. Chain of custody records will also be copied to the project record files (refer to Section 3.6). For complete chain of custody protocols refer to Section 3.1.7.

2.6.6 Analytical Laboratory Records Results received from the laboratories will be documented both in report form and in an electronic format. Laboratory documentation includes copies of the signed chain of custody forms, laboratory confirmation reports including information on how samples have been batched and the analyses requested, data packages including the laboratory report and the electronic data deliverable (EDD), and any change requests or corrective action requests. Section 5.1.3 presents the project’s laboratory reporting requirements in detail. The deliverable (“data package” or “report”) issued by the laboratories will include data necessary to complete validation of laboratory results in accordance with specifications included in Section 5.2.2.


Original reports and electronic files received from laboratories will be maintained with the project quality records (refer to Section 3.6).

2.6.7 Project Data Reports An annual DSR will be prepared following data collection, evaluation and interpretation, and will be submitted to the Agencies following the schedule provided in Table 2. The DSR will include copies of all field data, daily logbook entries, and laboratory analytical results. These data will reside in the project database, and will also be stored in Montana’s Groundwater Information Center (GWIC) Database along with historical data that is maintained by the Montana Bureau of Mines and Geology (MBMG). Atlantic Richfield, or their designee, will provide a summary of landowner specific data to the individual landowners.

2.6.8 Quality Records Quality records are defined as completed, legible documents that furnish objective evidence of the quality of items or services, activities affecting quality, or the completeness of data. These records will be organized and managed by the RA entity and will include, at a minimum: • This QAPP and any approved revisions or addenda; • Approved versions of the SSHASP and any addenda; • Copies of field SOPs for field data collection, with any updates, revisions or addenda to those

SOPs; • Incoming and outgoing project correspondence (letters, telephone conversation records, faxes

and e-mail messages); • Copies of completed access agreements for the individual properties sampled; • Individual property maps, including any field drawings and field photographs; • Field documentation forms; • Copies of all bound field logbooks; • Copies of all field data sheets; • Continuous monitoring data (see Section 3.6); • Copies of all sample chain of custody forms; • Copies of all laboratory agreements and amendments; • Laboratory data packages (report and electronic); • Documentation of field and/or laboratory audit findings and any corrective actions; and • Draft and final delivered versions of all reports and supporting procedures such as statistical

analyses, numerical models, etc. 3.0 MEASUREMENT AND DATA ACQUISTITION

This section addresses all aspects of project design and implementation for generating and acquiring data. Implementing these elements ensures that appropriate methods for sampling, sample handling, laboratory analyses, field and laboratory QC, instrument/equipment testing, inspection, maintenance, instrument/equipment calibration, data management and data security are used for all phases of the QAPP.


3.1 Sampling Process and Design This QAPP has been developed to define the requirements for long-term groundwater monitoring of wells and springs at the Anaconda Smelter NPL Site. The primary goal of the QAPP is to provide POC water quality concentration data for evaluating performance standards and assessing the effectiveness and protectiveness of remedies at the Anaconda Smelter NPL Site. The QAPP will consist of measuring water levels and collecting water quality samples from the 97 groundwater monitoring wells and 27 non-well sampling points (26 springs and 1 tile drain) identified in Table 1 and shown on Figure 2. The COC metals and metalloids are the critical data drivers for the project. Other critical non-analytical information includes flow rates, static water levels, and land ownership. Data collected for informational purposes includes: weather, site conditions, field parameters, sample water conditions (i.e., color, odor), description of sampling locations, residential use information, and other information that adds to the overall understanding of the site. Table 6 presents a general summary of the types of sampling that will be conducted for each of the plan tasks that require field activity. These summarized items are further discussed in detail in the following subsections.

3.1.1 Monitoring Well Designation and Sample Frequency The monitoring locations to be sampled under this QAPP will be similar to those that were sampled under the ARWW&S OU Short-Term Groundwater Monitoring Sampling and Analysis Plan (SAP) Addendum No. 1 (Atlantic Richfield Company, 2009). Monitoring wells within each area of concern have different monitoring objectives and sampling frequencies, as shown in Table 1. The following monitoring well designations and sample frequencies have been established for the monitoring well network: • Point of Compliance (POC) Wells: Twenty-five (25) POC wells will be monitored twice

annually, once during low groundwater and once during high groundwater. The POC well results may be included as data in other reports and plans, such as performance standards compliance reports and groundwater management plans which will compare the data to performance standards to determine if exceedances are occurring and if contingency measures are necessary. A new well installed as a POC must show no exceedance of a water quality standard for at least 4 consecutive sampling events before it may be identified to serve as a POC well.

• 5-Year Wells: Fifty-three (53) 5-year wells will be monitored in accordance with the

frequencies shown in Table 1. The 5-year well results will be included as data in evaluating the effectiveness and protectiveness of Remedies in meeting performance standards and in support of the 5-year reviews. For the purpose of this Plan, the first 5-year groundwater monitoring sampling will be conducted in 2019 to support the 2020 5-Year Review.


In addition to these wells, two other types of wells will be monitored as 5-year wells. These are as follows: • Event Driven Wells (EDWs): Fourteen (14) EDWs are located within the Old Works WMA.

Ten (10) of the 14 wells will be monitored if and when a high groundwater event is detected within the Old Works WMA, as determined by continuous monitoring of well MW-213. A groundwater elevation greater than 5,156.5 feet above mean sea level (amsl) will trigger the event driven sampling. A continuous reading transducer and telemetry system has been installed in well MW-213 to monitor the water level at a data logger collection rate of 1 measurement per hour. The telemetry system will be set up to notify an email list if a groundwater elevation level exceeds the trigger value of 5,156.5 feet amsl. If and when such high groundwater occurs, the EDWs sampling will begin 2 weeks following the peak water level, with all sampling completed within the following 2 weeks. The remaining four wells identified as EDWs are POC or 5-year review wells and their scheduled sampling dates will be adjusted to meet the 2-week window for sampling EDWs if the trigger elevation is reached. If dissolved cadmium exceeds 15 parts per billion (ppb) for any EDW, that well will subsequently be sampled semi-annually, on a schedule coinciding with ongoing POC well monitoring, until the dissolved cadmium is less than 15 ppb. Once the dissolved cadmium concentration is found to be less than 15 ppb, the monitoring frequency will revert to the schedule shown in Table 1. Note that four of the EDWs are also POC wells, and will be sampled semi-annually regardless of cadmium concentrations.

• Engineered Cover Wells: Eight (8) monitoring wells have been designated as wells within the Opportunity Ponds WMA that will be monitored semi-annually for 5 years following cover installation, then annually once every 5 years. Refer to Table 7 for the sampling schedule for each engineered cover well.

• Town of Opportunity Well: One (1) monitoring well will be monitored semi-annually as a

supplement to the eight POC wells located along the north boundary of the South Opportunity TI Zone. Although sampled on the same schedule as the POC wells, this supplemental well is not subjected to statistical analyses.

Sampling of monitoring wells will be completed such that the seasonal fluctuation of the water table is captured by the low and high water sampling events. An analysis was completed under the ARWW&S OU Short-Term Groundwater Monitoring Sampling and Analysis Plan (SAP) Addendum No. 1 (Atlantic Richfield Company, 2009) of existing groundwater elevation data to determine the most appropriate time each year to conduct the low and high groundwater sampling events such that the seasonal fluctuations of groundwater within the ARWW&S site are captured by the monitoring. As determined in the analysis, the low groundwater event will be conducted between February and March and the high groundwater event will be conducted between June and August each year. Timing of sampling may be altered based on additional data collection. Each groundwater sampling event will start by collecting synoptic water levels. The water level at each monitoring well in the network will be collected during the first few days of each monitoring event prior to collecting any groundwater samples. The water level at each well will also be measured just prior to purging and sampling the well.


3.1.2 Groundwater Sampling from Monitoring Wells

The goal of groundwater sampling is to provide a snapshot of the alluvial aquifer at high- and low-water table conditions across the site and to confirm that performance standards are being met. Additional objectives are to evaluate the effectiveness and protectiveness of Remedies in meeting performance standards. All well monitoring and sampling activities will be performed in accordance with the field SOPs provided in Appendix A1. General well monitoring activities will include the following steps: • Gather equipment and mobilize to sampling location using maps and GPS coordinates. • Use a portable submersible pump to pump at a stable flow until field parameters stabilize or

three well bore volumes of water have been removed. The water removed will be discharged directly to the ground, away from any surface water body. Collect the sample, and filter and preserve the sample as necessary following SOPs provided in Appendix A.

• Decontaminate the pump and associated equipment between wells. • Label the sample, record all information in the applicable field logbook, and take photographs

of sampling locations as necessary. • Securely package all samples and transport to the field office. The necessary field equipment needed for groundwater sampling will include the following: • Hard copy of the QAPP; • Field notebook, pens, camera, batteries and cell phone; • Maps of well locations and padlock keys; • GPS; • pH, SC, temperature, DO, and ORP water quality meters; • Submersible pump(s); • Peristaltic pump and disposable tubing; • Water-level meter; • Sample bottles; • 0.45 micron (µm) filters; • High Density Polyethylene (HDPE) bailers; • Nitric acid preservative (if needed), deionized (DI) water, and decontamination solutions; • Sample coolers, ice, and tape; and • Required Level D Personal Protective Equipment (PPE) including: work gloves, latex

sampling gloves, hard hats, long-sleeved shirts, safety glasses with side shields, and steel-toed boots.

All monitoring well groundwater samples will be securely packaged and transported back to the analytical laboratory for the specified analysis in Table 1. All sampling methods, including storage, handling, and shipping procedures will follow field SOPs as further discussed in Section 3.3. The estimated number of well monitoring samples to be collected based on sample frequency discussed in Section 3.1.1 is summarized in Table 8. If sampling sites become inaccessible during sampling and monitoring activities, Agency oversight personnel will be contacted and it will be logged in the logbook. Sampling crews will re-visit the inaccessible sampling site, as necessary,


to obtain a sample during the appropriate sampling time frame. If a sample cannot be obtained during the appropriate time frame, it will be recorded as a deviation to this QAPP and further discussed with Agency oversight personnel.

3.1.2.1 Sample Analysis and Procedures Table 1 provides the parameters to be analyzed for each monitoring well. In addition to the specified parameters, the following field parameters will be collected: temperature, pH, ORP, DO, and SC. Analytical results will be reported using a simplified format (i.e., without full data packages) including data tables with detection limit qualifiers and QC summary tables as further discussed in Section 5.0.

3.1.3 Groundwater Expression Sampling Spring sampling will be conducted once every five years in the spring, when flow is most likely to be occurring from the groundwater expression. Additionally, one tile drain will be sampled semi-annually each 5 years. Groundwater expressions (springs) were previously sampled during high groundwater in 2014 as part of the 5-year review held in 2015 to characterize the shallow groundwater system at the Anaconda Smelter NPL Site. For the purpose of this Plan, the first spring and tile drain sampling will occur in 2019 to provide data for the 5-year review to be held in 2020. The spring and tile drain locations are shown on Figure 2 and provided in Table 1. All spring sampling activities will be performed in accordance with the field SOPs provided in Appendix A1. General spring sampling activities will include the following steps: • Gather equipment and mobilize to sampling location using maps and GPS coordinates. • Identify the seep to be sampled. If possible, determine flow rate. • Measure and record field parameters by placing the probe directly in the seep or spring channel

or using the water collected in the bucket. • Collect water samples for analyses directly from the discharge, taking care to minimize

incorporation of sand or debris following the SOPs provided in Appendix A. • Label the sample, record all information in the applicable field logbook, and photograph each

sampling location.

The necessary field equipment needed for the spring sampling will include the following: • Hard copy of QAPP; • Field notebook, pens, camera, batteries, and cell phone; • Maps of former seep/spring sampling locations; • Portable flume; • Sample coolers, ice, and tape; • Sample bottles; • GPS; • 0.45 micron (µm) filters ; • Peristaltic pump and tubing; • pH, SC, temperature, DO and ORP water quality meters; • Nitric acid preservative (if required);


• Paper towels, DI water, decontamination solutions ,and sprayer; and • Required Level D PPE including: work gloves, latex sampling gloves, hard hats, long-sleeved

shirts, safety glasses with side shields, and steel-toed boots. All spring samples will be securely packaged and transported back to the analytical laboratory for specified analysis included in Table 1. All sampling methods, including storage, handling, and shipping procedures will follow field SOPs as further discussed in Section 3.3. The estimated number of spring samples to be collected based on sample frequency discussed in Section 3.1.1 and summarized in Table 9. If sampling sites become inaccessible during sampling and monitoring activities, Agency oversight personnel will be contacted and it will be logged in the logbook. Sampling crews will re-visit the inaccessible sampling site, as necessary, to obtain a sample during the appropriate sampling time frame. If a sample cannot be obtained during the appropriate time frame, it will be recorded as a deviation to this QAPP and further discussed with Agency oversight personnel.

3.1.3.1 Sample Analysis and Procedures The springs and tile drain samples will be sampled for dissolved arsenic and other analytes, as specified in Table 1. The following field parameters will be collected: temperature, pH, ORP, DO, and SC. Analytical results will be reported using a simplified format (i.e., without full data packages) including data tables with detection limit qualifiers and QC summary tables as further discussed in Section 5.0.

3.1.4 Sample Disposal Prior to collecting groundwater samples, initial purging of groundwater is required (see SOP-DE-03: Investigation Derived Waste Handling). The purged water will be disposed of onto the ground near the sampling location, in a manner as to not disturb the integrity of the sample to be collected. Disposable equipment and investigation-derived waste used during sample collection will be immediately bagged in garbage bags after it is used, so it does not cross-contaminate unused disposable equipment and is easy to dispose of in a waste disposal facility. Samples collected and shipped to the laboratory for analyses will be held until analyses have been completed and holding times have been exceeded. The laboratory will be responsible for appropriate sample disposal.

3.1.5 Sample Labeling and Identification All water samples collected will have a unique sample ID that follows an alpha-numeric coding system for identification as summarized in Table 10. The alpha-numeric coding label for each sample will include all necessary information for proper identification of the type of sample collected, the sample location, and the date the sample was collected. An appropriately labeled tag will be placed on the sample collection bottle. The sample ID will be recorded in the field logbook and will match the sample ID on the collection bottle and chain of custody form. Refer to Section 3.1.7 for chain of custody protocols.


3.1.6 Field Documentation

All field entries will be recorded in a bound field logbook, as discussed in Section 2.6.2, and all project documentation entries will be consistent with SOP-SA-05: Project Documentation. Photographs or field activities will be taken as necessary using a digital camera, refer to Section 2.6.3. An electronic copy and/or a hard copy of the photographs will be placed in task files in the field office after each day of field activities. Supporting documentation from the bound field logbooks or field data sheets will be photocopied and placed in the task files to accompany the photographs once the field activities are complete.

3.1.7 Sample Handling, Chain of Custody and Shipping All water samples collected will follow water sample packaging and shipping procedures outlined in SOP-SA-01: Soil and Water Sample Packaging and Shipping. Water samples will be preserved, if required, according to SOP-SA-02: Sample Preservation and Containerization for Aqueous Samples during sample collection. After sample collection and labeling, the groundwater samples will be placed in separate plastic bags to keep the samples isolated and to keep the sample containers and labels clean and dry. The samples will be packaged in a plastic lined, if necessary, insulated cooler and surrounded with non-contaminating packaging materials to reduce movement during shipping. Samples will be transported to the laboratory in the insulated coolers with double bagged ice as necessary to maintain temperature <6 degrees Celsius (ºC) but above freezer per Guidelines Establishing Test Procedures for the Analysis of Pollutants Under the Clean Water Act; Analysis and Sampling Procedures; Final Rule. 40 CFR Parts 136, 260 et al. (EPA, 2012) until receipt by the analytical laboratory. The insulated coolers will be properly labeled describing the content of the cooler (e.g., this side up, fragile, etc.) and be taped closed for transport. The samples will be maintained under strict chain of custody protocols per SOP-SA-04: Chain of Custody Forms for Environmental Samples. The Field Team Leader or designated Field Sampler will initiate the chain of custody form for the transfer of the samples. A chain of custody form will be completed and accompany every sample. The chain of custody form will include the project code, project name, sampler’s signature, sample ID, date and time sampled, analysis requested, remarks, relinquishing signature, date and time, and received signature, date and time. A chain of custody form will be included for each shipping container (insulated cooler) of samples to be delivered to the laboratory for analysis in order to meet appropriate holding time requirements. The chain of custody for a shipping container will list only those samples in that shipping container. Any documentation, including chain of custody forms, should be placed inside a sealed plastic bag. The sampling personnel whose signature appears on the chain of custody form is responsible for the custody of the samples from the time of sample collection until custody of the samples is transferred to a designated laboratory, a courier or to another project employee for the purpose of transporting the sample to the designated laboratory. Custody is transferred when both parties complete the portion of the chain of custody form under "Relinquished by" and "Received by.” During the custody transfer process, signatures, printed names, company names, dates and times are required to be documented on the chain of custody form. Upon transfer of custody, the sampling personnel who relinquished the samples will retain the third sheet (pink copy) of the


chain of custody, if available. When the samples are shipped by a common carrier, a Bill of Lading supplied by the carrier will be used to document the sample custody, and its identification number will be entered on the chain of custody. Copies, receipts and carbons of Bills of Lading will be retained as part of the permanent documentation in the project file. It is not necessary for courier personnel to sign the chain of custody. One copy of each chain of custody form will be filed as a temporary record of sample transfer by the Field Sampler. The original form will accompany the samples and will be returned to the contractor as part of the contracted laboratory QA/QC requirements. The original form will be filed as part of the project’s permanent records.

3.1.8 Laboratory Sample Handling and Storage Upon receipt by the laboratory, the samples will be inspected for sample integrity. The chain of custody will be immediately signed, dated and reviewed by laboratory personnel to verify completeness. Any unacceptable samples will be identified and segregated and the Contractor QA Officer will be notified. Any discrepancies between the chain of custody and sample labels will be communicated immediately to the Field Team Leader. The laboratory will provide the Field Team Leader and Contractor QA Officer with a copy of the chain of custody and associated sample-receipt information within two working days of receipt of samples. The sample-receipt information routinely provided will include sample receipt date, sample IDs transcribed from the chain of custody, sample matrix type and list of analyses to be performed for each sample. Broken custody seals, damaged sample containers, sample labeling discrepancies between container labels and the chain of custody form and analytical request discrepancies will be noted on the chain of custody form. The Field Team Leader and Contractor QA Officer will be notified of any discrepancies or non-conformances; these issues will be addressed and resolved before samples are analyzed. The laboratory will be responsible for following their internal custody procedures from the time of sample receipt until sample disposal. Samples and extracts will be stored in a secure area controlled by the laboratory’s designated sample custodian. Samples will be removed from the shipping container and stored in their original containers unless damaged. Damaged samples will be disposed in an appropriate manner after notifying the Field Team Leader and Contractor QA Officer, and authorization to dispose of is received and documented. In addition, samples will be stored after completion of analyses in accordance with contractual requirements. 3.2 Laboratory Methods The water samples collected under this QAPP will be analyzed for metals as outlined in Table 1. The approved analytical laboratory will use standard laboratory procedures and methods for analyses of the metals. The sample preparation and analyses methods to be used by the approved laboratory are described in Section 3.2.1 and Section 3.2.2.


3.2.1 Sample Preparation Methods

The water samples will be prepared for metals and other parameter analyses by the laboratory in accordance with the laboratory SOPs, as necessary. Preparation methods, including equipment calibration methods are outlined in the laboratory SOPs, provided in Appendix A2.

3.2.2 Sample Analysis Methods The majority of the samples collected from the fieldwork efforts will be analyzed by the approved analytical laboratory for the following COCs: arsenic, cadmium, copper, lead, and zinc. Some samples will only be analyzed for one COC (arsenic), depending upon the area or zone where the sample was collected (see Table 1). Additional required analytes are also outlined in Table 1. Sample preparations and analyses will be in accordance with laboratory SOPs and practices. A summary of sample analyses and preparations are provided in Table 11. The laboratory’s current method detection limits (MDLs) and reporting limits (RLs) for the analytes to be analyzed are provided in Table 12. 3.3 Quality Assurance/Quality Control Sample QC protocols will be consistent with SOP-SA-03A Field Quality Control Samples for Water Sampling and will include one field duplicate, one field bottle blank, and 1 rinsate blank collected for every 20 primary samples or once per sampling event, whichever is more frequent. . A temperature blank will additionally be collected for every cooler shipped to the laboratory to ensure the samples were maintained within the required temperature of <6 ºC but above freezer per Guidelines Establishing Test Procedures for the Analysis of Pollutants Under the Clean Water Act; Analysis and Sampling Procedures; Final Rule. 40 CFR Parts 136, 260 et al. (EPA, 2012). Any deviation from the SOPs or this QAPP will be identified in the logbook and discussed in the annual DSR. All sampling and monitoring activities will follow the field SOPs. All field SOPs were developed from the CFRSSI SOPs (ARCO, 1992), and represent updated versions of those SOPs for sampling and monitoring activities under this QAPP. A list of the field SOPs to be followed during the Plan and the corresponding CFRSSI SOPs (ARCO, 1992) are provided in Table 13.

3.3.1 Field Quality Control Samples Field QC samples are used to identify any biases from transportation, storage, and field handling processes during sample collection, and to determine sampling precision. All field QC samples will be shipped with field samples to the laboratory per SOP-SA-01: Soil and Water Sample Packaging and Shipping. Brief descriptions of these QC samples to be collected during sampling activities described in this are provided below along with instructions for their frequencies of collection and analyses. Field Duplicate A field duplicate is a second sample collected from the same location, in immediate succession to the primary sample, using identical techniques. The duplicate sample will have its own sample


number. Duplicate samples are sealed, handled, stored, shipped, and analyzed in the same manner as the primary sample. Both the primary sample and duplicate sample will be analyzed for identical chemical parameters by the laboratory. The analytical results of the primary and duplicate sample will be compared to determine sampling precision. Field duplicate samples will be collected at a frequency of 1 per 20 samples or once per sampling event, whichever is more frequent. Field Blank or Bottle Blank A field blank is a sample bottle containing DI or analyte-free water and appropriate preservatives and is prepared in the field. A sample bottle is randomly chosen from each lot of bottles received by the contract laboratory or supplier, and DI or analyte-free water is poured directly into the sample bottle while in the field, preserved, and shipped to the laboratory with the field samples. Field blanks must be prepared in the field, and will help evaluate the potential for possible contamination from the sampling environment. The field blank will have its own unique sample number and will be recorded in the project logbook as a field blank or bottle blank. Field blanks will be prepared at a frequency of 1 per 20 samples collected. Equipment, Cross Contamination, or Rinsate Blank Equipment blanks are collected after completion of decontamination of sampling equipment or prior to sampling activities. An equipment blank is prepared by running distilled, DI or analyte-free water through or over the cleaned, decontaminated sampling equipment, placing it in a sample collection bottle and adding the appropriate chemical preservatives. Equipment blanks will assess the adequacy of the decontamination process, as well as, the potential contamination of samples by the containers, preservatives and filters. The appropriate sample number will be placed on the collection bottle and recorded in the project logbook as an equipment blank. All sample containers collected for a natural sample should be duplicated for an equipment blank. A minimum of 1 equipment blank is required for every 20 natural samples collected. Temperature Blank A temperature blank is a vial of water that accompanies the samples that will be opened and tested upon arrival at the laboratory to ensure that the temperature of the contents of the sampling shipping container was within the required <6 ºC but above freezer per Guidelines Establishing Test Procedures for the Analysis of Pollutants Under the Clean Water Act; Analysis and Sampling Procedures; Final Rule. 40 CFR Parts 136, 260 et al. (EPA, 2012). One temperature blank is required for each cooler shipped to the laboratory.

3.3.2 Laboratory Quality Control Samples Laboratory QC samples are introduced into the measurement process to evaluate laboratory performance and sample measurement bias. Laboratory QC samples may be prepared from environmental samples or generated from standard materials in the laboratory per the internal laboratory SOPs. Laboratory SOPs to be followed for the purposes of this QAPP, as necessary, are provided in Table 14. All laboratory SOPs are provided in Appendix A2, and are generally summarized below. The appropriate type and frequency of laboratory QC samples associated with each method are specified in Table 4.


Method Blank (MB) One Method blank (MB) sample should be prepared and analyzed with with every sample preparation batch or every 20 samples whichever is more frequent. Method blanks are analyte free or DI water subjected to the same procedures (preparation and analysis) as the primary samples. Control limits vary based on the laboratory method performed; values are given in Table 4. Failure will trigger corrective action and the blanks will be re-analyzed. All samples affected will be footnoted with the appropriate flag to document contamination in the blank. Laboratory Control Sample (LCS) One Laboratory Control Samples (LCS) should be prepared and analyzed with every sample preparation batch or every 20 samples, whichever is more frequent. Control limits vary based on the laboratory method performed; values are given in Table 4. If the LCS is found to be high and the samples non-detect, the laboratory will not take corrective action as the samples are not impacted by the high bias. The LCS will only be qualified for the outliner only. Matrix Spike (MS) / Matrix Spike Duplicate (MSD) Matrix Spikes (MS) and Matrix Spike Duplicates (MSD) are prepared and analyzed at different frequencies based on the laboratory method performed (see Table 4). The control limits also depend on the method used and all of the values are listed in Table 4. If the percent recovery for the MS and MSD fall outside the control limits, the results are flagged that they are outside acceptance criteria along with the parent sample. If the RPD exceeds the acceptance criteria, the MSD sample and associated parent sample need to be flagged. Post Digestion Spike (PDS) Post Digestion Spikes (PDS) are prepared and analyzed at different frequencies based on the laboratory method performed (see Table 4). The control limits also depend on the method used and all of the values are listed in Table 4. Internal Standard An internal standard is introduced automatically with every sample. Control limits are within 30% of the true value. If the recovery is outside the criteria, sample is re-analyzed at a 5 times dilution. pH Calibration Check The pH calibration check is performed immediately after calibration of the pH probe and should be within 0.10 pH units. If the acceptance criterion is not met, terminate analysis, correct the problem, recalibrate and attempt a new pH calibration check. Laboratory Control Sample Duplicate (LCSD) One laboratory control sample duplicate (LCSD) samples should be prepared and analyzed for with every sample preparation batch or for every 20 samples analyzed, whichever is more frequent. Control limits vary based on the QC action used; values are given in Table 4. If the LCSD is found to be high and the samples non-detect, the laboratory will not take corrective action as the samples are not impacted by the high bias. The LCSD will only be qualified for the outliner only.


Initial Calibration Verification (ICV) / Continuing Calibration Verification (CCV) The initial calibration verification must be performed immediately after the pH calibration check. The continuing calibration verification must be analyzed and reported every 10 samples and at the end of the analytical run to ensure calibration accuracy. Control limits are within 10% of the true value and failure will trigger corrective action and re-analysis of samples since the last compliant CCV. Initial Calibration Blank (ICB) and Continuing Calibration Blank (CCB) A calibration blank must be analyzed immediately after every ICV and CCV. The ICB and CCBs must be less than the reporting limit unless otherwise specified by the client or QAPP. Failure will trigger corrective action and a single re-analysis of the respective failing QC is allowed. If the re-analysis is outside the acceptance criteria, the analysis must be terminated, the problem corrected, the instrument recalibrated and the calibration verified. Serial Dilution A serial dilution should be prepared and analyzed for every 20 samples analyzed. Control limits for a five-fold dilution must agree within 10% of the original determination if the analyte’s concentration is greater than 50 times the MDL. Failure will trigger corrective action and the original sample and dilution will be re-analyzed. Serial Dilution of Post Digestion Spike Serial dilution of PDS does not have a set frequency for analysis. Control limits for a five-fold dilution must agree within 10% of the original determination, and failure will trigger corrective action (see Table 4). Duplicate Sample Duplicate samples are prepared and analyzed at different frequencies based on the laboratory method performed; all information is given in Table 4. The control limits also depend on the method used and all of the values are listed in Table 4. Failure will trigger corrective action and the parent sample will be re-analyzed in duplicate to confirm either the parent sample result or duplicate result. Pad Weight Verification Pad weight verification is performed on 1 pad per box of 100 pre-weighed total suspended solids (TDS) pads. Control limits are within 0.0005 grams of the weight specified by the manufacturer. Failure will trigger corrective action; if outside the acceptance criteria, attempt verification on a second pad in the lot. If the second is also outside the acceptance criteria, discard the lot. 3.4 Instrument/Equipment Testing, Inspection and Maintenance In order to ensure continual quality performance of any instruments or equipment, testing, inspection and maintenance will be performed and recorded as described in this section.

3.4.1 Field Equipment Field equipment will be examined to verify that it is in proper operating order prior to its first use. Equipment, instruments, tools, gauges and other items requiring preventative maintenance will be


serviced and/or calibrated in accordance with the manufacturer’s specified recommendations, as necessary. Field equipment will be cleaned (decontaminated) and safely stored between each use. Any routine maintenance recommended by the equipment manufacturer will also be performed and documented in field logbooks. Calibration of field equipment will be completed in the field at the beginning of each day and recorded in the field logbooks. Any equipment deficiencies or malfunctions during fieldwork will be recorded as appropriate in the field logbooks. All field equipment preparation, calibration methods and storage and handling procedures will follow the appropriate field SOPs listed in Table 12.

3.4.2 Laboratory Equipment Instruments used by the laboratories will be maintained in accordance with each laboratory’s QA Plan requirements and analytical method requirements. All analytical measurement instruments and equipment used by the laboratory will be controlled by a formal calibration and preventive maintenance program. The laboratories will keep maintenance records and make them available for review, if requested. Laboratory preventive maintenance will include routine equipment inspection and calibration at the beginning of each day or each analytical batch, per the laboratory’s internal SOPs and method requirements. 3.5 Inspection/Acceptance of Supplies and Consumables All supplies and consumables received for the project (e.g., sampling equipment, calibration standards, etc.) will be checked to ensure satisfactory condition, and free of defects that would affect their performance. The types of equipment that will be needed to complete sampling activities are described in the relevant field SOPs. Inspections of field supplies will be performed by the Field Team Leader or Field Team Members. The personnel at each laboratory will be responsible for performing inspections of laboratory supplies in accordance with their QA program. 3.6 Data Management Procedures This section describes the management of data for the project including field and laboratory data. The QAPP quality records will be maintained by Atlantic Richfield. These records, either electronic or hard copy in form, may include: • Project work plans with any approved modifications, updates, and addenda; • Individual property maps (hard copy or scanned field drawings and electronic files); • Project QAPP, including this QAPP, with any approved modifications, updates, addenda, and

any approved corrective or preventative actions; • Access agreements from property owners; • Field documentation (including logbooks, data sheets, and photographs in accordance with

SOP-SA-05: Project Documentation); • Chain of custody records;


• Laboratory documentation (results received from the laboratory will be documented both in report form and in an electronic format); and

• DSR. Data collected from the continuous monitoring transducer and telemetry system will be maintained on the home station computer. The data will be saved as a Microsoft Access database file (.mbd). The electronic database file records will also be maintained on a central server system with backup scheduled on a daily basis, and on an external hard drive. Hard copy field and laboratory records will be maintained in the project’s central data file, where original field and laboratory documents are filed chronologically for future reference. These records are also scanned to produce electronic copies. The electronic versions of these records are maintained on a central server system with backup scheduled on a daily basis. All field and laboratory data and supporting documentation will be subject to appropriate review to ensure the accuracy and completeness of original data records prior to uploading into the project database. Field data that has been reviewed and approved in a hard copy format will be entered into electronic data files for upload to the project database. All manual data entry into an electronic format will be reviewed by a separate party before such data are incorporated into the database. Laboratory EDDs provided in Microsoft Excel format and correlating PDF data packages (simplified format) will be reviewed as part of the internal data review process. Following these review steps, field and laboratory electronic data files will be imported to the project database. Standardized data import formats and procedures will be used to upload both field and laboratory data into the electronic database. Standardized parameter names, numerical formats and units of measure may be applied to the original information to facilitate comparability across all datasets and within the database. The electronic database will be formatted in a digital format compatible with the Montana Bureau of Mines and Geology (MBMG) Ground-Water Information Center (GWIC) database. Once the electronic database has been updated with all final (approved and verified) data collection information, the database information will be copied and transferred to the GWIC database. The GWIC database is maintained on a secure server with off-site backup. The project data will be retrievable over the internet from the GWIC site (http://mbmggwic.mtech.edu/), and will allow public access to historical and current records for monitoring locations included within the scope of this QAPP. 4.0 ASSESSMENT AND OVERSIGHT Assessment and oversight of data collection and reporting activities are designed to verify that sampling and analyses are performed in accordance with the procedures established in this QAPP. The audits of field and laboratory activities include two independent parts: internal and external audits. Internal audits will be performed by Atlantic Richfield, their contractor or a contracted laboratory as necessary. External audits will be performed by the EPA as necessary. Performance and systems audits of field and laboratory data collection and reporting procedures are described in this section.


http://mbmggwic.mtech.edu/

4.1 Corrective Actions Corrective action is the process of identifying, recommending, approving and implementing measures to counter unacceptable procedures or out-of-QC performance which can affect data quality. Corrective action can occur during field activities, laboratory analyses and data assessment. Non-conforming equipment, items, activities, conditions and unusual incidents that could affect data quality and attainment of the project’s quality objectives will be identified, controlled and reported in a timely manner. For the purpose of this QAPP, a non-conformance is defined as a malfunction, failure, deficiency or deviation that renders the quality of an item unacceptable or indeterminate in meeting the project’s quality objectives. Corrective actions implemented by field personnel will follow appropriate field SOPs (Appendix A1), as necessary. Corrective action in the laboratory may occur prior to, during and after initial analyses. A number of conditions such as broken sample containers, preservation or holding-time issues and potentially high-concentration samples may be identified during sample log-in or just prior to analyses. Corrective actions to address these conditions will be taken in consultation with the Contractor QA Officer and reported on a Corrective Action Report (CAR) included in Appendix B. In the event that corrective action requests are not in complete accordance with approved project planning documents, the EPA will be consulted and concurrence will be obtained before the change is implemented. If during analyses of the samples, the associated laboratory QC results fall outside of the project’s performance criteria, the laboratory should initiate corrective actions immediately. Table 4 indicates the performance criteria for specific analytical methods and the appropriate corrective actions for the laboratory to complete if laboratory QC results are outside of the project specifications. Following consultation with laboratory analysts and section leaders, it may be necessary for the Contractor QA Officer to approve implementing a corrective action. These conditions may include dilution of samples, additional sample extract cleanup, or automatic re-analysis when certain QC criteria are not met, etc. If the laboratory cannot correct the situation that caused the non-conformance and an out-of-control situation continues to occur or is expected to occur, then the laboratory will immediately contact the Contractor QA Officer and request instructions regarding how to proceed with sample analyses. Completion of any corrective action should be evidenced by data once again falling within the project’s performance criteria. If this is not the case, and an error in laboratory procedures or sample collection and handling procedures cannot be found, the results will be reviewed by the Contractor QA Officer and CPM to assess whether re-analysis or re-sampling is required. All corrective actions taken by the laboratory will be documented in writing by the Laboratory Project Manager and reported to the CPM and Contractor QA Officer. In the event that corrective action requests are not in complete accordance with approved project planning documents, the EPA will be consulted and concurrence will be obtained before the change is implemented. All corrective action records will be included in the QAPP’s quality records.


4.2 Corrective Action during Data Assessment During data assessment, the Contractor QA Officer may identify the need for corrective action. Potential types of corrective action may include re-sampling by the field team, re-analysis of samples by the laboratory or re-submitting data packages with corrected clerical errors. The appropriate and feasible corrective actions are dependent upon the ability to mobilize the field team and whether the data to be collected is necessary to meet the required QA objectives (e.g., the holding time for samples is not exceeded, etc.). In the event that corrective action requests are not in complete accordance with approved project planning documents, the EPA will be consulted and concurrence will be obtained before the change is implemented. Corrective actions of this type will be documented by the Contractor QA Officer on a CAR and will be included in any subsequent reports. During laboratory data assessment, if POC well results show exceedances, Atlantic Richfield will verbally notify the Agencies immediately upon review of results. 4.3 Quality Assurance Reports to Management After investigations are complete, Atlantic Richfield will prepare an annual DSR summarizing the sampling activities described in the QAPP. The report will describe specific field activities performed during implementation of the QAPP and the physical characteristics of the study area. Each report will include field documentation, documentation of field QC procedures, and results of all field and laboratory audits. The report will also contain a discussion of the data quality assessment. The data quality discussions will contain, on a routine basis, the results of any associated field and laboratory audits, information generated on achieving specific DQOs and a summary of any corrective actions that were implemented and their immediate results on the project. A detailed listing of any deviations from the approved QAPP will also be provided with an explanation for each deviation and a description of the effect on data quality and usability, if any. The CPM and Contractor QA Officer are responsible for preparation of the Report. The report will be submitted in draft form to the EPA for review. Upon receipt of comments, the draft report will be revised to address the comments and re-submitted to the EPA for final approval. 5.0 DATA REVIEW AND USABILITY The following sections address the final project checks conducted after the data collection phase of the project is completed to confirm that the data obtained meet the project objectives and to estimate the effect of any deviations on data usability. 5.1 Data Review and Verification The process to be used for reviewing and verifying field data and the internal laboratory data reduction process are described in the following sections. Laboratory data reporting requirements, which describe how results are conveyed to data users, are also discussed.


5.1.1 Field Data Review

Raw field data will be entered in field logbooks and/or field data sheets per appropriate field SOPs, which will be reviewed for accuracy and completeness by the Field Team Leader before those records are considered final. The overall quality of the field data from any given sampling round will be further evaluated during the process of data reduction and reporting. Field data reduction procedures will be minimal in scope compared to those implemented in the laboratory setting. Field data review will include verification that any QC checks and calibrations, if necessary, are recorded properly in the field logbooks and/or data sheets and that any necessary and appropriate corrective actions were implemented and recorded. Such data will be written into field logbook and/or data sheets immediately after measurements are taken. If errors are made, results will be legibly crossed out, initialed and dated by the field member, and corrected in a space adjacent to the original (erroneous) entry. Later, the Field Team Leader will proof the field logbooks and/or data sheets to determine whether any transcription errors have been made by the field crew. If transcription errors have been made, the Field Team Leader and field crew will address the errors to provide resolution. If appropriate, field measurement data will be entered into electronic files for import to the project database. Data entries will be made from the reviewed field data sheets or logbooks, and all data entries will be reviewed for accuracy and completeness by a separate party before the electronic file is provided to the database manager. Electronic files of field measurement data will be maintained as part of the project’s quality records.

5.1.2 Laboratory Data Review Internal laboratory data reduction procedures will be according to each laboratory’s Quality Management Plan. At a minimum, paper records will be maintained by the analysts to document sample identification number and the sample tag number with sample results and other details, such as the analytical method used (e.g., method SOP #), name of analyst, the date of analysis, matrix sampled, reagent concentrations, instrument settings and the raw data. These records will be signed and dated by the analyst. Secondary review of these records by laboratory personnel will take place prior to final data reporting to Atlantic Richfield. The laboratory will appropriately flag unacceptable data in the data package.

5.1.3 Laboratory Data Reporting Requirements The laboratory will prepare data packages for transmittal of results and associated QC information to Atlantic Richfield or their designee. At a minimum, the data packages will include the case narrative, and all sample results, units and QC sample results. The laboratory will prepare data packages for transmittal of results and associated QC information to Atlantic Richfield, or their designee, in general accordance with the US EPA Contract Laboratory Program (CLP) Statement of Work for Inorganic Superfund Methods (Multi-Media, Multi-Concentration) ISM01.2 (EPA, 2010). Deviations from these specifications may be


acceptable provided the report presents all of the requested types of information in an organized, consistent and readily reviewable format.

5.1.4 Laboratory Electronic Data Deliverable Each data package, as described above, will be accompanied by an EDD prepared by the laboratory. Additional laboratory QC data can be included in the EDD. The EDDs will be cross checked against corresponding data reports to confirm consistency in results reported in these two separate formats. This cross check will take place as part of the data review process.

5.1.5 Specific Quality Control/Assessment Procedures The accuracy, precision, completeness and representativeness of analytical data will be described relative to the project’s control limits through a process of field and laboratory data quality review. Results from these reviews will be documented in a DSR format prepared for all data users. Any qualification of the data resulting from that review will also be incorporated into the project’s electronic database so that all data users are aware of any uncertainties associated with individual results. 5.2 Internal Data Review Data review is the process of verifying that information generated relative to a given sample is complete and accurate. Data review procedures will be performed for both field and laboratory operations as described below.

5.2.1 Field Quality Control Data The results of field QC sample analyses associated with each laboratory data package will be reviewed to allow for evaluation of field blanks and other field QC samples and further indications of the data quality. If a problem is identified through the review of field QC data, all related field samples will be identified, and if possible, corrective actions can be instituted and documented on a CAR. In the event that corrective action requests are not in complete accordance with approved project planning documents, the EPA will be consulted and concurrence will be obtained before the change is implemented. If data are compromised due to a problem identified via field QC sample review, appropriate data qualifications will be used to identify the data for future data users. Handling, preservation and storage of samples collected during the QAPP will be monitored on an on-going basis. The project laboratories will document sample receipt including proper containers and preservation at the time samples are logged in by the laboratory. The sample receipt records (a required data package deliverable), as well as the chain of custody documentation, will also be assessed during data review.

5.2.2 Laboratory Chemistry Data The second level of review will be performed by the Contractor QA Officer, or their designee, and will include a review of laboratory performance criteria and sample-specific criteria. One hundred percent (100%) of the data will be reviewed. Additionally, the Contractor QA Officer will


determine whether the DQOs have been met and will calculate the data completeness for the project. Data quality review is a process to determine if the data meet project-specific DQOs. The data quality review will include verification of the following: • Compliance with the QAPP; • Proper sample collection and handling procedures; • Holding times; • Field QC results; • Instrument calibration verification; • Laboratory blank analysis; • Detection limits; • Laboratory duplicates; • MS/MSD percent recoveries and RPDs; • Surrogate percent recoveries; • Data completeness and format; and • Data qualifiers assigned by the laboratory. Qualifiers that may be applied to the data include the following: • U The analyte was analyzed for but was not detected above the reporting limit. • J The analyte was positively identified; the associated numerical value is an estimate of the

concentration of the analyte in the sample. • UJ The analyte was not detected above the sample reporting limit. However, the reporting

limit is approximate and may or may not represent the actual limit of quantitation necessary to accurately and precisely measure the analyte in the sample.

• R The sample results are rejected due to serious deficiencies in the ability to analyze the sample and meet QC criteria. The presence or absence of the analyte cannot be verified.

A Data Quality Assessment (DQA) will be performed to determine whether the project-specific DQOs have been satisfied. The DQA consists of five steps that relate the quality of the results to the intended use of the data: • Step 1: Review DQOs and sampling design; • Step 2: Conduct preliminary data review; • Step 3: Apply Statistical test(s) as described in this QAPP to the data set; • Step 4: Verify assumptions; and • Step 5: Draw conclusions about the quality of the data (data report will not include

interpretation of results, but will state conclusions regarding the quality of the results). If, as a result of the DQA process, it is determined that data do not satisfy all DQOs, then corrective action(s) should be recommended and documented in the data reporting. Corrective actions include, but are not limited to, revision of the DQOs, based on the results of the investigation, or collection of more information or data. It may be determined that corrective actions are not


required, or the decision process may continue with the existing data, with recognition of the limitations of the data. Data validation checklists for metals analysis by ICP and other laboratory analyses are included in Appendix C. A checklist for summarizing the field QC results is also included in Appendix C along with a level A/B criteria screening checklist. Results of the QA review and/or validation will be included in any subsequent report, which will provide a basis for meaningful interpretation of the data quality and evaluate the need for corrective actions.


6.0 REFERENCES

AERL, 2000. Anaconda Regional Water, Waste and Soils Operable Unit (ARWW&S OU) Short-

Term Groundwater Monitoring Sampling and Analysis Plan (SAP). February 14, 2000. ARCO, 1992. Clark Fork River Superfund Site Investigations (CFRSSI) Standard Operating

Procedures (SOPs). September 1992. Atlantic Richfield Company, 2009. ARWW&S Short-Term Groundwater Monitoring Sampling

and Analysis Plan (SAP) Addendum No. 1. March 2009. CDM, 2013a. Draft Anaconda Smelter NPL Site Long-Term Ground Water Monitoring Plan.

April 24, 2013. CDM, 2013b. Draft Anaconda Smelter NPL Site Groundwater Management Plan (GWMP).

January 11, 2013. DEQ, 1995. Montana Numeric Water Quality Standards – Circular WQB-7. December 1995. DEQ, 2010. Montana Numeric Water Quality Standards – Circular DEQ-7. August 2010. EPA, 1998. Anaconda Smelter NPL Site, Anaconda Regional Water, Waste and Soils Operable

Unit Record of Decision (ROD). September 1998. EPA, 2000. Addenda to the Clark Fork River Superfund Site Investigations Data

Management/Data Validation Plan. February 15, 2000. EPA, 2001. EPA Requirements for Quality Assurance Project Plans (QA/R-5). Washington DC:

EPA, Office of Environmental Information. EPA/240/B-01/003. Available at http://www.epa.gov/quality/qs-docs/r5-final.pdf.

EPA, 2005. Intergovernmental Data Quality Task Force, Uniform Federal Policy for Quality

Assurance Project Plans: Evaluating, Assessing, and Documenting Environmental Data Collection and Use Programs, Final, Version 1. March 2005.

EPA, 2006. Guidance on Systematic Planning Using the Data Quality Objectives Process (QA/G-

4). Washington DC: EPA, Office of Environmental Information. EPA/240/B-06/001. Available at http://www.epa.gov/quality/qs-docs/g4-final.pdf.

EPA, 2010. Contract Laboratory Program (CLP) Statement of Work for Inorganic Superfund

Methods (Multi-Media, Multi-Concentration) ISM01.2. January 2010. EPA and DEQ, 2011. Anaconda Smelter NPL Site, Anaconda Regional Water, Waste and Soils

Operable Unit, Record of Decision (ROD) Amendment. September 2011.


http://www.epa.gov/quality/qs-docs/r5-final.pdf

http://www.epa.gov/quality/qs-docs/g4-final.pdf

EPA, 2012. Guidelines Establishing Test Procedures for the Analysis of Pollutants Under the Clean Water Act; Analysis and Sampling Procedures; Final Rule. 40 CFR Parts 136, 260 et al. May 18, 2012.

PTI, 1992. Clark Fork River Superfund Site Invenstigations (CFRSSI) Quality Assurance Project Plan (QAPP). May 1992

Software Solinst Telemetry System (STS) Gold Com Agent version 1.1.1


FIGURES

Figure 1: Project Organization Chart

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MW-263MW-264MW-261MW-262

MW-273

MW-206D

MW-251MW-252

MW-253MW-254

MW-255

MW-256

MW-257

MW-82M

MW-85M

MW-90M

MW-259MW-274

MW-265MW-266

MW-267 MW-268

MW-269MW-270

MW-271MW-272

MW-258

C2-AL1

D3-AL1

E2-AL1

F2-BR

FH-2

IW-01MW-204 MW-206 MW-207

MW-208

MW-209

MW-211

MW-212MW-213

MW-214

MW-216MW-218d

MW-218sMW-219

MW-220

MW-224

MW-225

MW-230

MW-231

MW-232

MW-233

MW-240MW-241

MW-242

MW-245eMW-245s

MW-247

MW-248dMW-248eMW-248s

MW-249s

MW-250dMW-250s

MW-26MW-26M

MW-31MMW-72

MW-85

MW-90

NGP-1

OD-3S

SH-3WGP-1

MW-235

B4-BR

OD-3D

IW-05TI-AMW-201

LF-4MW-205

MW-227 MW-210

MW-249d

MW-9

MW-82

A1-BR2

A2-BR

MW-244

SP98-30

SP98-31 SP98-26

SP98-27

SP98-32

SP99-01SP97-20

SP98-34

SP97-12

SST-26

SP97-31SP98-37

SP98-36SST-1

SP97-19

SST-30

SP98-28

SP98-20

SP98-8

SP98-16

SP98-23

SST-29

MW-31

MW-24

MW-243

MW-25

OD-2DOD-2S

SP-07-01

SP-07-02

SP-07-03

WCT-27

35 36 31 32 33 34 35 36 314 3 322 331 6 5 4 3 2 1 6 5 4 3 2 16 5 4 3 2 19 610 511 412 7 8 9 10 11 12 7 8 9 10 11 12 7 8 9 10 11 1216 715 814 913 18 17 16 15 14 13 18 17 16 15 14 13 18 17 16 15 14 13 1821 22 1723 1624 19 20 21 22 23 24 19 20 21 22 23 24 19 20 21 22 23 2428 1927 2026 21

25 30 29 28 27 26 25 30 29 28 27 26 25 30 29 28 27 26 25 3033 2934 35 2836 31 32 33 34 35 36 3132

33 3435 36 31 32 33 34 35 36

5

314

323

332 1 6 5 4 3 2 1

6 5 4 3 2 1 65 4 3 2 1 6 5 4

89 710 911 1012 11 12 7 89 10 11 12 7

8 9 10 11 12 7 8 916 1815 1714 1613 15 14 13 18 17 16 15 14 13 1817 16 15 14 13 18 17 16

21 1922 2023 2124 22 23 24 19 20 21 22 23 24 1920 21 22 23 24 19 20 2128 3027 2926 2825 27 26

2530 29 28 27 26 25 30

29 28 27 26 25 30 29 2833 3134 3235 3336 34 35 36 31 32 33 34 35 36 31 32 33 34 35 36 31 32 334 63

5241

3 2 1 6 5 4 3 2 1 6 5 4 3 2 1 6 5 49 10 11 12 7 8 9 10 711 812 9 10 11 12 7 8 9 10 11 12 7 8 9

FIGURE 2 ARWW&S OULONG-TERMGROUNDWATERMONITORING PLAN

DISPLAYED AS:PROJECTION/ZONE: MSPDATUM: NAD 83UNITS: FEETSOURCE: PIONEER

Path: \\192.168.252.15\Project$\AnaData\AR\ARWWS\Site Wide Documents\ARWW&S Site Wide Groundwater\DATA FROM CDM\GW_MONITORING_CO_PLN-001-15.mxd

0 8,000 16,0004,000Feet

DATE: 3/4/2015

OLD WORKS HAA

ANACONDA

OLD WORKS WMA

NORTH OPPORTUNITY TI ZONES

OPPORTUNITY PONDS/SMELTER HILL WMAs

BEDROCK TI ZONES

SOUTH OPPORTUNITY TI ZONES

BLUE LAGOON AOC

OPPORTUNITY

WARM SPRINGS

LEGEND

WELL

" OPPORTUNITY WELL" OPPORTUNITY PONDS COVER WELL" EVENT DRIVEN WELL" 5-YEAR REVIEW

OPPORTUNITY TILE DRAIN

SPRING

SURFACE EXPRESSION OF GROUND WATER

ROADS

STREAMS

COUNTY LINE

PUBLIC LAND SURVEY SYSTEM

BEDROCK TI ZONE

NORTH OPPORTUNITY TI ZONE

SOUTH OPPORTUNITY TI ZONE

WASTE MANAGEMENT AREA (WMA)

POINT OF COMPLIANCE

5-YEAR REVIEW NOTES:

1) SAMPLING FREQUENCIES ARE PROVIDED ON TABLE 1.

2) POC/EVENT DRIVEN WELLS ARE SHOWN AS POC WELLS.

3) ALL BOUNDARIES ARE APPROXIMATE. FINAL BOUNDARIESTO BE DETERMINED.

4) ALL MONITORING WELL AND SPRING LOCATIONS AREAPPROXIMATE.

TABLES

TABLE 1: ARWWS OU LONG‐TERM GROUNDWATER MONITORING PLAN

Well ID Alias Well ID Type Purpose Frequency Location COC List 1,2OTHER

ANALYTESADD'L ANALYTES @ 5‐

YEAR REVIEW 2SCREEN

INTERVAL [FT]

FH‐2 Well 5‐year Review 2 seasons each 5 years Stucky Ridge As None Gen. Chemistry 7 ‐ 17MW‐248d MW-248D Well 5‐year Review 2 seasons each 5 years Stucky Ridge As None Gen. Chemistry 90 ‐ 110MW‐248e MW-248E Well 5‐year Review 2 seasons each 5 years Stucky Ridge As None Gen. Chemistry 160 ‐ 180MW‐248s MW-248S Well 5‐year Review 2 seasons each 5 years Stucky Ridge As None Gen. Chemistry 34 ‐ 54SP97‐20 Spring 5‐year Review 1 season each 5 years Stucky Ridge As None Gen. Chemistry N/ASP98‐26 Spring 5‐year Review 1 season each 5 years Lost Creek Expansion Area As None Gen. Chemistry N/ASP98‐27 Spring 5‐year Review 1 season each 5 years Lost Creek Expansion Area As None Gen. Chemistry N/ASP98‐28 Spring 5‐year Review 1 season each 5 years Stucky Ridge As None Gen. Chemistry N/ASP98‐30 Spring 5‐year Review 1 season each 5 years Lost Creek Expansion Area As None Gen. Chemistry N/ASP98‐31 Spring 5‐year Review 1 season each 5 years Lost Creek Expansion Area As None Gen. Chemistry N/ASP98‐32 Spring 5‐year Review 1 season each 5 years Stucky Ridge As None Gen. Chemistry N/ASP98‐34 Spring 5‐year Review 1 season each 5 years Stucky Ridge As None Gen. Chemistry N/ASP99‐01 Spring 5‐year Review 1 season each 5 years Stucky Ridge As None Gen. Chemistry N/A

F2‐BR Well 5‐year Review 2 seasons each 5 years Smelter Hill Loop Track As None Gen. Chemistry 71 ‐ 94MW‐233 Well 5‐year Review 2 seasons each 5 years Smelter Hill – Mill Creek As None Gen. Chemistry 10 ‐ 14MW‐245d MW-245D Well 5‐year Review 2 seasons each 5 years Weather Hill ‐ Lost Horse Cr As None Gen. Chemistry 154 ‐ 164MW‐245e MW-245E Well 5‐year Review 2 seasons each 5 years Weather Hill ‐ Lost Horse Cr As None Gen. Chemistry 214 ‐ 234MW‐245s MW-245S Well 5‐year Review 2 seasons each 5 years Weather Hill ‐ Lost Horse Cr As None Gen. Chemistry 104 ‐ 124MW‐249d MW-249D Well 5‐year Review 2 seasons each 5 years Mill Creek ‐ Cabbage Gulch As None Gen. Chemistry 184 ‐ 201MW‐249s MW-249S Well 5‐year Review 2 seasons each 5 years Mill Creek ‐ Cabbage Gulch As None Gen. Chemistry 8 ‐ 18MW‐250d MW-250D Well 5‐year Review 2 seasons each 5 years Mill Creek ‐ Joyner Gulch As None Gen. Chemistry 63 ‐ 83MW‐250s MW-250S Well 5‐year Review 2 seasons each 5 years Mill Creek ‐ Joyner Gulch As None Gen. Chemistry 7 ‐ 16NGP‐1 Well 5‐year Review 2 seasons each 5 years Mt. Haggin/Smelter Hill TI Zone As None Gen. ChemistryWGP‐1 Well 5‐year Review 2 seasons each 5 years Mt. Haggin/Smelter Hill TI Zone As None Gen. ChemistrySH‐3 Spring 5‐year Review 1 season each 5 years Mt. Haggin/Smelter Hill TI Zone As None Gen. Chemistry N/A

SP97‐12 Spring 5‐year Review 1 season each 5 years Mt. Haggin/Smelter Hill TI Zone As None Gen. Chemistry N/ASP97‐19 Spring 5‐year Review 1 season each 5 years Mt. Haggin/Smelter Hill TI Zone As None Gen. Chemistry N/ASP97‐31 Spring 5‐year Review 1 season each 5 years Mt. Haggin/Smelter Hill TI Zone As None Gen. Chemistry N/ASP98‐16 Spring 5‐year Review 1 season each 5 years Mt. Haggin/Smelter Hill TI Zone As None Gen. Chemistry N/ASP98‐20 Spring 5‐year Review 1 season each 5 years Mt. Haggin/Smelter Hill TI Zone As None Gen. Chemistry N/ASP98‐23 Spring 5‐year Review 1 season each 5 years Mt. Haggin/Smelter Hill TI Zone As None Gen. Chemistry N/ASP98‐36 Spring 5‐year Review 1 season each 5 years Mt. Haggin/Smelter Hill TI Zone As None Gen. Chemistry N/ASP98‐37 Spring 5‐year Review 1 season each 5 years Mt. Haggin/Smelter Hill TI Zone As None Gen. Chemistry N/ASP98‐8 Spring 5‐year Review 1 season each 5 years Mt. Haggin/Smelter Hill TI Zone As None Gen. Chemistry N/ASST‐1 Spring 5‐year Review 1 season each 5 years Mt. Haggin/Smelter Hill TI Zone As None Gen. Chemistry N/ASST‐26 Spring 5‐year Review 1 season each 5 years Mt. Haggin/Smelter Hill TI Zone As None Gen. Chemistry N/ASST‐29 Spring 5‐year Review 1 season each 5 years Mt. Haggin/Smelter Hill TI Zone As None Gen. Chemistry N/ASST‐30 Spring 5‐year Review 1 season each 5 years Mt. Haggin/Smelter Hill TI Zone As None Gen. Chemistry N/A

A1‐BR2 Well 5‐year Review 2 seasons each 5 years Smelter Hill As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 160 ‐ 180A2‐BR Well 5‐year Review 2 seasons each 5 years Smelter Hill As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 60 ‐ 80B4‐BR Well 5‐year Review 2 seasons each 5 years Smelter Hill As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 65 ‐ 85C2‐AL1 Well 5‐year Review 2 seasons each 5 years Smelter Hill As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 52 ‐ 72D3‐AL1 Well 5‐year Review 2 seasons each 5 years Smelter Hill As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 22 ‐ 42E2‐AL1 Well 5‐year Review 2 seasons each 5 years Smelter Hill (northeast) As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 19 ‐ 39MW‐210 Well 5‐year Review 2 seasons each 5 years Anaconda Ponds Northwest Toe As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 37 ‐ 46MW‐211 Well 5‐year Review 2 seasons each 5 years Anaconda Ponds Northwest Toe As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 103 ‐ 118MW‐212 Well POC Semi‐Annually North of Triangle Waste As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 39 ‐ 54MW‐214 Well POC Semi‐Annually North toe of Opportunity Ponds As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 6 ‐ 15MW‐216 Well POC Semi‐Annually East toe of Opportunity Ponds As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 5 ‐ 14

STUCKY RIDGE/LOST CREEK

MOUNT HAGGIN/SMELTER HILL AREA

OPPORTUNITY PONDS/SMELTER HILL WMA




YEAR REVIEW 2SCREEN

INTERVAL [FT]

MW‐218d MW-218D Well 5‐year Review 2 seasons each 5 years Anaconda Ponds Middle Toe As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 240 ‐ 249MW‐218s MW-218S Well 5‐year Review 2 seasons each 5 years Anaconda Ponds Middle Toe As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 70 ‐ 85MW‐219 Well 5‐year Review 2 seasons each 5 years Anaconda Ponds Northeast Toe As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 60 ‐ 74MW‐220 Well 5‐year Review 2 seasons each 5 years Anaconda Ponds ‐ Toe East As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 85 ‐ 95MW‐258 NW-6s; NW6S Well POC Semi‐Annually Anaconda Ponds ‐ Toe East As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 35 ‐ 45MW‐227 Well 5‐year Review 2 seasons each 5 years East corner of Smelter Hill WMA As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 27 ‐ 37MW‐244 Well 5‐year Review 2 seasons each 5 years Smelter Hill (northwest) As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 31 ‐ 41MW‐247 Well 5‐year Review 2 seasons each 5 years Smelter Hill (northwest) As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 65.5 ‐ 84MW‐243 Well 5‐year Review 2 seasons each 5 years Triangle Waste Area As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 40 ‐ 50MW‐253 Well 5‐year Review 2 seasons each 5 years Triangle Waste Area As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 67 ‐ 87MW‐254 Well 5‐year Review 2 seasons each 5 years Triangle Waste Area As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 56 ‐ 76MW‐256 Well 5‐year Review 2 seasons each 5 years Triangle Waste Area As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 75 ‐ 95MW‐26 Well POC Semi‐Annually Northeast toe of Opportunity Ponds As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 6 ‐ 16MW‐26M Well POC Semi‐Annually Northeast toe of Opportunity Ponds As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 60 ‐ 70MW‐31 Well 5‐year Review Semi‐Annually after cover installed3 East toe of Opportunity Ponds As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 6 ‐ 16MW‐31M Well 5‐year Review Semi‐Annually after cover installed3 East toe of Opportunity Ponds As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 6 ‐ 16MW‐82 Well 5‐year Review Semi‐Annually after cover installed3 Inside East toe of Opportunity Ponds As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 40 ‐ 50MW‐82M Well 5‐year Review Semi‐Annually after cover installed3 Inside East toe of Opportunity Ponds As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 70 ‐ 80MW‐85 Well 5‐year Review Semi‐Annually after cover installed3 Interior of Opportunity Ponds As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 45 ‐ 56MW‐85M Well 5‐year Review Semi‐Annually after cover installed3 Interior of Opportunity Ponds As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 75 ‐ 85MW‐90 Well 5‐year Review Semi‐Annually after cover installed3 Interior of Opportunity Ponds As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 56 ‐ 66MW‐90M Well 5‐year Review Semi‐Annually after cover installed3 Interior of Opportunity Ponds As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 85 ‐ 95MW‐273 NW-5s; NW-05S Well POC Semi‐Annually Opportunity Ponds South Flank As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 10 ‐ 20MW‐265 NW-1-OPd; NW01D Well POC Semi‐Annually East toe of Opportunity Ponds As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 66 ‐ 76MW‐266 NW-1-OPs; NW-01S Well POC Semi‐Annually East toe of Opportunity Ponds As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 9 ‐ 19MW‐267 NW-2-OPd; NW-02D Well POC Semi‐Annually East toe of Opportunity Ponds As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 64 ‐ 74MW‐268 NW-2-OPs; NW-02S Well POC Semi‐Annually East toe of Opportunity Ponds As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 8 ‐ 18MW‐269 NW-3-OPd; NW-03D Well POC Semi‐Annually East toe of Opportunity Ponds As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 62 ‐ 72MW‐270 NW-3-OPs; NW-03S Well POC Semi‐Annually East toe of Opportunity Ponds As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 12 ‐ 22MW‐271 NW-4-OPd; NW-04D Well POC Semi‐Annually East toe of Opportunity Ponds As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 71 ‐ 81MW‐272 NW-4-OPs; NW-04S Well POC Semi‐Annually East toe of Opportunity Ponds As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 10 ‐ 20MW‐24 Well 5‐year Review 2 seasons each 5 years North toe of Opportunity Ponds As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 8 ‐ 18MW‐25 Well 5‐year Review 2 seasons each 5 years North toe of Opportunity Ponds As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 4 ‐ 14

IW‐01 Well Event Driven Event Driven NE Quarter Section 2 As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 22 ‐ 42IW‐05 Well 5‐year Review 2 seasons each 5 years NE Quarter Section 2 As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 21 ‐ 41LF‐4 Well 5‐year Review 2 seasons each 5 years NW Quarter Section 1 As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 32 ‐ 42

MW‐201 Well 5‐year Review 2 seasons each 5 years NE Quarter Section 2 As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 18 ‐ 28MW‐204 Well Event Driven Event Driven Old Works Red Sands As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 33 ‐ 43MW‐205 Well 5‐year Review 2 seasons each 5 years NE Quarter Section 1 As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 27 ‐ 37MW‐206 Well Event Driven Event Driven Section 1 west of sewer lagoons As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 28 ‐ 43MW‐206d MW-206D Well Event Driven Event Driven Section 1 west of sewer lagoons As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 53 ‐ 73MW‐207 Well POC/Event Driven Semi‐Annually/Event Driven SE corner of Old Works WMA As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 77 ‐ 92MW‐208 Well Event Driven Event Driven SE Quarter Section 31 As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 47 ‐ 67MW‐209 Well Event Driven Event Driven SE Quarter Section 31 As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 49 ‐ 69MW‐213 Well Event Driven Event Driven Old Works Red Sands As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 32 ‐ 41MW‐240 Well Event Driven Event Driven SE Quarter Section 32 As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 80 ‐ 90MW‐241 Well Event Driven Event Driven SE Quarter Section 31 As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 50 ‐ 60MW‐242 Well Event Driven Event Driven West of Old Works WMA As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 60 ‐ 70MW‐251 Well POC/Event Driven Semi‐Annually/Event Driven NE corner of Old Works WMA As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 56 ‐ 76MW‐252 Well POC/Event Driven Semi‐Annually/Event Driven West of Old Works WMA As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 55 ‐ 75

OLD WORKS WMA




YEAR REVIEW 2SCREEN

INTERVAL [FT]

MW‐255 Well POC/Event Driven Semi‐Annually/Event Driven West of Old Works WMA As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 75 ‐ 95MW‐72 Well 5‐year Review 2 seasons each 5 years SW Quarter Section 31 As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 25 ‐ 35TI‐A Well 5‐year Review 2 seasons each 5 years NW Quarter Section 2 As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 25 ‐ 35

MW‐263 LTW-1-SOd; LTW-1-SOD; LTW-1D Well POC Semi‐Annually North of HWY. 1, NE Section 16 As Fe Gen. Chemistry 30 ‐ 40MW‐264 LTW-1-SOs; LTW-1-SOS; LTW-1S Well POC Semi‐Annually North of HWY. 1, NE Section 16 As Fe Gen. Chemistry 13 ‐ 23MW‐261 LTW-3-SOd; LTW-3-SOD; LTW-3D Well POC Semi‐Annually North of HWY. 1, Section 15 As Fe Gen. Chemistry 30 ‐ 40MW‐262 LTW-3-SOs; LTW-3-SOS; LTW-3S Well POC Semi‐Annually North of HWY. 1, Section 15 As Fe Gen. Chemistry 9 ‐ 19MW‐225 Well 5‐year Review 2 seasons each 5 years SW Quarter Section 14 As Fe Gen. Chemistry 7 ‐ 17MW‐232 Well 5‐year Review 2 seasons each 5 years Mount Haggin Ranch As Fe Gen. Chemistry 6 ‐ 15MW‐231 Well 5‐year Review 2 seasons each 5 years Willow Creek As Fe Gen. Chemistry 6 ‐ 15MW‐9 Well Town of Opportunity Semi‐Annually West of Highway 1 and Fairmont Rd. As Fe Gen. Chemistry 41 ‐ 46MW‐259 LTW-4-SOD; LTW-4D Well POC Semi‐Annually Section 16 ‐ Hwy 1 As Fe Gen. Chemistry 28 ‐ 38MW‐274 LTW-4R-SOS; LTW-4SR Well POC Semi‐Annually Section 16 ‐ Hwy 1 As Fe Gen. Chemistry 7 ‐ 27OD‐2D Well 5‐year Review 2 seasons each 5 years Northeast of Opportunity As Fe Gen. Chemistry 29 ‐ 34OD‐2S Well 5‐year Review 2 seasons each 5 years Northeast of Opportunity As Fe Gen. Chemistry 14 ‐ 19OD‐3D Well 5‐year Review 2 seasons each 5 years East Opportunity near Willow Creek As Fe Gen. Chemistry 30 ‐ 35OD‐3S Well 5‐year Review 2 seasons each 5 years East Opportunity near Willow Creek As Fe Gen. Chemistry 9 ‐ 14WCT‐27 Tile Drain 5‐year Review 2 seasons each 5 years Hwy 1 at Sidney Street As Fe Gen. Chemistry N/A

MW‐235 Well 5‐year Review 2 seasons each 5 years Blue Lagoon As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 3 ‐ 13MW‐257 Well 5‐year Review 2 seasons each 5 years Blue Lagoon As ‐ Cd ‐ Cu ‐ Pb ‐ Zn Fe ‐ Mn ‐ SO4 Gen. Chemistry 3 ‐ 13

SP‐07‐01 Surface expression of ground water 5‐year Review 1 season each 5 years North Opportunity As N/ASP‐07‐02 Surface expression of ground water 5‐year Review 1 season each 5 years North Opportunity As N/ASP‐07‐03 Surface expression of ground water 5‐year Review 1 season each 5 years North Opportunity As N/AMW‐224 Well 5‐year Review 2 seasons each 5 years North Opportunity As 12 ‐ 22MW‐230 Well 5‐year Review 2 seasons each 5 years North Opportunity As 5 ‐ 15

1. The following field parameters will also be monitored: pH, temperature, Eh, SC, DO, and water levels.2. K, Na, Ca, Mg, Fe (if not on ‘other analytes’ list), sulfate [if not on ‘other analytes’ list], Cl, bicarbonate, carbonate, hardness, and TDS.3. New wells in new cover areas (engineered cover wells) will be sampled semi‐annually for 5 years, then annually once every 5 years. See Table 7 for engineered cover wells sampling schedule.

BLUE LAGOON AREA

DUTCHMAN CREEK AREA

SOUTH OPPORTUNITY/YELLOW DITCH AREA

TABLE 2: WORK SCHEDULE

Dates: Tasks:

First Quarter 2015 Develop Quality Assurance Project Plan (QAPP). February/March Perform low-water groundwater monitoring and sampling.

Second/Third Quarter Evaluate low-water groundwater results for comparison to site performance standards at POC wells. Submit tables of POC water quality results to EPA and DEQ.

Late-June/August Perform high-water groundwater monitoring and sampling. Perform event triggered groundwater sampling, as necessary.

Fourth Quarter of Sampling Year/ First Quarter of Following

Year

Evaluate high-water groundwater results for comparison to site performance standards at POC wells. Submit tables of POC water quality results to EPA and DEQ.

Prepare DSR.

TABLE 3: WATER QUALITY PERFORMANCE STANDARDS

COC

ARWW&S ROD Water Quality Performance Standards1

2011 ROD Amendment Water Quality Performance Standards2

Groundwater Human Health Standard (µg/L)

Groundwater Human Health Standard (µg/L)

Arsenic 18 103 Cadmium 5 5 Copper 1,000 1,000 Lead 15 15 Zinc 5,000 2,000

1 ARWW&S ROD standards based upon Montana Numeric Water Quality Standards – Circular WQB-7, December 1995. (DEQ, 1995). 2 2011 ROD Amendment standards based upon Montana Numeric Water Quality Standards – Circular DEQ-7, (DEQ, 2010). 3 This standard is waived for groundwater within TI Zones as identified in the 2011 ROD Amendment. *Standards for metals in groundwater are based on the dissolved metals portion of the sample. **Water collected from springs (surface expressions of groundwater) is considered to be both surface water and groundwater. These samples are filtered-acidified for analysis of the dissolved metals portion of the sample and are subject to the 2011 ROD Amendment Standards above.

TABLE 4: PRECISION, ACCURACY AND COMPLETENESS CALCULATION EQUATIONS

Characteristic Formula Symbols

Precision (as relative percent difference, RPD)

𝑅𝑅𝑅𝑅𝑅𝑅 =�𝑥𝑥𝑖𝑖 − 𝑥𝑥𝑗𝑗�

�𝑥𝑥𝑖𝑖 + 𝑥𝑥𝑗𝑗

2 �× 100 xi, xj: replicate values of x

Precision (as relative standard deviation, RSD, otherwise known as coefficient of variation)

𝑅𝑅𝑅𝑅𝑅𝑅 =𝜎𝜎�̅�𝑥

× 100 σ: sample standard deviation x�: sample mean

Accuracy (as percent recovery, R, for samples without a background level of the analyte, such as reference materials, laboratory control samples and performance evaluation samples)

𝑅𝑅 =𝑥𝑥𝑡𝑡

× 100 x: sample value t: true or assumed value

Completeness (as a percentage, C) 𝐶𝐶 =

𝑛𝑛𝑁𝑁

× 100

𝑛𝑛: number of valid data points produced

𝑁𝑁: total number of samples taken

TABLE 5: SUMMARY OF LABORATORY QUALITY ASSURANCE/QUALITY CONTROL CHECKS

Action Frequency Control Limit Corrective Action1

Method Blank (MB)

Prepared and analyzed for every batch of 20 or less samples digested. For 6010C – Carried through the appropriate steps of the analytical process. These steps may include, but are not limited to, prefiltering, digestion, dilution, filtering and analysis.

Less than the absolute value of the reporting limit (RL).

If the concentration in the MB is greater than the RL, samples associated with that MB must be reprepared, unless the samples are nondetect or greater than 10 times the blank contamination. When reporting data with a hit in the MB, all samples affected will be footnoted with the appropriate flag to document contamination in the blank. Exception: If sample result is less than 10 times the blank contamination and sample cannot be reanalyzed, report sample with appropriate qualifier to indicate an estimated value. Client must be alerted and authorize this condition.

Laboratory Control Sample (LCS)

Prepared and analyzed for every batch of 20 or less samples digested.

80-120% for 6010B; 6010C; 6020/6020A; SM 2540-B, -C, and –D; and EPA 160.4 80-120% for 200.7 and 200.8 For tests undergoing volatizing by EPA 160.4, RPD < 20%

If the percent recovery for the LCS falls outside the control limits the analyses should be terminated, the problem corrected, and the samples associated with that LCS re-analyzed. If reanalysis of the samples fail, the samples affected by the failing LCS elements need to be re-digested and re-analyzed.


Exception: if LCS fails high and samples are ND the data may be reported with appropriate qualification.

Matrix Spike (MS) / Matrix Spike Duplicate (MSD)

One MS/MSD per batch for 6010B and 6010C. If >10 samples for 200.7, an additional MS is required. One per 20 samples for 6020 and 6020A. The spikes are performed at a minimum frequency of 10% for SM 2320B. Samples identified as field blanks cannot be used for spike sample analysis. One per 10 samples for 200.8, EPA 300.0/SW-846 Method 9056A. Clients may have requirements that create a higher frequency of MS/MSD samples.

75-125% for 6010B, 6010C, 6020/6020A 70-130% for 200.7 and 200.8 80-120% for SM 2320B 20% RPD for the MS/MSD 90-110% for EPA 300.0/SW-846 Method 9056A

If the percent recovery for the MS and MSD fall outside the control limits, the results are flagged that they are outside acceptance criteria along with the parent sample. If the RPD exceeds the acceptance criteria, the MSD sample and associated parent sample need to be flagged. SM 2320B: If acceptance criteria are not met for the MS/MSD, batch data may be qualified as long as the LCS/LCSD are within their respective acceptance criteria. 6020/6020A/200.8: If LCS and MBs are acceptable, the MS/MSD chromatogram should be reviewed and it may be reported with appropriate footnote indicating matrix interferences. Perform a PDS on any elements that failed to meet criteria. EPA 300.0/SW-846 Method 9056A – If the concentration of matrix spike is less than 25% of the background concentration of the matrix, the matrix spike


recovery should not be calculated.

Post Digestion Spike (PDS)

Required if reporting by 6010C and MS/MSD fail outside 75-125%. If the PDS also fails then a 5 times dilution is made of the PDS. One per batch if there is a MS failure for 6020/6020A/200.8.

75-125% for 6010B 80-120% for 6010C and 6020/6020A/200.8

6010B /6010C: If PDS fails data is qualified. 6020/6020A/200.8: If the element fails to meet the recovery criteria, then the dilution test on the PDS must be performed. If the dilution test fails, it is determined to be matrix interference.

Internal Standard

Introduced automatically with every sample for EPA 6010B, 6010C, and EPA 200.7.

70-130%

If the recovery is outside the criteria, sample is reanalyzed at a 5 times dilution.

pH Calibration Check

Immediately after calibration of the pH probe for SM 2320B.

±0.10 pH units If the acceptance criterion is not met, terminate analysis, correct the problem, recalibrate and attempt a new pH calibration check.

Laboratory Control Sample Duplicate (LCSD)

One per batch of up to 20 samples. An LCSD must be substituted in the event of insufficient sample volume for a duplicate sample. An LCSD must be performed quarterly for EPA 300.0/SW-846 Method 9056A to generate data points to determine a precision limit for the laboratory.

For SM 2320B, RPD 20% For SM 2540-B, -C, and –D, RPD < 10% For tests undergoing volatizing by EPA 160.4, RPD < 20% For EPA 300.0/SW-846 Method 9056A, until sufficient data points (>20 points) have been generated, ≤ 20 % RPD

If acceptance criteria are not met for the LCSD a single reanalysis of the respective failing QC is allowed. If the reanalysis is outside the acceptance criteria, the analysis must be terminated, the problem corrected, the instrument recalibrated, and the calibration reverified.

Initial Calibration Verification (ICV) / Continuing

An ICV must be conducted immediately after pH calibration check (pH 5.0 Buffer).

90-110%

If acceptance criteria are not met for the ICV a single reanalysis of the respective failing QC is allowed. If the reanalysis


Calibration Verification (CCV)

A CCV standard must be analyzed and reported every ten samples and at the end of the analytical run to ensure calibration accuracy.

is outside the acceptance criteria, the analysis must be terminated, the problem corrected, the instrument recalibrated, and the calibration reverified. If the deviation of the CCV is greater than ±10%, the analysis must be stopped and the problem corrected. All samples analyzed since the last compliant CCV must be reanalyzed.

Initial Calibration Blank (ICB) and Continuing Calibration Blank (CCB)

A calibration blank must be analyzed immediately after every ICV and CCV.

The ICB and CCB’s must be less than the reporting limit unless otherwise specified by the client or QAPP.

If acceptance criterion is not met for the ICB/CCB, a single reanalysis of the respective failing QC is allowed. If the reanalysis is outside the acceptance criteria, the analysis must be terminated, the problem corrected, the instrument recalibrated and the calibration reverified. A failing ICB/CCB may be accepted if the affected sample results are non-detect or at least 10 times greater than the failing result. Batch data must be qualified accordingly.

Serial Dilution

One per batch of 20 samples or less.

Fivefold dilution must agree within ± 10% of the original determination if analyte concentration is >50 times the MDL.

If criteria is not met, original sample and dilution will be reanalyzed.


Serial Dilution of Post Digestion Spike

Required by certain client QAPPs. This is not a standard practice.

Fivefold dilution must agree within ± 10% of the original determination.

If this fails data is qualified.

Duplicate Sample

Once every 10 samples for SM 2540-B, -C, and –D and EPA 160.4. One for every 20 samples for 6020 and 6020A.

For SM 2540-B, -C, and –D; RPD ≤ 10% For tests undergoing volatizing by EPA 160.4, RPD < 20% For 6020 and 6020A, %Diff ≤ 20%

Reanalyze the parent sample in duplicate to confirm either the parent sample result or duplicate result. If either the parent sample or the duplicate is below the MDL, RPD is not generated and no further action is necessary. Exception: If the results of the sample and duplicate are less than 5x the RL, the data can be reported with the D8 qualifier and no further corrective action unless it is suspected that the data is in error for any other reason.

Pad Weight Verification (not reported)

One pad per box of 100 (pre-weighed TDS pads) is weighed and the weight is logged on the certificate that is included in the box with the pad. This documentation is filed with the certificates of analysis for all materials received in the wet chem department.

± 0.0005 g of the weight specified by the manufacturer

If outside the acceptance criteria, attempt verification on a second pad in the lot. If the second is also outside the acceptance criteria, discard the lot.

1Corrective actions are sequential for cases indicating multiple corrective actions. If the first corrective action is not sufficient to bring analysis back into control, the second action noted will be implemented. 2 Laboratory analyses will reported in simplified data packages, and not all QC samples listed in this table will be provided. Laboratory QC samples will be provided by the laboratory upon request.

TABLE 6: SUMMARY OF SAMPLING AND MONITORING ACTIVITIES

Task Event Proposed

Time Frame

Media Estimated Number

of Samples*

Monitoring Wells. Sampling of wells at high water and low water.

Low-water table sampling

Feb.-March Groundwater 871

High-water table sampling July-Aug. Groundwater 871

Springs and Seeps. Sampling of known springs and seeps at high flow.

High-flow sampling May-June Groundwater/

Surface Water

282

Event Sampling. Sampling of Old Works event driven monitoring wells.

High-flow sampling June-July Groundwater 14

*Does not include QA samples. 1 New wells in new cover areas (engineered cover wells) are semi-annually sampled for the first 5 years following cover installation, then are annually sampled once every 5 years. 2 Includes one tile drain that is sampled semi-annually every 5 years.

TABLE 7: ENGINEERED COVER WELLS SAMPLING SCHEDULE

Well ID Last Semi-Annual Sampling Year1

MW-90 2015 MW-90M 2016 MW-85 2014

MW-85M 2016 MW-82 2019

MW-82M 2019 MW-31 2014

MW-31M 2014 1Engineered Cover Wells will be sampled semi-annually for the first 5 years after cover installation, then annually once every 5 years.

TABLE 8: MONITORING WELL SAMPLE SUMMARY

1New wells in new cover areas (engineered cover wells) will be sampled semi-annually for 5 years, then annually once every 5 years. 2Includes four (4) wells that are POC/Event Driven. 3Estimated based on one event driven sampling event.

Med

ia

Task Purpose Frequency

Num

ber

of

Sam

plin

g L

ocat

ions

Nat

ural

Sa

mpl

es

(est

imat

e)

Gro

undw

ater

Monitoring Wells

5-year Review

2 seasons each 5 years 53 106

Semi-annually after cover installed1 8 16

POC Semi-Annually 252 50

Event Driven Event Driven 142 143

Town of Opportunity Semi-Annually 1 2

TABLE 11: SUMMARY OF SAMPLE ANALYSES AND PREPARATIONS

Task Measurement Endpoint Preservation Holding Time

Container Size/ Analytical

Requirement Analytical Method

and Reference

Matrix: Water (wells and springs)

Monitoring Wells

Dissolved metals/ metalloids

Calcium, magnesium, sodium, potassium, iron

Sulfate, chloride, hardness, TDS, and total alkalinity

Field Parameters: temp, pH, ORP, DO, SC, water level

Metals and hardness: field filtered(dissolved), acidified* Major anions, TDS, alkalinity: Cooled** with no preservative.

Metals and hardness – 6 months TDS– 7 days Sulfate and chloride– 28 days Total alkalinity – 14 days

Metals/Hardness: 250 mL high-density polyethylene (HDPE) bottle with HNO3 Major ions/TDS/Sulfate/ Chloride/Alkalinity: 500 mL HDPE bottle

Dissolved metals and hardness - EPA 200.8 TDS – EPA 160.4 (2540C) Sulfate – EPA 300.0 Chloride – EPA 300.0 Total Alkalinity – Standard Methods 2320B

Springs/ Seeps

Dissolved arsenic Field Parameters: temp, pH, ORP, DO, SC, flow

Dissolved arsenic: field filtered (dissolved), acidified*

Metals: 250 mL HDPE bottle with HNO3

Dissolved arsenic - EPA 200.8

* After filtering, acidify to pH <2 with HNO3. ** Cool to <6C but above freezer per Guidelines Establishing Test Procedures for the Analysis of Pollutants Under the Clean Water Act; Analysis and Sampling Procedures; Final Rule. 40 CFR Parts 136, 260 et al. (EPA, 2012) Bottles may be provided by the laboratory as certified, pre- cleaned sample bottles.

TABLE 12: METHOD DETECTION LIMITS

AND REPORTING LIMITS

Analyte Analytical Method MDL (µg/L) RL (µg/L) Arsenic*

EPA 200.8

0.250 0.50 Cadmium* 0.033 0.080 Calcium 8.385 40.0 Copper* 0.216 1.0 Iron 8.015 50 Lead* 0.046 0.10 Magnesium 2.846 10.0 Potassium 8.342 50.0 Sodium 18.240 50.0 Zinc* 2.500 5.0 Sulfate

EPA 300 0.60 1.20

Chloride 0.60 1.20 Carbonate Standard Method

2320B 2.5 5.0

Bicarbonate 2.5 5.0 Total Dissolved Solids

EPA 160.4 (Standard Method 2540C) 5.0 10.0

*Constituent of Concern (COC) Carbonate/Bicarbonate used to calculate Total Alkalinity Magnesium/Calcium used to calculate Hardness

TABLE 13: PROJECT SAMPLING FIELD SOP REFERENCES

Referenced CFRSSI SOP # Field SOP # Subject

G-8

SOP-DE-01 Personal Decontamination SOP-DE-02 Equipment Decontamination – Inorganic Contaminants

SOP-DE-02A Equipment Decontamination – Pumps for Well Sampling SOP-DE-03 Investigation Derived Waste Handling

G-10 SOP-G-01 Determining and Recording Station Locations GW-1 SOP-GW-02 Sampling with a Bailer GW-5 SOP-GW-03 Depth to Water Level Measurements HG-1

SOP-GW-08 Sampling Seeps and Springs HG-2

GW-1

SOP-GW-10 Purging and Sampling with a 12-Volt Submersible Pump

SOP-GW-10B Purging and Sampling with a Grundfos Redi-Flo Submersible Pump

SOP-GW-10C Purging and Sampling with a Peristaltic Pump NA SOP-GW-13 Sampling Groundwater from a Tap

NA SOP-GW-14 Field Water Quality Measurements Using the Geotech Multi-Probe Flowblock Flow Through Device

GW-8 SOP-GW-15 Continuous Groundwater Level Monitoring G-5 SOP-SA-01 Soil and Water Sample Packaging and Shipping

HG-4 SOP-SA-02 Sample Preservation and Containerization for Aqueous Samples

G-6 SOP-SA-03A Field Quality Control Samples for Water Sampling SOP-SA-03B Preparation of Equipment Rinsate Blanks For Submersible Pumps

G-7 SOP-SA-04 Chain of Custody Forms for Environmental Samples G-3

SOP-SA-05 Project Documentation G-4

SW-1 SOP-SW-01 Surface Water/Stream Sampling NA SOP-SW-02 Field Sample Filtration

SW-7 SOP-SW-03 Temporary Installation of Flumes for Flow Measurement and Surface Water Sampling

NA SOP-SW-04 Sampling Surface Water with the Scienceware 8 Liter Churn Splitter

HG-8 SOP-WFM-01 Field Measurement of pH in Water SOP-WFM-02 Field Measurement of Oxygen Reduction Potential in Water

HG-7 SOP-WFM-03 Field Measurement of Specific Conductance HG-6 SOP-WFM-04 Field Measurement of Water Temperature SW-6 SOP-WFM-05 Stream Flow Measurement with Marsh McBirney Flow Meter HG-8 SOP-WFM-07 Field Measurement of Dissolved Oxygen

HG-10 SOP-WFM-08 Field Turbidity Measurement NA SOP-WFM-09 Bucket and Stopwatch Method for Measuring Flow

TABLE 14: LABORATORY SOPs

Laboratory SOP Reference Methods

Inductively Coupled Plasma Atomic Emission Spectroscopy

EPA 6010B, 6010C, and EPA 200.7

Alkalinity, Titrimetric (Automated Titration Technique) SM 2320B Metals Analysis by ICP/MS EPA 6020/6020A/200.8 Measurement of Solids in Water and Wastewater SM 2540-B, -C, and -D, and EPA 160.4 Determination of Inorganic Anions by Ion Chromatograph

EPA 300.0/SW-846 Method 9056A

Appendix A1

Field Standard Operating Procedures

SOP-DE-01; PERSONAL DECONTAMINATION

PROCEDURES

DATE ISSUED: 12/03/14 REVISION: 0 PAGE 1 of 2

PURPOSE To provide standard instructions for decontamination of all personnel leaving a contaminated area.

SCOPE This practice has been prepared for the Contracting workforce and applies to work carried out by and on behalf of the Contractor. All members of the Contracting workforce who conduct the work shall be trained and competent in the risk-assessed work described below.

WORK INSTRUCTIONS The following instructions are intended to provide sufficient guidance to perform the task in a safe, accurate, and reliable manner. Should these instructions present information that is inaccurate or unsafe, operations personnel must bring the issue to the attention of the Project Manager and the appropriate revisions made. All work carried under this SOP will be consistent with procedures and policies described in the appropriate Operation, Maintenance, and Monitoring (O&M) Plan (where applicable), appropriate Site Specific Health and Safety Plan (SSHASP), and the Contractor’s Corporate Health and Safety Plan (HASP).

TASK INSTRUCTIONS 1. Wash/

Remove outer contaminated items.

Remove nitrile or latex gloves by grasping the outside of the opposite glove near the wrist. Pull and peel the glove away from the hand, turning the glove inside out with the contaminated side now on the inside. Hold the removed glove in the opposite gloved hand. Slide one or two fingers of the ungloved hand under the wrist of the remaining glove. Peel glove off from the inside, creating a bag for both gloves. If wearing protective coveralls such as Tyvec suites, brush built up material off the suit, only if in designated decontamination zone. Unzip the coverall and begin rolling that outwards, rolling it down over your shoulders. Place both hands behind your back and pull down each arm until completely removed. Sit down and remove each shoe then roll the coveralls down (ensuring the contaminated side is not touched or comes into contact with clothing) over your knees until completely removed. If there is not a designated decontamination zone, remove PPE carefully to contain material and place it in the appropriate disposal container. For instructions to remove additional PPE not described in this document, refer to the project’s HASP. Wash with soap (nonphosphate) and tap water the outer, more heavily contaminated items, such as boots. Rinse the items in tap water.

2. Wash inner contaminated items.

If necessary, wash with soap (nonphosphate) and tap water the inner, less contaminated items. Rinse the items in tap water.

3. Store/ transport items.

Store/transport contaminated items in a separate designated area to prevent cross contamination prior to disposal.

4. Dispose of Dispose of contaminated clothing and equipment in accordance with

SOP-DE-01; PERSONAL DECONTAMINATION

PROCEDURES


contaminated items.

site/project, client, and/or federal and state requirements.

5. Contact the Safety and Health Manager.

For contaminants other than those found typically at uncontrolled hazardous waste sites, such as asbestos, PCB, PCE, etc. see the Safety and Health Manager.

Information about Emergency Decontamination: 1. During life-

saving process.

If the decontamination procedure is essential to the life-saving process, decontamination must be performed immediately.

2. During heat-related illness.

If heat-related illness develops, protective clothing should be removed as soon as possible. Wash, rinse, and/or cut off protective clothing/equipment.

3. When medical treatment is needed.

If medical treatment is required to save a life, decontamination should be delayed until the victim is stabilized. Wrap the victim to reduce contamination of others. Alert medical personnel to the emergency and instruct them about potential contamination. Instruct medical personnel about specific decontamination procedures.

DRAWINGS, DOCUMENTS, AND TOOLS/EQUIPMENT The following documents should be referenced to assist in completing the associated task.

P&IDS

DRAWINGS

RELATED SOPs/PROCEDURES/

WORK PLANS

TOOLS In general, the following items will be needed: soap, tap water, tarps, decontamination tubs, brushes, and sprayers. The SAP or Quality Assurance Project Plan (QAPP) will describe additional items needed for decontamination.

FORMS/CHECKLIST

SOP-DE-02; EQUIPMENT DECONTAMINATION -

INORGANIC CONTAMINANTS


PURPOSE To provide standard instructions for equipment decontamination (inorganic contaminants – heavy metals).


NOTES All equipment leaving the contaminated area of a site must be decontaminated. Decontamination methods include removal of contaminants through physical, chemical, or a combination of both methods. Decontamination procedures are to be performed in the same level of protection used in the contaminated area of a site. In some cases, decontamination personnel may be sufficiently protected by wearing one level lower protection. The information for site specific equipment decontamination and personnel protection levels, as detailed in the Sampling and Analysis Plan (SAP), work plan, and Site-Specific Health and Safety Plan (SSHASP), should be followed. The following decontamination procedures are for typical uncontrolled hazardous waste sites. For a specific or unusual contaminant, such as dioxins, see the SSHASP and consult with the Safety and Health Manager. Decontamination procedures should be used in conjunction with methods to prevent contamination of sampling and monitoring equipment. If practical, one-time-use equipment should be used, and disposed of in accordance with the SAP, work plan, and SSHASP.


TASK INSTRUCTIONS 1. Remove gross

contamination. Remove gross contamination with a tap water rinse. If available, use pressurized or gravity flow tap water. If not, a 5-gallon bucket of tap water and a stiff brush may be used.

2. Wash equipment.

Wash equipment in a solution of soap (no phosphate) and tap water with a stiff brush.

3. Triple rinse equipment.

Triple rinse the equipment with tap water. Then, rinse the equipment with de-ionized or distilled water.

4. Rinse equipment with nitric acid/distilled water mixture.

If specified in the SAP, work plan, or SSHASP, rinse the equipment with a mixture of 10:1 nitric acid in distilled water (10 parts water to 1 part nitric acid). In many cases, the tap water and de-ionized water rinses will be sufficient. If a nitric rinse is used, rinse the equipment again with distilled water.




5. Air dry equipment.

Place equipment on plastic sheeting or foil to air dry.

6. Transport/ store equipment.

Wrap equipment in foil or plastic wrap to transport or store.

7. Triple rinse decontamination equipment.

Triple rinse equipment (i.e., brushes, buckets, tubs, etc.) used in the decontamination process with water, preferably pressurized.

8. Wash decontamination equipment.

Agitate the equipment used in the decontamination process in the soap/tap water solution. (The tub which holds the solution will only have the water rinse)

9. Triple rinse decontamination equipment.

Triple rinse equipment with tap water.

10. Store and label decontamination equipment.

Place equipment in appropriate areas, so they are used only for decontamination purposes. Label the equipment, if necessary.

11. Dispose of decontamination solutions.

Use a waste water container to properly dispose of the soap/tap water solution, the tap water rinse, and the de-ionized water rinse. When contaminants have been identified, either in the solutions or elsewhere on the site, solutions should be disposed of appropriately as discussed in the SAP, work plan, or SSHASP. If they are hazardous (e.g., characteristic, listed, etc.), dispose of them as such. Note: when using other than the above mentioned solutions, check with the Safety and Health Manager and the Project Manager. Some solvents must be evaporated.

12. Measure effectiveness of procedures.

Effectiveness of the decontamination procedures will be measured using field equipment rinsate blanks (see the Site-Specific Quality Assurance Project Plan).





P&IDS

DRAWINGS


WORK PLANS

SOP-DE-01 Personnel Decontamination Procedures.

TOOLS Five 5-gallon buckets, tap water, stiff brushes, soap, de-ionized or distilled water, nitric acid (if required), plastic sheeting or foil, tarps, decontamination tubs and buckets, and sprayers. If additional items for decontamination are needed, they will be listed on the SAP.

FORMS/CHECKLIST

SOP-DE-02A; EQUIPMENT DECONTAMINATION –

PUMPS FOR WELL SAMPLING


PURPOSE To provide standard instructions for equipment decontamination to pumps for well sampling.



TASK INSTRUCTIONS Notes: All non-disposable or non-dedicated equipment used for sampling or monitoring

activities must be decontaminated prior to leaving a site. Decontamination methods include removal of contaminants through physical methods, chemical cleaning or a combination of both methods. Decontamination of equipment should be performed in the same level of protection as worn during sampling. In some cases, personnel may be sufficiently protected during decontamination activities by wearing one level lower of PPE. Requirements for site specific equipment decontamination and personnel protection levels as detailed in the sampling and analysis plan (SAP), work plan (WP) or site specific Health and Safety Plan (HASP) should be followed. The following decontamination procedures are for typical uncontrolled hazardous waste sites. For a specific or unusual contaminant such as dioxins, the decontamination procedures should be discussed in the SAP, WP and or HASP. Decontamination procedures should be used in conjunction with storage methods that prevent contamination of cleaned sampling and monitoring equipment. One time use equipment is preferred if practical, and should be disposed of in accordance with the site-specific HASP, SAP or WP. Dedicated equipment should be used, when practical for long term sampling at a location. Prior to the sampling event review the HASP and SAP to determine if purge and decontamination water needs to be contained and and/or proper disposal and storage requirements. When preparing a SAP/HASP determine if water from all stages of the decontamination procedure needs to be contained or if only water from initial stages of the process requires containment. As part of the planning process in determining a method for storage and disposal of purge and decontamination fluids, the amount of water that could be generated during the sampling event, and the type and concentrations of potential contaminants should be estimated. If needed the proper equipment for either storage or disposal should be available on-site at the start of sampling. Water can be contained at the sampling location or on site in tanks, barrels or buckets for later disposal. Purge and decontamination water stored on the site can be sampled and analyzed so that the proper




disposal method can be determined. Waste water could also be removed at the time of sampling with a pump truck to a disposal site.

Decontamination Procedures for Inorganic Contaminants

1. Decontamination Procedures for Inorganic Contaminants

1. Set up the decontamination station. If water needs to be contained, place a sheet of plastic on the ground or a small swimming pool in the decontamination area. Wrap the edges of the plastic sheeting around pieces of PVC or boards to form a small pool to prevent any spilled water from running onto adjacent ground. All decontamination activities should take place within this confined area. If containment of decontamination fluids is required, set up a means of collecting the water (bucket, hose, barrel, etc.)

2. Remove pump from the well making sure that tubing and pump do not

contact the ground surface. If disposable or dedicated tubing is being used, remove tubing from the pump and place in appropriate storage/refuse container. Don a new pair of gloves and if needed add a small piece of tubing to pump.

3. Place pump in decontamination container containing tap water. The

size of the pump and amount of tubing needing decontamination will determine the size of the container. The container can range from a stainless steel pan which holds 1 -2 gallons for the smaller 12 volt submersible pumps with a small amount of tubing to a 5 gallon bucket or similar large container that will hold the larger pumps such as the Grunfoss Redi-Flo II and larger 12V submersible pumps . The pump should be placed in a container that is tall enough to submerge the pump, and is easy to pour additional fluid into. Non-dedicated tubing such as that on the Grunfoss Redi-Flo II will be decontaminated on the reel or for smaller amounts of reusable tubing typically found on the 12 volt submersible pumps, the tubing and electric cord will be coiled as it is removed from the well and placed in a bucket dedicated to decontamination.

4. If not done previously, don a new pair of nitrile gloves. 5. Pour tap water into the container to cover the pump. Turn the pump on

and continue pouring tap water into the container until all water from the well has been flushed from the pump and tubing. The amount will depend on the amount of tubing associated with the pump and can range from 1 gallon for the smaller pumps to 5 gallons for the Grunfoss pumps. If the water purged from the well was turbid or colored, the water flowing from the pump discharge can be monitored to determine when the well water has been removed. If the water is to be contained make sure it is discharged throughout the decontamination process into the appropriate container.

6. Add a very small pinch or drop of non-phosphate soap (use Liquinox©

or Alconox©) to the container and turn on pump. Continue pouring tap




water into the container to flush the pump until the soapy water has been pumped through the entire length of tubing.

7. Turn the pump off and place it in a second container for a de-ionized

(DI) water flush of the soapy water. Pour DI water into the container to cover the pump. Turn the pump on and continue pouring DI water into the container until the soapy water has been flushed from the system. This water should be discharged over any tubing that will be reinserted into the next well. Keep in mind that this process is to remove contaminants from the pump and tubing so that they are not introduced to the next well. Make sure that the tubing is thoroughly rinsed. Water purged from the next well will flush remaining DI water from the tubing.

8. Turn the pump off, empty water from the bucket containing tubing if

necessary and place pump and tubing into a bucket dedicated for pump storage. The Grunfoss Redi-Flow II pump should be returned to the pump holder on the reel, remember to rinse the pump holder with DI water between wells. Care should be taken to keep tubing and pumps from touching the ground or other surface during transport and storage. A plastic bag can be placed over the container holding the pump or a dedicated plastic container can be used to transport or store the pump.

9. If containment is required empty the water remaining in the

decontamination containers into the storage/disposal container. Cover the dedicated decontamination containers with plastic, foil or a lid to prevent contaminants from entering the containers during transport or storage. Empty the water in the swimming pool or plastic into the storage container by scooping the water into the disposal container. If needed a funnel dedicated to the project can be used to help in getting water into the container.

Decontamination Procedures for Organic Contaminants

1. Decontamination Procedures for Organic Contaminants

It is strongly recommended that disposable or dedicated tubing be used for all organic contaminant sampling.

If a submersible pump is required for sampling, a stainless steel pump that can be taken apart for cleaning is recommended.

If free product is detected in a well, use disposable tubing or a bailer to collect the sample as purging large amounts of product through tubing makes it almost impossible to clean.

1. Set up the decontamination station. If water needs to be contained, place a sheet of plastic on the ground or a small swimming pool in the decontamination area. Wrap the edges of the plastic sheeting around pieces of PVC or boards to form a small pool to prevent any spilled water from running onto adjacent ground. All decontamination




activities should take place within this confined area. If containment of decontamination fluids is required, set up a means of collecting the water (bucket, hose, barrel, etc.).

2. Remove pump from the well making sure that tubing and pump do not

contact the ground surface. If disposable or dedicated tubing is being used, remove tubing from pump and place in appropriate storage/refuse container. Don a new pair of nitrile gloves. Wipe pump with a paper towel wetted with DI or methanol (or solvent specified in the SAP/WP/HASP). Add a small piece of tubing to pump. If tubing is to be reused, wet a paper towel with a small amount of DI or methanol (or other solvent specified in the SAP) and wipe pump and tubing as it is removed from the well.

3. Place pump in decontamination container containing tap water. The

size of the pump and amount of tubing needing decontamination will determine the size of the container. The container can range from a stainless steel pan which holds 1 -2 gallons for the smaller 12 volt submersible pumps with a small amount of tubing to a 5 gallon bucket or similar large container that will hold the larger pumps such as the Grunfoss Redi-Flo II and the larger 12V submersible pumps. The pump should be placed in a container that is tall enough to submerge the pump, and is easy to pour additional fluid into. Non-dedicated tubing such as that on the Grunfoss Redi-Flo II will be decontaminated on the reel or for smaller amounts of reusable tubing on the 12 volt submersible pumps, the tubing and electric cord will be coiled as it is removed from the well and placed in a bucket dedicated to decontamination.

4. If not done previously, don a new pair of nitrile gloves. 5. Pour tap water into the container to cover the pump. Turn the pump on

and continue pouring tap water into the container until all water from the well has been flushed from the pump and tubing. The amount will depend on the amount of tubing associated with the pump and can range from 1 gallon for the smaller pumps to 5 gallons for the Grunfoss pumps. If the water purged from the well was turbid or colored, the water flushing from the pump discharge can be monitored to determine when the well water has been removed. If the water is to be contained make sure it is discharged throughout the decontamination process into the appropriate container.

6. Add a very small pinch or drop of non-phosphate soap (use Liquinox©

or Alconox©) to the container and turn on pump. Continue pouring tap water into the container to flush the pump until the soapy water has at least been pumped through the entire length of tubing.

7. At this time a small amount of methanol or solvent can be run through




the pump, depending on the expected contaminants. Turn off the pump and place it into a container holding the appropriate solvent. Turn the pump on and run the solvent through the pump. Make sure that a container is available to catch and retain the used solvent. Turn the pump off.

8. If using a stainless steel pump that can be taken apart, follow the

manufacturer’s directions, dissemble the pump, wipe all parts of the pump with methanol, DI or other solvent and reassemble.

9. Place the pump in a container for a de-ionized (DI) water flush of the

pump and tubing. Pour DI water into the container to cover the pump. Turn the pump on and continue pouring DI water into the container until the solvent (methanol) has been flushed from the system. This water should be discharged over any tubing that will be reinserted into the next well. Keep in mind that this process is to remove contaminants from the pump and tubing so that they are not introduced to the next well. Make sure that the tubing is thoroughly rinsed. Water from the next well will be run through the tubing prior to sampling, any DI water remaining will be flushed from the pump during the purging.

10. Turn the pump off, empty water from the bucket containing tubing if

necessary and place pump and tubing into a bucket dedicated for pump storage. The Grunfoss Redi-Flow II pump should be returned to the pump holder on the reel, remember to rinse the pump holder with DI water between wells. Care should be taken to keep tubing and pumps from touching the ground or other surface during transport and storage. A plastic bag can be placed over the container holding the pump or a dedicated plastic container can be used to transport or store the pump.

11. If containment is required empty the water remaining in the

decontamination containers into the storage/disposal container. Cover the dedicated decontamination containers with plastic, foil or a lid to prevent contaminants from entering the containers during transport or storage. Empty the water in the swimming pool or plastic into the storage container by scooping the water into the disposal container. If needed a funnel dedicated to the project can be used to help in getting water into the container

EQUIPMENT USED FOR DECONTAMINATION

1. Equipment Used for Decontamination:

1. Rinse equipment used in the decontamination process with tap water, preferably pressurized. Do not rinse the container labeled DI!

2. Keep decontamination equipment separated so that it is only used for

decontamination. Make sure it’s labeled appropriately. DISPOSAL OF DECONTAMINATION SOLUTIONS




1. Disposal of Decontamination Solutions

1. Dispose of the soap/tap water solution and the de-ionized water rinse as detailed in the SAP/WP or site specific HASP.

2. Dispose of the solvent rinse residue into proper waste containers. Be

sure to check with the health and safety officer and the project manager for disposal requirements. For example, some solvents can be evaporated. EFFECTIVENESS OF DECONTAMINATION

1. Effectiveness of Decontamination

1. Effectiveness of the decontamination procedures will be measured using field equipment rinsate blanks (see the site-specific Quality Assurance Project Plan and SOP-SA-03B Preparation of Equipment Rinsate Blanks for Submersible Pumps).

DRAWINGS, DOCUMENTS, AND TOOLS/EQUIPMENT

The following documents should be referenced to assist in completing the associated task. P&IDS

DRAWINGS Map with site location and sample locations.


WORK PLANS

SOP-SA-03B Preparation of Equipment Rinsate Blanks for Submersible Pumps

TOOLS Pump, nitrile gloves, small swimming pool, plastic sheeting, pieces of PVC or boards, tap water, stainless steel pan or 5 gallon bucket/similar large container (to fit pump), decontamination containers (with lid), Liquinox© or Alconox, DI water, plastic bag. Optional: bucket, hose, barrel, etc. for water containment, funnel, methanol.

FORMS/CHECKLIST

SOP-DE-03; INVESTIGATION DERIVED WASTE

HANDLING


PURPOSE To provide standard instructions for handling investigation-derived waste in accordance with EPA protocols and DEQ guidance. Investigation-derived waste may be generated during a Site Assessment (SA), Site Investigation (SI), or Remedial Investigation (RI).



TASK INSTRUCTIONS 1. Collect and

dispose of decontamination fluids.

Collect and dispose of decontamination fluids by using one of the following methods:

- Send fluids to a Treatment, Storage, and Disposal (TSD) facility. - Evaporate fluids. - Tread fluids using an activated carbon or air sparging unit. - Temporarily store fluids until determined if they are contaminated.

Dispose of decontamination fluids, generated from cleaning equipment used in background sampling or for sampling in areas where past results indicate that contaminants are below standards, to the ground surface.

2. Discharge groundwater from developing and purging wells.

If past monitoring results and laboratory analysis indicate that all contaminants are below groundwater standards, discharge groundwater generated from developing and purging monitoring wells to the ground surface.

3. Collect/label/ store contaminated groundwater from developing and purging wells.

If past monitoring results indicate that one or more contaminants are above groundwater standards, collect the purged water and potentially contaminated water. There may be instances (e.g., inclement weather) where purge water and/or decontamination water will be temporarily stored in drums or tanks to be treated on site with granulated activated carbon or air sparging. If the water is determined by laboratory analysis to contain contaminants above groundwater standards and cannot be treated on site, store the water on site until shipping/disposal arrangements can be made. If the water is visibly contaminated, drum, label, and store the water on site until shipping/disposal arrangements are made. Label all containers stored on site with the following information: date, time, contents, any corresponding analytical data,

SOP-DE-03; INVESTIGATION DERIVED WASTE

HANDLING


collection location, contact person, and contact agency, etc.

4. Return soils back to borehole.

Unless it is visibly contaminated, place soil and/or cuttings from monitoring well installation back in the borehole.

5. Collect/label/ store contaminated soils from installing wells.

If the soil is visibly contaminated, drum, label, and store the soil/cuttings on site until shipping/disposal arrangements are made. Drum and label soils from borings/well installations located in previously sampled areas that are known to be contaminated. Leave these soils on site until shipping/disposal arrangements are made.

6. Pack and dispose of one-time use equipment and PPE.

Pack disposable equipment intended for one-time use and personal protective equipment (PPE) materials for appropriate disposal. Double bag the disposable equipment and PPE utilized for sampling and dispose of it as a solid waste in the local landfill. Package, drum, and label disposable equipment and PPE utilized for sampling visibly contaminated sites or sites known to be contaminated from previous monitoring. Leave equipment and PPE on site until shipping/disposal arrangements are made.

7. Dispose of samples not used for analysis.

Laboratories will dispose of the portions of the samples submitted, but not used for analysis. If samples are retained and not sent for analysis, they need to be returned to the site prior to remediation or disposed of according to federal and state regulations.


P&IDS

DRAWINGS


WORK PLANS

SOP-DE-02 Equipment Decontamination.

TOOLS Five 5-gallon buckets, tap water, stiff brushes, soap, de-ionized or distilled water, nitric acid (if required), plastic sheeting or foil, tarps, decontamination tubs and buckets, sprayers, storage containers, labels, and shovels.

FORMS/CHECKLIST

SOP-G-01; DETERMINING AND RECORDING

STATION LOCATIONS


PURPOSE To provide standard instructions for determining and recording station locations.



TASK INSTRUCTIONS Notes: The geographic coordinates of all locations at which samples are collected (stations)

must be known to allow accurate data interpretation and to allow resampling of the same location. In addition to the geographic coordinates of the station, an estimate of the accuracy of those coordinates must be provided. This SOP describes methods by which station coordinates, and the accuracy of those coordinates, are to be determined.

Station locations are to be reported to the data management standards outlined in the approved SAP/QAPP. Depending on the availability of information from the Geographic Information System (GIS), one of the following two general approaches should be taken to determine the location of new stations.

Approach 1 – Reference to Features within GIS Coverage

1. Approach 1 – reference to features within GIS coverage

Approach 1 may be used whenever the area to be sampled falls within the region for which the project specific GIS has high resolution vector coverage and the sampling stations are within 100 feet of a permanent landmark identifiable on GIS maps. A high-resolution coverage is one derived from maps with a scale of 1:2,400 or larger. The procedure of using this approach is as follows:

1. At least four weeks prior to sampling, meet with the GIS staff and determine the scale, area, and features to be included on GIS maps to be used by field personnel; in special circumstances a shorter lead time may be possible.

2. On the GIS maps supplied, mark each location with a small “x”. Write the station identifier next to the “x”. On the border of the map, record the distance to each landmark within 100 feet, and estimate of the potential error associated with the marked location (if appropriate), and any other brief comment useful to describe the station’s location.

3. When data are submitted to the U.S. EPA, include the annotated map.


STATION LOCATIONS


Approach 2 – Surveying of Station Location

1. Approach 2 – Surveying of station location

Approach 2 should be used whenever the area to be sampled is outside the region of high-resolution GIS coverage or when the area within the region of high-resolution GIS coverage but there are no landmarks within 100 feet. This approach may also be used whenever Approach 1, described above, is allowable, at the discretion of field personnel.

Either conventional surveying of a Global Positioning System (GPS) must be used to identify the location of each station. GPS surveys must be differentially corrected, using a coarse-acquisition (C-A) level or better GPS receiver within 25-meter accuracy unless stricter standards are required by the project-specific SAP. An estimate of the absolute accuracy (in feet) must be made by the operator of the surveying instrument.

For each station, the location, the estimated error, the surveying method used, and any applicable narrative description of the location must be recorded. The location must be expressed in Montana State Plane coordinates, based on NAD 83 datum.

Use of Public Lands Survey Data

1. Use of public lands survey data

In addition to state plane coordinates (or in lieu of state plane coordinates if such information is not available) station location data can be provided in terms of Public Lands Survey (PLS) township, range, section, and sub-section designations. PLS section information should be presented in terms of grid cell codes instead of narrative form (an example of the narrative form is: “NE quarter of SW quarter of SW quarter of Section 21”). Grid cell codes are more concise and more amenable to computerized manipulation.

Grid cell codes consist of the section number followed by letters to indicate the quadrants. Quadrants are lettered starting with “A” in the northeast quadrant, “B” in the northwest quadrant, “C” in the southwest quadrant, and “D” in the southeast quadrant, as the following figure illustrates:

B A

C D


STATION LOCATIONS


Each quadrant can be successively subdivided in a similar manner:

B A

B A D

C D

PLS quadrants are coded starting with the largest and proceeding to the smallest. Therefore, the NE quarter of the SE quarter of the SE quarter of the NW quarter of section 21 would be coded as:

21BDDA

Recording of Elevation Data

1. Recording of Elevation Data

Measurements (or estimates) of the vertical as well as the horizontal position of each station should be made. The information to be recorded in association with each elevation observation includes:

• The method used to determine the station elevation (e.g., altimeter, GPS, survey, topographical map interpolation);

• The vertical coordinate datum (National Geodetic Vertical Datum 1929 or North American Vertical Datum 1983); and

• An estimate of the potential error associated with the recorded elevation (in feet).

Resampling of a Station

1. Resampling of a Station

Some locations (stations) may be sampled more than once during different investigations. If it is known that stations sampled during the current investigation (survey) were previously sampled and are described in previous reports, the relationship between old and new station identifiers should be recorded. Specifically, the following information should be included with the station description:

• Station identifier used for the current survey; • Identity of previous survey (s) (i.e., survey name and code) under which the

station was sampled; and • Station identifiers used for each previous survey.

Summary

1. Summary Complete and accurate records of station locations are necessary to allow meaningful data interpretation and resampling. Either of two methods described above may be used to record the locations at which samples are collected. If


STATION LOCATIONS


stations are within 100 feet of a landmark within GIS’1:2,400 coverage, then the station locations may be marked on a GIS map. Otherwise, the station location must be surveyed using either conventional or GPS techniques.

The information to be maintained for each station includes the following:

• Station ID; • Station coordinates in Montana State Plane Zone 3 coordinates; • Station elevation; • An estimate of the horizontal and vertical error of the station location; • An indication of the method used to locate the station (marked GIS map,

GPS, or conventional survey); • An indication of the method used to estimate station elevation; • The address of the parcel containing the station, if appropriate; • A brief narrative description of the station location; and • The correspondences to any station IDs established under previous surveys.





WORK PLANS

TOOLS Global Positioning System (GPS) FORMS/CHECKLIST

SOP-GW-02; SAMPLING WITH A BAILER


PURPOSE To provide standard instructions for sampling with a bailer.



TASK INSTRUCTIONS 1. Determine

water level in the well.

Using clean, non-contaminating equipment (e.g., an electronic depth to water level indicator (avoid indicating paste)) (per SOP-DE-02 Equipment Decontamination), determine the water level in the well. Refer to SOP-GW-03 Depth to Water Level Measurements for instructions. If required, check for the presence of free or floating product with an interface probe or clear bailer. Calculate the fluid volume in the casing and determine the appropriate volume of water to be purged prior to any sample collection.

2. Collect sample with bailer.

Attach a clean, decontaminated bailer to clean line for lowering and raising the bailer into the well. A disposable or dedicated bailer is preferred. Make sure the knot will not come loose. Lower bailer slowly until it contacts water surface. The bailer should not contact the bottom of the well. Allow bailer to sink slowly and fill with a minimum of surface disturbance. Slowly raise bailer to surface. Do not allow bailer line to contact the ground surface.

3. Discharge purged water into appropriate container.

Use bottom discharge device to slowly discharge purged water into an appropriate container, or pour slowly from top of bailer. Purged water shall be disposed of in accordance with the site-specific Sampling and Analysis Plan (SAP), client disposal requirements and/or SOP-DE-03 Investigation Derived Waste Handling.

4. Acquire sufficient purge volume.

Repeat task #2 as needed to acquire sufficient purge volume.

SOP-GW-02; SAMPLING WITH A BAILER


5. Pour water into appropriate containers.

Once sufficient purge volume has been collected, use bottom discharge device or pour slowly from top of bailer into appropriate sample containers.

6. Acquire sufficient sample volume.

Repeat task #2 as needed to acquire sufficient sample volume.

7. Preserve and cap the samples.

If water is being collected for volatile organic compounds analysis, place preservative in vials (if appropriate, prior to filling). Check that a Teflon liner is present in cap if one is required. After filling, secure the cap tightly. Check for air bubbles. To check for air bubbles: turn the VOC bottle upside down, tap lightly, turn right side up, see if any bubbles float to the top. If you see a bubble, remove lid, add additional water, and reseal.

8. Label the samples.

Label the sample bottle with an appropriate tag/label. Be sure to complete the tag with necessary information. Record the information in the field logbook and complete all chain-of-custody documents.

9. Transport the samples.

Place the properly labeled sample bottle in an appropriate carrying container maintained at 4°C +/- 2°C throughout the sampling and transportation period.

10. Decontaminate bailer.

Decontaminate bailer thoroughly after each use according to SOP-DE-02 Equipment Decontamination.



DRAWINGS


WORK PLANS

SOP-DE-02 Equipment Decontamination, SOP-DE-03 Investigation Derived Waste Handling, and SOP-GW-03 Depth to Water Level Measurements.

TOOLS Electronic depth to water level indicator, disposable or dedicated bailer, buckets, sample bottles, clean string, and field logbook.

FORMS/CHECKLIST

SOP-GW-03; DEPTH TO WATER LEVEL

MEASUREMENTS


PURPOSE To provide standard instructions for conducting depth to water level measurements.



TASK INSTRUCTIONS Electric Depth to Water Indicator:

1. Inspect well casing.

Inspect well and casing for a marked measuring point. If no measuring point is marked, locate the north side of the well and establish a marking point. Choose the point for ease of accurately reading the measuring tape.

2. Test the water level indicator.

Test that the water level indicator is on and working by pushing the test button on the indicator and checking the buzzer sound level and/or checking for the light. Make sure the equipment is clean and decontaminated per SOP-DE-02 Equipment Decontamination Procedures.

3. Lower the sensor.

Lower the sensor probe slowly into the well to minimized disturbance of water when it is encountered. As the sensor is lowered down the well, the buzzer and/or flashing light will indicate contact with water. Be aware that sensor may indicate water prior to actual water level, if the probe contacts condensation on the well casing.

4. Align probe cable.

Once the buzzer has sounded, align the marked probe cable with the designated marking point and gently raise and lower the probe until the exact mark on the probe cable, when water is encountered, is identified.

5. Record information.

Record this information in the project logbook as the depth to water (DTW). In addition, record where the marking point was located (e.g., top of casing [TOC], top of PVC [TOPVC], inner PVC [IPVC]) to help maintain continuity, if subsequent DTW readings are needed from this well.

6. Reel in equipment.

Reel in sensor probe.

7. Decontaminate equipment.

Decontaminate all equipment prior to re-use per SOP-DE-02 Equipment Decontamination.

SOP-GW-03; DEPTH TO WATER LEVEL

MEASUREMENTS


Chalked Measuring Tape Depth to Water Measurements:

1. Coat tape with chalk.

Make sure the equipment is clean and decontaminated per SOP-DE-02 Equipment Decontamination Procedures. Coat the lower three to five feet of tape with chalk and lower into well. Listen for weight to contact water and lower tape an additional 0.5 foot.

2. Record information.

Record measure point and pull tape carefully from well. Read the wetted chalk mark and record. Subtract the wetted chalk mark from the measure point for true depth to water.

3. Decontaminate equipment.

Decontaminate all equipment prior to re-use per SOP-DE-02 Equipment Decontamination.



DRAWINGS Map with well locations.


WORK PLANS

SOP-DE-02 Equipment Decontamination.

TOOLS Water level indicator or measuring tape and chalk, and field logbook. FORMS/CHECKLIST

SOP-GW-08; SAMPLING SEEPS AND

SPRINGS


PURPOSE To provide standard instructions for sampling seeps and springs.



TASK INSTRUCTIONS 1. Identify

sampling location.

Identify a sampling location from which the sample is to be collected. This point must be as close to the actual seep as possible to reduce contact time with the atmosphere and potential for surface contamination. Make sure the sampling equipment is clean and decontaminated per SOP-DE-02 Equipment Decontamination Procedures.

2. Label sample bottles.

Label the sample bottle with an appropriate tag/label. Be sure to complete the tag with necessary information. Put clear tape over the tag/label. Record the information in the field logbook and complete all chain-of-custody documents.

3. Collect water sample.

If possible, submerge the container under the water or hold in flow until full. If the water is not deep enough to do this, use a smaller decontaminated or new container that can be filled or partially filled and slowly transfer the water to the sampling containers. The cap of the sampling container could also be used to fill the bottle. Care must be taken to not disturb the bottom sediments and incorporate them into the sample. If the water is still too shallow, use a new single-use plastic scoop or a decontaminated stainless steel scoop to collect sample by pressing the flat bottom against bank, allowing very little water flow disturbance. Slowly transfer water to appropriate sample containers. Preserve as necessary according to the SAP.

4. Collect water sample (with peristaltic pump).

Depending on the type of analysis, a portable peristaltic pump could also be used to pump water into the sample containers. Refer to SOP-GW-10C Purging and Sampling with peristaltic pump. Using new disposable or decontaminated tubing, place the end of the tubing into the water flow being very careful to keep the inlet off of the bottom. Bottom sediments should not be sucked up into the sample container. Slowly fill each sample container. Filtered samples can be collected by attaching a filter to the outflow portion of the

SOP-GW-08; SAMPLING SEEPS AND

SPRINGS


tubing and directing the flow into a sample container.

5. Store and transport sample bottles.

Place the properly labeled sample bottle in an appropriate carrying container maintained at 4°C +/- 2°C throughout the sampling and transportation period.





WORK PLANS

SOP-DE-02 Equipment Decontamination, SOP-GW-10C Purging and Sampling with peristaltic pump.

TOOLS Sample bottles, peristaltic pump, coolers, and field logbook.

FORMS/CHECKLIST

SOP-GW-10; PURGING AND SAMPLING

WITH A 12-VOLT SUBMERSIBLE PUMP


PURPOSE To provide standard instructions for purging and sampling with a 12-volt submersible pump.



TASK INSTRUCTIONS Note Sampling wells in order of increasing chemical concentrations is preferred.

1. Determine the


Using clean, non-contaminating equipment (e.g., an electronic depth to water level indicator (avoid indicating paste)), per SOP-DE-02 Equipment Decontamination, determine the water level in the well. Refer to SOP-GW-03 Depth to Water Level Measurements for instructions. Calculate the fluid volume in the case ("casing volume") and record in the logbook.

2. Attach tubing to the pump outlet.

Attach the appropriate disposable or decontaminated tubing to the pump outlet. Teflon or Teflon lined tubing is preferred when sampling for VOCs, SVOCs, pesticides, and PCBs. PVC, polyethylene, and polypropylene tubing can be used when sampling for inorganics. Note: all down-hole and potentially wetted surfaces must also be non-contaminating/non-contributing, per SOP-DE-02 Equipment Decontamination. This includes power and suspension cables and compressed gas or sample tubing. The pump should also be constructed of materials compatible with the required sample analysis.

3. Lower pump and tubing into well.

Lower the pre-cleaned pump and tubing gently into the well to the predetermined sampling zone. The mid-point of the saturated screen is used by convention as the location of the pump intake. Chemical concentrations or permeability considerations may require pump placement in a different zone; this will be indicated in the Sampling and Analysis Plan (SAP) or work plan. If possible, keep the pump at least 2 feet from the bottom of the well to avoid mobilization of particulates in the bottom of the well.

4. Start the pump and adjust the pump’s speed.

Attach the leads of the electrical wire to a 12-volt battery to start the pump. The tubing end should be placed in a bucket for containment prior to starting the pump. Adjust the pump speed until an appropriate discharge rate is achieved. The pump should discharge at an extraction rate that avoids drawing down the water level




below the pump intake. Measure the discharge rate using a bucket or similar container and a stop watch. Record this information in the logbook. If the recharge rate is slower than an attainable extraction rate using the pump and the well becomes essentially dewatered (e.g., water level falls below the intake level), the well should be allowed to recover sufficiently to fill all the appropriate sample containers. If possible, do not move the pump intake during this process. Samples may then be collected even though parameters have not stabilized.

5. Dispose of purged water and measure purge volume.

Collect and dispose of purged water in accordance with SOP-DE-03 Investigation Derived Waste Handling. Measure and record the total purge volume.

6. Monitor and record field parameters and depth to water level measurements.

During well purging, monitor indicator field parameters including pH, conductivity, and temperature. The SAP or work plan may indicate other field parameters that need to be monitored, such as ORP, DO, and turbidity. Water quality parameters will be considered stable when three consecutive readings (generally 2-5 minutes apart) are as follows:

a. Temperature range is no more than +/- 1 degree Celsius (°C); b. pH varies by no more than 0.1 pH units; and c. Specific conductivity readings are within 3% of the average.

Field parameters, as well as, depth to water level measurements should be recorded in the logbook or on field data sheets.

7. Collect samples.

Purge a minimum of three casing volumes and/or until water quality parameters stabilize. Once these conditions occur, sampling can commence. VOC samples should be collected first and directly into pre-preserved sample containers. Fill the sample containers by allowing pump discharge to flow gently down the side of the bottle with minimal entry turbulence. Cap each bottle as filled. Add preservative as required by analytical methods to samples immediately after collection, if not collected in pre-preserved containers. If a filtered sample is required, an in-line high capacity (0.45 µm) should be inserted into the discharge hose after the other sample containers are filled. Fill the sample bottle and preserve immediately, and then cap the bottle.


Label the sample bottles with an appropriate tag/label. Be sure to complete the tag with necessary information. Record the information in the field logbook and complete all chain-of-custody documents.

9. Transport sample bottles.

Place the properly labeled sample bottles in an appropriate carrying container maintained at 4°C +/- 2°C throughout the sampling and transportation period.




10. Decontaminate pump.

The pump will be thoroughly decontaminated after each use, according to SOP-DE-02 Equipment Decontamination.





WORK PLANS


TOOLS Electronic depth to water level indicator, submersible pump, tubing, 12-volt battery, sampling bottles, water quality meters, buckets, cooler, and field logbook.

FORMS/CHECKLIST

SOP-GW-10B; PURGING AND SAMPLING

WITH A GRUNDFOS REDI-FLO SUBMERSIBLE PUMP


PURPOSE To provide standard instructions for purging and sampling with a Grundfos Redi-Flo Submersible Pump.




1. Determine the


Using clean, non-contaminating equipment (e.g., an electronic depth to water level indicator (avoid indicating paste)), per SOP-DE-02 Equipment Decontamination, determine the water level in the well. Refer to SOP-GW-03 Depth to Water Level Measurements for instructions. Calculate the fluid volume in the case (“casing volume”) and record in the logbook.

2. Unload equipment.

Unload the Grundfos Redi-Flo Submersible Pump rig, generator, and controller from the vehicle.

3. Ground the generator.

Ground the generator and plug in the controller to the generator. The Grundfos Redi-Flo Submersible Pump is designed for two inch well casings, if the casings have a larger diameter, place a shroud on the submersible pump and make sure the fittings are tight so it will not fall off.

4. Lower pump and tubing into well.

Lower the pre-cleaned (per SOP-DE-02 Equipment Decontamination) pump and tubing gently into the well to the predetermined sampling zone. The mid-point of the saturated screen is used by convention as the location of the pump intake. Chemical concentrations or permeability considerations may require pump placement in a different zone, this will be indicated in the Sampling and Analysis Plan (SAP) or work plan. If possible, keep the pump at least 2 feet from the bottom of the well to avoid mobilization of particulates in the bottom of the well.

5. Attach the pump rig to the controller.

Attach the pump rig to the controller and after attaching the discharge tubing, place the tubing end in a bucket to contain the discharge.

6. Start the controller.

Start the controller following the instructions in the operating manual. Slowly increase the speed on the controller until discharge occurs and then set the pump at an appropriate discharge rate. The pump should discharge at an extraction rate that




avoids drawing down the water level below the pump intake.

7. Measure and record the discharge rate.

Measure the discharge rate using a bucket or similar container and a stop watch. Record this information in the logbook. If the recharge rate is slower than the lowest attainable extraction rate using the pump and the well becomes essentially dewatered (e.g., water level falls below the intake level), the well should be allowed to recover sufficiently to fill all the appropriate sample containers. If possible do not move the pump intake during this process. Samples may then be collected even though parameters have not stabilized.

8. Dispose of purged water and record total purge volume.



During well purging, monitor indicator field parameters including pH, conductivity, and temperature. The SAP or work plan may indicate other field parameters that need to be monitored, such as eH, DO, and turbidity. Water quality parameters will be considered stable when three consecutive readings (generally 2-5 minutes apart) are as follows:


Field parameters, as well as, depth to water level measurements should be recorded in the logbook or on field data sheets.

10. Collect samples.

Purge a minimum of three casing volumes and/or until water quality parameters stabilize. Once these conditions occur, sampling can commence. VOC samples should be collected first and directly into pre-preserved sample containers. Fill the sample containers by allowing pump discharge to flow gently down the side of the bottle with minimal entry turbulence. Cap each bottle as filled. Add preservative as required by analytical methods to samples immediately after collection, if not collected in pre-preserved containers. If a filtered sample is required, an in-line high capacity (0.45 µm) should be inserted into the discharge hose after the other sample containers are filled. Fill the sample bottle and preserve immediately; cap the bottle.








13. Decontaminate pump.

The pump will be thoroughly decontaminated after each use, according to SOP-DE-02 Equipment Decontamination.





WORK PLANS


TOOLS Electronic depth to water level indicator, Grundfos Redi-Flo Submersible Pump, generator, controller, stop watch, discharge hose, buckets, water quality meters, sample bottles, cooler, and field logbook.

FORMS/CHECKLIST

SOP-GW-10C; PURGING AND SAMPLING

WITH A PERISTALTIC PUMP


PURPOSE To provide standard instructions for purging and sampling with a peristaltic pump.




1. Determine the


Using clean, non-contaminating equipment (e.g., an electronic depth to water level indicator (avoid indicating paste)), per SOP-DE-02 Equipment Decontamination, determine the water level in the well. Refer to SOP-GW-03 Depth to Water Level Measurements for instructions. Calculate the fluid volume in the case (“casing volume”) and record in the logbook. If depth to mid-point of screen is over 8 meters, choose alternative system.

2. Measure tubing to be used.

Measure the appropriate amount of disposable or decontaminated tubing to be inserted into the well. Add an additional two to four feet of tubing that will remain outside the well and attach to the soft tubing in the peristaltic pump. Teflon or Teflon lined tubing is preferred when sampling for VOCs, SVOCs, pesticides, and PCBs. PVC, polyethylene and polypropylene tubing can be used when sampling for inorganics.

3. Insert tubing into the well.

Insert the tubing into the well to the predetermined sampling zone. The mid-point of the saturated screen is used by convention as the location of the tubing end. Chemical concentrations or permeability considerations may require tubing placement in a different zone. This will be indicated in the Sampling Analysis Plan (SAP) or work plan. If possible keep the tubing at least 2 feet from the bottom of the well to avoid mobilization of particulates in the bottom of the well.

4. Measure and record the discharge rate.

Insert the soft tubing into the peristaltic pump following the instructions in the operating manual. Insert the hard tubing into the soft tubing end. Start the pump head and adjust the pump speed until an appropriate discharge rate is achieved. The pump should discharge at an extraction rate that avoids drawing down the water level below the pump intake. Measure the discharge rate using a bottle or beaker and a stop watch. Record this information in the logbook. If the recharge rate is slower than an attainable extraction rate using the pump and the well becomes essentially dewatered (e.g., water level falls below the intake level), the well should




be allowed to recover sufficiently to fill all the appropriate sample containers. If possible, do not move the pump intake during this process. Samples may then be collected.

5. Dispose of purged water and record total purge volume.



During well purging, monitor indicator field parameters including pH, conductivity, and temperature. The SAP or work plan may indicate other field parameters that need to be monitored, such as eH, DO, and turbidity. Water quality parameters will be considered stable when three consecutive readings (generally 2-5 minutes apart) are as follows:


Field parameters should be recorded in the logbook or on field data sheets.

7. Collect samples.

Purge a minimum of three casing volumes and/or until water quality parameters stabilize. Once these conditions occur, sampling can commence. In general, VOC samples should not be collected when using a peristaltic pump. If VOC analysis is required, collect the VOC samples first and then place them directly into pre-preserved sample containers. Fill the sample containers by allowing pump discharge to flow gently down the side of the bottle with minimal entry turbulence. Double check for bubbles as this method tends to produce them. Cap each bottle as filled. Add preservative as required by analytical methods to samples immediately after collection, if not collected in pre-preserved containers. If a filtered sample is required, an in-line high capacity (0.45 µm) should be inserted into the discharge end of the soft tubing after the other sample containers are filled. Fill the sample bottle and preserve immediately; cap the bottle. To check for air bubbles: turn the VOC bottle upside down, tap lightly, turn right side up, see if any bubbles float to the top. If you see a bubble, remove lid, add additional water, and reseal.





10. Dispose of Tubing used in the well sampling will be disposed of in accordance with SOP-DE-




used tubing. 03 Investigation Derived Waste Handling.





WORK PLANS


TOOLS Sample bottles, water quality meters, 5-gallon buckets, electronic depth to water level indicator, peristaltic pump, stop watch, cooler, and field logbook.

FORMS/CHECKLIST

SOP-GW-13; SAMPLING GROUNDWATER

FROM A TAP


PURPOSE To provide standard instructions for sampling groundwater from a tap.



TASK INSTRUCTIONS 1. Determine the


Using clean, non-contaminating equipment (e.g., an electronic depth to water level indicator (avoid indicating paste)), per SOP-DE-02 Equipment Decontamination, determine the water level in the well. Refer to SOP-GW-03 Depth to Water Level Measurements for instructions. Record the information in the logbook and calculate the fluid volume in the casing. In the case of a public water supply or a well used for drinking water, it is preferable not to measure depth to water to prevent any potential for contamination. If the depth to water is needed, the well needs to be carefully opened and the electronic level indicator needs to be thoroughly decontaminated (per SOP-DE-02 Equipment Decontamination) before and after being lowered into the well.

2. Identify the tap closest to the wellhead.

For existing public water supply, domestic, irrigation, or commercial wells, identify the tap closest to the wellhead, which is not impacted by a water treatment system, pressure tank, or anything which may alter the water quality of the groundwater.


Purge the well by running the tap. During well purging, monitor indicator field parameters including pH, conductivity, and temperature. The Sampling Analysis Plan (SAP) or work plan may indicate other field parameters that need to be monitored, such as eH, DO, and turbidity. Water quality parameters will be considered stable when three consecutive readings (generally 2-5 minutes apart) are as follows:


Field parameters as well as the depth to water level measurements should be recorded in the logbook or on field data sheets. Record the final purge volume in the field logbook.

4. Collect samples.

Once water quality parameters stabilize sampling can commence. Samples will be collected from the tap. The flow shall be turned down to a steady, non-aerated stream. VOC samples should be collected first and directly into pre-preserved

SOP-GW-13; SAMPLING GROUNDWATER

FROM A TAP


sample containers. Fill the sample containers by allowing water to flow gently down the side of the bottle with minimal entry turbulence. Cap each bottle as filled. Add preservative as required by analytical methods to samples immediately after collection if not collected in pre-preserved containers. If a filtered sample is required, attach a Teflon hose to the tap and an in-line high capacity (0.45 µm) to the end of the hose. Fill the sample bottle. Alternately, samples can be collected in a clean sample container and filtered using a peristaltic pump with clean disposable tubing into the sample bottle. Fill the sample bottle and preserve immediately. Cap the bottle.









WORK PLANS

SOP-DE-02 Equipment Decontamination and SOP-GW-03 Depth to Water Level Measurements.

TOOLS Sampling bottles, hoses, buckets, peristaltic pump, stop watch, cooler, and field logbook.

FORMS/CHECKLIST

SOP-GW-14; FIELD WATER QUALITY

MEASUREMENTS USING THE GEOTECH MULTI-PROBE

FLOWBLOCK FLOW THROUGH DEVICE


PURPOSE To provide standard instructions for setting up Geotech Multi-Probe Flowblock (Geotech Flowblock) flow through device for measuring field water quality parameters.



TASK INSTRUCTIONS Notes: The Geotech Flowblock flow through device can be used directly in-line with most

groundwater pumping systems such as the Grundfos RediFlo2™, Geotech SS Geosub, Geotech Bladder Pump, or Geopump Peristaltic Pump, and equivalent pumps. The Geotech Flowblock is designed for minimal sample volume (low-flow sampling) to reduce stirring dependence of sensors. The flowrate can vary from 100 mL/min to 1 gpm (3.8 L/min). No laboratory samples will be taken from water that has flowed through the Geotech Flowblock or the quick-connect barbs. Samples will be collected from tubing that was cut before contact with the Geotech Flowblock or the quick-connect barbs. The Geotech Flowblock does not need to be decontaminated between samples as it will not be in contact with laboratory samples. The Geotech Flowblock should be flushed between sample sites with tap or deionized (DI) water to flush out accumulated sediment.

Refer to the following SOPs for the sampling setup in which the Geotech Flowblock will be used: SOP-GW-02 Sampling with A Bailer SOP-GW-10 Purging And Sampling with A 12-Volt Submersible Pump SOP-GW-10A Purging And Sampling with A Low Flow Submersible Pump SOP-GW-10B Purging And Sampling with Grunfoss Redi-Flow Submersible Pump SOP-GW-10C Purging And Sampling with A Peristaltic Pump SOP-GW-13 Sampling Groundwater From A Tap Prior to using the Geotech Flowblock, pH, specific conductivity, ORP, and DO field





parameter meters need to be calibrated per the following SOPs: SOP-WFM-01 Field Measurement of pH In Water SOP-WFM-02 Field Measurement of Oxygen Reduction Potential in Water SOP-WFM-03 Field Measurement of Specific Conductance SOP-WFM-04 Field Measurement of Water Temperature SOP-WFM-07 Field Measurement of Dissolved Oxygen

1. (Option 1) Set up Geotech Flowblock

The Option 1 set up is shown in Figure 1 below. This option can be used when using a pump that can be adjusted to a very low flow, such as the peristaltic pump and the low flow submersible pump.

1. Cut a piece of new silicon tubing. Use this tubing to connect the connecting valve to the Geotech Flowblock. Use a hose clamp to attach the tubing to the connecting valve. A hose clamp may also be needed to attach the tubing to the Geotech Flowblock.

2. Attach pump tubing to the connecting valve with a hose clamp. 3. Insert probes in the appropriate grommets in the Geotech Flowblock as depicted

on Figure 1. Loosen the grommet to insert probes. The black cap on the pH and ORP columns (the center 2 grommets) may need to be removed to get the probes inserted. Make sure that the gasket present on each column stays on either the probe or in the block. Push the probes to bottom of each column and slightly tighten the black caps on the grommets.

4. Start pump and raise each probe to release pressure and get the associated column to fill. Once it is full, tighten the black cap on the grommets and move to the next probe (moving from inlet to outlet). If the columns are not filling, cover the end of the outlet discharge tubing and tighten the grommets as each column fills. No air bubbles should be present in the columns. If an air bubble is present loosen the grommet, raise the probe, wait for the bubble to disperse and lower the probe and retighten the grommets. Adjust flow using pump controls so that water is not spurting out of block.

5. The pump speed may need to adjusted during purging as the reduction of head may require adjustment of flow through the Geotech Flowblock.





Figure 1. Geotech Flowblock

1. (Option 2) Set up Geotech Flowblock with Relief Valve Port

Note: The relief valve port will be used if flow is greater than the Geotech Flowblock can handle and to collect turbidity samples for field measurement.

The Option 2 set up is shown in Figure 2 below. This set up should be used for pumping situations where flow cannot be adjusted low enough that all water can flow through the Geotech Flowblock.

Cut one piece of silicon tubing to connect the relief valve to the Geotech Flowblock. Use a hose clamp and attach tubing to the outlet directly across from the input on the relief valve. Using a hose clamp attach the other end of the tubing to the Geotech Flowblock.

Attach pump tubing to the inlet on the relief valve with a hose clamp. Cut (2) 18-inch pieces of silicon tubing to handle discharge.

Attach one piece of this tubing to the other outlet on the relief valve. This will provide a way to discharge water that cannot flow through the Geotech Flowblock. Laboratory samples will not be collected from the relief valve; however water for field turbidity measurements will be collected from this valve.

The second piece of silicon tubing will be attached to the outlet side of the Geotech Flowblock. This silicon tubing needs to be long enough to discharge to the bucket or container that is being used to measure volume.





Insert probes in the appropriate grommets in the Geotech Flowblock as depicted on Figure 2. Loosen the grommet to insert a probe. The black cap on the pH and ORP columns (the center 2 grommets) may need to be removed to get the probes inserted. Make sure that the gasket present on each column stays on either the probe or in the block. Push the probes to bottom of each column and slightly tighten the black caps on the grommets.

Start pump and raise each probe to release pressure and get the associated column to fill. Once it is full, tighten the black cap on the grommets and move to the next probe (moving from inlet to outlet). If the columns are not filling, cover the end of the outlet discharge tubing and tighten the grommets as each column fills. No air bubbles should be present in the columns. If an air bubble is present loosen the grommet, raise the probe, wait for the bubble to disperse and lower the probe and retighten the grommets. Adjust flow using pump controls and the relief valve so that water is not spurting out of block. The pump and or relief valve port may need to be adjusted during purging, as the reduction of head may require the adjustment of flow through the Geotech Flowblock.

Figure 2. Geotech Flowblock with Relief Valve Port






Adjust pumping rate as needed to maintain a minimal drawdown of <0.1 m (<4 inches). Time, flowrate and drawdown should be recorded in the logbook or on field data sheets. During well purging, monitor field parameters including pH, conductivity, and temperature. The SAP or work plan may indicate other field parameters that need to be monitored, such as ORP (eH), DO, and turbidity. Water quality parameters will be considered stable when three consecutive readings (generally 2-5 minutes apart) are as follows:

a. Temperature range is no more than +/- 1 degree Celsius (°C); b. pH varies by no more than 0.1 pH units; c. Specific conductivity readings are within 3% of the average; d. ORP varies by no more than 10 mV units; e. DO readings are within 10% of the average; and f. Turbidity readings are within 10% of the average.

Field parameters should be recorded in the logbook or on field data sheets.

2. Collect samples.

Purge until water quality parameters stabilize. Once these conditions occur, sampling can commence by following SOP-SA-02 Sample Preservation and Containerization for Aqueous Samples. Cut the tubing just above the Connector Valve or Relief Valve and collect the samples directly from the tubing. In general, VOC samples should not be collected when using a peristaltic pump. If VOC analysis is required, collect the VOC samples first and then place them directly into pre-preserved sample containers. Fill the sample containers by allowing pump discharge to flow gently down the side of the bottle with minimal entry turbulence. Double check for bubbles as this method tends to produce them. Cap each bottle as filled. Add preservative as required by analytical methods to samples immediately after collection, if not collected in pre-preserved containers. To check for air bubbles: turn the VOC bottle upside down, tap lightly, turn right side up, see if any bubbles float to the top. If you see a bubble, remove lid, add additional water, and reseal. If a filtered sample is required, an in-line high capacity (0.45 µm) should be inserted into the discharge end of the tubing after the other sample containers are filled. Fill the sample bottle and preserve immediately; cap the bottle.

3. Label, store, and ship samples.

Label the sample bottle as appropriate and place in a cooler. Ship with other samples in accordance with SOP-SA-01 Soil and Water Sample Packaging and Shipping.

4. Dispose of Tubing used in the well sampling will be disposed of in accordance with SOP-DE-





used tubing. 03 Investigation Derived Waste Handling.





WORK PLANS

SOP-GW-02 Sampling with A Bailer SOP-GW-10 Purging And Sampling with A 12-Volt Submersible Pump SOP-GW-10A Purging And Sampling with A Low Flow Submersible Pump SOP-GW-10B Purging And Sampling with Grunfoss Redi-Flow Submersible Pump SOP-GW-10C Purging And Sampling with A Peristaltic Pump SOP-GW-13 Sampling Groundwater From A Tap SOP-WFM-01 Field Measurement of pH In Water SOP-WFM-02 Field Measurement of Oxygen Reduction Potential in Water SOP-WFM-03 Field Measurement of Specific Conductance SOP-WFM-04 Field Measurement of Water Temperature SOP-WFM-07 Field Measurement of Dissolved Oxygen SOP-SA-02 Sample Preservation and Containerization for Aqueous Samples SOP-SA-01 Soil and Water Sample Packaging and Shipping. SOP-DE-03 Investigation Derived Waste Handling

TOOLS Geotech Flowblock, sample bottles, sample preservatives, water quality meters, spare batteries for the field measurement meters, ORP, electrode storage, specific conductivity, pH and ORP electrode cleaner, pH 4, pH 7, and pH 10 buffer solutions, de-ionized water, 5-gallon buckets, electronic depth to water level indicator, pump, stop watch, beaker, cooler, ice, purge containers and field logbook/field data sheets.

FORMS/CHECKLIST

SOP-GW-15; CONTINUOUS GROUNDWATER

LEVEL MONITORING (SOLINST LEVELOGGER GOLD)

DATE ISSUED: 2/06/15 REVISION: 0 PAGE: 1 of 4

PURPOSE To provide standard instructions for using a pressure transducer datalogger for continuous groundwater level measurements.


WORK INSTRUCTIONS The following instructions are intended to provide sufficient guidance to perform the task in a safe, accurate, and reliable manner. Should these instructions present information that is inaccurate or unsafe, operations personnel must bring the issue to the attention of the Project Manager and the appropriate revisions made. All work carried under this SOP will be consistent with procedures and policies described in the appropriate Operation, Maintenance, and Monitoring (OM&M) Plan (where applicable), appropriate Site Specific Health and Safety Plan (SSHASP), and the Contractor’s Corporate Health and Safety Plan (HASP).

TASK INSTRUCTIONS

Installation 1. Program

transducer. It is recommended that transducers are programmed in the office rather than in the field to make sure everything is accurate (refer to manual for step-by-step instructions). The following information is needed when programming each transducer:

Project ID. Location. Level – Units in feet.

o Offset – Set to 0.0 feet. o Altitude – Set to 0.0 feet unless site topography varies over 1,000

feet in elevation (e.g., one transducer located in a valley while another transducer is located at the top of a hill).

o Density – 1.0 kg/L. Temperature – Units in degrees Celsius. Verification that the transducers and programming instrument (e.g., Solinst

Leveloader™) are using the most current software/firmware. 2. Determine the

site specific water column (static water level and total depth) and its variability.

Establish well specifics to determine water column (e.g., well log, if available) in an effort to bring enough supplies. Once in the field, verify water column information by using clean, non-contaminating equipment (e.g., an electronic depth to water level indicator [avoid indicating paste]), decontaminated per SOP-DE-02 Equipment Decontamination. Refer to SOP-GW-03 Depth to Water Level (DTW) Measurements, measure and record DTW in the logbook. For consistent water level readings, use the same DTW meter during each site visit.

3. Determine hanging height of transducer.

Determination of the transducer hanging depth in the well is site specific and depends on the well and the water level fluctuation in the area. The main priority is to keep the transducer submerged at all times while making sure it is off of the bottom of the well where sediments can build up over time. Determine a depth at which to install the transducer.

4. Determine set There are many different ways to secure the transducer at the top of the well and to




up to secure the transducer to the PVC/well casing.

keep it in place depending on well construction and the project budget. Kevlar string or Dyneema® fiber work well to hang the transducer at the desired depth. Neither will stretch much after installation. It is imperative that the transducer is unable to shift/slide/slip/etc. from its original hanging position after it is attached to the PVC or well casing. Again, this is site specific and should be verified with the PM. If direct read cables are used, they must be properly secured to assure the transducer hanging height does not change and should have a backup hanging system (e.g., Kevlar string) in the event the cable is cut. Never attach the transducer to anything removable (e.g., well cap). The easiest and most effective method for securing the transducer at a specified depth in the well is to install an eye-bolt or hook into the outer well casing (hook or eye should be to the inside of the casing). A large hose clamp over the inner PVC casing could also be used to secure the string. For security reasons, try to attach the string or direct read cable so that it is entirely contained within the outer well casing. Don a new pair of nitrile or latex gloves. Tie the string/fiber to the transducer. Measure the appropriate amount of string/fiber required to install the transducer at the determined depth plus a small amount to attach the string/fiber to the casing. While measuring the string/fiber, field personnel should wear latex or nitrile gloves and make sure the string/fiber does not contact the ground. Cut the string/fiber. If using a direct read cable, screw the direct read cable to the transducer. Care should be taken to only twist the connectors and not the cable. Measure out the appropriate amount of cable to install the transducer at the pre-determined depth, coil and secure any leftover cable with a zip tie. Secure the string/fiber to the hook, eye bolt or hose clamp at the top of the casing.

5. Start the transducer.

If needed, remove the cap from the transducer and/or direct read cable. Using special care to only twist the connectors and not the cables, connect to the transducer or direct read cable using either the Leveloader™ or a field laptop computer (pre-loaded with the most recent version of transducer specific software) using a PC connector cable. An optical reader can also be used in conjunction with the Leveloader™ or a field laptop computer to program the transducer. Check, and if needed, set the present date and time. Daylight savings time should never be accounted for and the transducer’s time should always be set to standard. The time should also be synced to an exact time (e.g., cell phone). Set the transducer for a future start time, never start at the current time. Double check the interval time set in the initial program set up (e.g. a reading every four hours, readings at 15-minute intervals, etc.). Set the future start time so that one of the interval loggings occurs at 12:00 AM. If transducers are to be installed in more than one well, set each transducer to start recording at the same future start time and the same logging interval. Once the programming is complete, close out of the program, and disconnect the transducer from the Leveloader™ or field laptop computer. Put the cap back on the transducer and/or the direct read cable, being careful to only twist the cap and not the cables.

6. Deploy the Confirm that the string/fiber is firmly attached to both the transducer and the top of




transducer. the well. Lower the transducer into the well slowly to the preset depth. Reconfirm that the string/fiber are firmly attached to the top of the well. Replace the well cap. Close and lock the well casing.

7. Barologger installation.

A Barologger will need to be installed to log barometric pressure. Barologger readings can be used to compensate any transducer data from wells that are within 1,000 feet of elevation and within a 20 miles radius. If possible, chose a well in a central location that allows all transducers being installed to fall within these criteria. Additional Barologgers will need to be installed if any transducers fall outside of these parameters. Following the manufactures operating manual, set the Barologger to start at the same time as the transducers and record at the same time interval. The following information should also be programmed into the Barologger:

Project ID. Location. Level – Units in kPa. Temperature – Units in degrees Celsius.

Installation of the Barologger is similar to installing a transducer. Cut a piece of Kevlar string or Dyneema® fiber to hang the Barologger at the desired height within the well casing. In an ideal situation the Barologger will be installed between the inner well casing (PVC) and the outer metal protective casing. The length of the string should allow the Barologger to hang down below the top of the inner well casing so it won’t be disturbed during monitoring/sampling activities, but short enough that it doesn’t touch the ground. The Barologger can also be installed within the inner well casing if there is not enough space between the inner and outer casing. The Barologger will need to be removed during sampling and monitoring activities with care to not remove when a logging interval is near as it could impact the specific reading. The Barologger can be hung from the same eye-bolt, hook or hose clamp as the transducer, or hung using its own dedicated setup.

Downloading 1. Measure the


The static water level must be measured prior to downloading the transducer. This insures the water column height was not compromised (e.g., pulling the transducer causing the water level to drop). Using clean, non-contaminating equipment (e.g., an electronic depth to water level indicator [avoid indicating paste]), decontaminated per SOP-DE-02 Equipment Decontamination, determine the water level in the well. Refer to SOP-GW-03 Depth to Water Level Measurements for instructions and record in the logbook. To ensure consistent water level readings an effort should be made to use the same DTW meter during each site visit.

2. Download data.

If a direct read cable was used in the well, connect to the transducer using either the Leveloader™ or a PC interface cable and the field laptop. If a direct read cable was not installed, don a pair of nitrile or latex gloves and remove the transducer from the well, noting the time on the field data sheet or in the field logbook. Place a piece of new plastic on the ground and place string on it as the transducer is removed from the well, alternately have field personnel collect the string so that it does not touch the ground during removal. Remove the cap from the transducer and/or direct read cable and place it in the optical reader or attach the PC interface cable (twist the connector, not the cable). Care should be taken not to misplace the cap removed




from the transducer or direct read cable. The field laptop computer should have the most current software/firmware. Using either the Leveloader™ or the field laptop computer download the data (refer to manual for step-by-step instructions). If a direct read cable is installed, also record the real-time measurements in the logbook.

3. Start the transducer.

Set the transducer to a future start at a specific time (e.g. every four hours, 15-minute intervals, etc.) with one of the intervals logging at 12:00 AM. Never start at the current time.

4. Reinstall the transducer.

When downloading is complete, put the cap back on the direct read cable or transducer taking care not to twist the cable only the connectors. Replace the direct read cable inside the well casing or reinstall the transducer into the well as discussed in Step 6 above. Once the transducer is back in place note the time in the logbook or on the field data sheet. Close and lock the well casing.

Maintenance 1. Battery Life Each transducer has a 10-year battery life (based on one reading/min). Prior to

transducer deployment, it is important to note the age of the instrument as well as monitor the battery level during each field visit. When reaching the end of the battery life, readings may begin to drift from the actual water levels. Periodic readings from the transducer should be compared to the manual water levels to help indicate the accuracy of the transducer and if it should be replaced.





WORK PLANS


TOOLS Electronic depth to water level indicator, appropriate instrument connecting cables, field laptop/Leveloader, and field logbook.

FORMS/CHECKLIST Cold weather (if applicable).

SOP-SA-01; SOIL AND WATER SAMPLE

PACKAGING AND SHIPPING


PURPOSE To provide standard instructions for soil and water sample packaging and shipping.



TASK INSTRUCTIONS 1. Preserve the

samples. Water samples will be preserved, if required, according to SOP-SA-02 Sample Preservation and Containerization for Aqueous Samples, and SOP-SA-02B Sample Preservation and Containerization for Aqueous Samples for VOAs.

2. Place the sample containers in Ziploc bags.

Based on the analytes requested (e.g., low level mercury, low level chromium, etc.), it may be necessary to place each filled sample container in separate Ziploc bags to prevent cross contamination, keep the container clean, dry, and isolated, and protect the sample label. In most cases, all sample containers collected from a specific sample location are placed in a large Ziploc bag and shipped together.

3. Package the samples.

Place samples in a cooler, which has been previously lined with a plastic bag. Surround the samples with non-contaminating packaging materials to reduce movement and absorb any leakage. Double bag the ice and place it in the cooler. Seal the plastic bag in the cooler to contain the samples, packing material, and ice.

4. Review and sign COC forms.

The Field Team Leader or their designated representative will double check the chain-of-custody (COC) forms to assure those samples recorded on the COC forms are in the cooler. The Field Team Leader or the designated representative will then sign the chain-of-custody form to relinquish custody. One copy of the signed COC form will remain with the Field Team Leader. Make a photocopy of the completed forms, if there are no carbon copies available.

5. Tape paper work to cooler.

Place paper work in a sealed Ziploc bag and tape it to the inside of the cooler lid.

6. Bag samples for separate analytical batches.

If the shipping cooler contains more samples than can be analyzed in one analytical batch, the laboratory may request that the samples in the cooler be bagged for separate analytical batches. This may be necessary so that the appropriate Quality Control/Quality Assurance samples are included in each analytical batch. In this case, fill out separate COC forms for each batch and include the forms in the

SOP-SA-01; SOIL AND WATER SAMPLE

PACKAGING AND SHIPPING


appropriate plastic bags. Place the COC forms for each batch in a sealed Ziploc bag. The COC forms for each batch should be placed at the top of the plastic bag so that they are clearly visible to laboratory personnel when they open the plastic bags.

7. Label the cooler.

Label the cooler with the appropriate labels to describe the content of the cooler (e.g., NOS, flammable liquids, flammable solids, this side up, fragile, etc.). Close the cooler and place the appropriate shipping labels (e.g., overnight shipping from Federal Express, UPS, or the United States Postal Service or equivalent) on the lid of the cooler.

8. Sign COC seals.

The Field Team Leader or the designated representative will sign COC seals and place the signed seals over the opening edge of the cooler.

9. Tape the cooler.

Place tape over the custody seals and around the cooler.

10. Transport the cooler.

Transport the cooler(s) to a secure storage, to the shipping agent, or directly to the laboratory. If shipping the cooler, follow established federal and state regulations depending on cooler content.

Notes

Bagging of samples and lining of coolers is not necessary, if samplers transport the samples directly to the laboratory.



DRAWINGS


WORK PLANS

SOP-SA-02 Sample Preservation and Containerization for Aqueous Samples, and SOP-SA-02B Sample Preservation and Containerization for Aqueous Samples for VOAs.

TOOLS Plastic bags, Ziploc bags, non-contaminating packaging materials, tape, COC seals, ice, and cooler.

FORMS/CHECKLIST Chain-of-custody (COC) forms.

SOP-SA-02; SAMPLE PRESERVATION AND

CONTAINERIZATION FOR AQUEOUS SAMPLES


PURPOSE This SOP covers aqueous samples being analyzed for commonly requested organic, inorganic and RADCHEM parameters. Guidance is provided on industry standard containers, preservatives, analytical methods and holding times associated with sample collection.



TASK INSTRUCTIONS Notes Most bottles come certified and preserved from the laboratory. If bottles do not

contain preservatives, field personnel will add it at the time of water sample collection. If bottles are not certified, a triple rinse with the water to be sampled will be done before collecting the sample. Preservative will be added to the sample container after triple rinse and before sample collection. The following information was supplied from Pace Analytical Services. If another laboratory is contracted for analyzing samples, verify with the laboratory the appropriate containers, preservatives and holding time limits for the required analyses. If a different analytical method is specified in the Sampling and Analysis Plan (SAP) from those listed below verify with the contracted laboratory for sampling method, container requirements, preservative and holding time limits.

Label Sample Label samples as per SOP-SA-01 Soil and Water Sample Packaging and Shipping.




Organic Parameters in Aqueous Samples

Parameter

Method

Container

Preservative

Max Hold Time

EPA Drinking

Water EPA Water EPA Waste

SW-846

Aromatic and Halogenated Volatiles

601/602 8021 3 - 40mL vials pH<2 HCl, ≤6°C, Na2S2O3 if

Cl present 14 Days (7 days for

aromatics if unpreserved)

Base/Neutrals and Acids 625 8270 1L Amber Glass ≤6°C, Na2S2O3 if Cl present 7/40 Days

Base/Neutrals, Acids & Pesticides

525.2 1L Amber Glass

pH <HCI, sodium sulfite if Cl present

14/30 Days

Diesel Range Organics 8015 1L Amber Glass ≤6°C, Na2S2O3 if Cl present 7/40 Days

Dioxins and Furans 1613B 1L Amber Glass ≤6°C, Na2S2O3 if Cl present 1 Year

Dioxins and Furans 8290 1L Amber Glass ≤6°C, Na2S2O3 if Cl present 30/45 Days

Dissolved Organic Carbon Method 5310 250 ml Amber GlassField Filter from an

Unpreserved Sample into an pH<2 H2SO4, ≤6°C

28 days

EDB & DBCP 504.1 8011 40mL vials ≤6°C, Na2S2O3 if Cl present 14 Days

Explosives 8330/8332 1L Amber Glass ≤6°C 7/40 Days

Gasoline Range Organics 8015 40mL vials pH<2 HCl 14 Days

Haloacetic Acids 552.1/552.2 40mL Amber vials NH4Cl, ≤6°C 14/7 Days if extracts stored

at ≤6°C or 14/14 Days if extracts stored at ≤-10°C

Herbicides, Chlorinated 515.1/515.3 8151 1L Amber Glass ≤6°C, Na2S2O3 if Cl present 7/40 Days for 8151; 14/28 Days for 515.1/515.3

PCBs, Organochlorine 8082 1L Amber Glass ≤6°C; Na2S2O3 if Cl present 1 Year/1Year

PCBs & Pesticides, Organochlorine 608 1L Amber Glass ≤6°C; Na2S2O3 if Cl present 7/40 Days

Pesticides, Organochlorine 8081 1L Amber Glass ≤6°C, Na2S2O3 if Cl present 7/40 Days

Pesticides, Organophosphorus 8141 1L Amber Glass pH 5-8 with NaOH or H2SO4; ≤6°C, Na2S2O3 if Cl Present

7/40 Days

Polynuclear Aromatic Hydrocarbons 8270 SIM 1L Amber Glass ≤6°C, Na2S2O3 if Cl present 7/40 Days

Volatiles 624 8260 3 - 40mL vials pH<2 HCI; ≤6°C 14 Days (7 Days for

aromatics if unpreserved)

Volatiles (see note 1) 524.2 40mL vials (in duplicate)

pH<2 HCI, ≤6°C, Na2S2O3 if Cl present

14 Days

1 Method 524.2 lists ascorbic acid as the preservative when residual chlorine is suspected, unless gases or Table 7 compounds are NOT compounds of interest and then sodium thiosulfate is the preservative recommended.




Inorganic Parameters in Aqueous Samples

Parameter

Method

Container

Preservative

Max Hold Time

EPA Water Standard Methods

EPA Waste SW-846

Acidity SM2310B Plastic/Glass ≤6°C 14 Days Alkalinity 310.2 SM2320B Plastic/Glass ≤6°C 14 Days

Anions by IC, including Br, Cl, F, NO2, NO3,o-Phos, SO4, bromate, chlorite, chlorate)

300.0

Plastic/Glass

≤6°C

All analytes 28 days except NO2, NO3, o-Phos (48

hours); chlorite (immediate); NO2/NO3 combo 28 days

Bacteria, Total Plate Count SM9221D Plastic/WK ≤6°C, Na2S2O3 24 Hours

BOD/cBOD SM5210B/Hach

10360

Plastic/Glass ≤6°C

48 hours Chloride SM4500Cl-C,E Plastic/Glass None 28 Days

Chlorine, Residual

330.5

SM4500Cl-D, E, G / Hach 8167

Plastic/Glass None

15 minutes

COD

410.4

SM5220C, D / Hach 8000

Plastic/Glass pH<2 H2SO4, ≤6°C

28 Days

Color

SM2120B,E

Covered Plastic, Acid Washed Amber Glass ≤6°C

24 Hours

Cyanide, Reactive Chapter 7 Plastic/Glass None 28 Days

Cyanide, Total and Amenable

335.4

SM4500CN-

A,B,C,D,E,G,I,N

9010/9012

Plastic/Glass

pH>12 NaOH; ≤6°C ascorbic acid if Cl

present

14 Days (24 hrs if sulfide present - applies to SM4500CN only)

Ferrous Iron SM3500Fe-D Glass None Immediate Flashpoint/Ignitability 1010 Plastic/Glass None 28 Days Fluoride SM4500Fl-C,D Plastic None 28 Days Hardness, Total (CaCO3) 130.1 SM2340B,C Plastic/Glass pH<2 HNO3 6 Months

Hexavalent Chromium

218.6

SM3500Cr-C,D 7196 Plastic/Glass ≤6°C

24 Hours, unless preserved per method, then 28 Days

Mercury 245.1/245.2 7470 Plastic/Glass pH<2 HNO3 28 Days

Mercury, Low Level

1631E

Fluoropolymer (Glass if Hg is only analyte being

tested)

12N HCl or BrCl

48 hours for preservation or analysis; 28 days to

preservation if sample oxidized in bottle; 90 days for

analysis if preserved Metals (ICP/ICPMS) 200.7/200.8 6010/6020 Plastic/Glass pH<2 HNO3 6 Months Nitrogen, Ammonia 350.1 SM4500NH3 Plastic/Glass pH<2 H2SO4, ≤6°C 28 Days Nitrogen, Kjeldahl 351.2 SM4500-Norg Plastic/Glass pH<2 H2SO4, ≤6°C 28 Days Nitrogen, Nitrate 352.1 SM4500-NO3 Plastic/Glass ≤6°C 48 Hours

Nitrogen, Nitrate & Nitrite, combined

353.2

SM4500-NO3


28 Days

Nitrogen, Organic 351.2 / 350.1 SM4500-Norg Calculation pH<2 H2SO4, ≤6°C 28 Days Odor SM2150B Glass ≤6°C 24 Hours

Oil and Grease/HEM

1664A

SM5520B 9070 Glass

pH<2 H2SO4 or HCl, ≤6°C

28 Days

Oxygen, Dissolved (Probe) SM4500-O Glass None 15 minutes Paint Filter Liquid Test. 9095 Plastic/Glass None N/A




Parameter

Method Container

Preservative Max Hold Time EPA Water Standard Methods EPA SW-846

Gamma Emitting Radionuclides (see note 2) 901.1 Plastic/Glass pH<2 HNO3 180 days Gross Alpha (NJ 48Hr Method) NJAC 7:18-6 Plastic/Glass pH<2 HNO3 48 hours Gross Alpha and Gross Beta (see note 2) 900.0 9310 Plastic/Glass pH<2 HNO3 180 days Radium-226 (see note 2) 903.0/903.1 Plastic/Glass pH<2 HNO3 180 days Radium-228 (see note 2) 904.0 9320 Plastic/Glass pH<2 HNO3 180 days Radioactive Strontium (see note 2) 905.0 Plastic/Glass pH<2 HNO3 180 days Total Alpha Radium (see note 2) 903.0 9315 Plastic/Glass pH<2 HNO3 180 days Total Uranium (see note 2) 908.0 D5174-97 Plastic/Glass pH<2 HNO3 180 days Tritium 906.0 Glass None 180 Days

Inorganic Parameters in Aqueous Samples (Cont.)

Parameter

Method

Container

Preservative

Max Hold Time

EPA Water Standard Methods

EPA Waste SW-846

Phenol, Total 420.1/420.4 9065/9066 Glass pH<2 H2SO4, ≤6°C 28 Days Phosphorus, Orthophosphate

365.1/365.3

SM4500P

Plastic Filter, ≤6°C

Filter within 15 minutes, Analyze within 48 hours

Phosphorus, Total

365.1 / 365.3 / 365.4

SM4500P


28 Days

Silica, Dissolved SM4500Si-D Plastic ≤6°C 28 Days Solids, Settleable SM2540F Glass ≤6°C 48 Hours Solids, Total SM2540B Plastic/Glass ≤6°C 7 Days Solids, Total Dissolved SM2540C Plastic/Glass ≤6°C 7 Days Solids, Total Suspended USGS I-3765-85 SM2540D Plastic/Glass ≤6°C 7 Days Specific Conductance 120.1 SM2510B 9050 Plastic/Glass ≤6°C 28 Days

Sulfate

375.2

SM4500S04 / ASTM D516 9036/9038 Plastic/Glass ≤6°C

28 Days

Sulfide, Reactive Chapter 7 Plastic/Glass None 28 Days

Sulfide, Total

SM4500S 9030 Plastic/Glass pH>9 NaOH and

ZnOAc; ≤6°C

7 Days Sulfite SM4500SO3 Plastic/Glass None 15 minutes Surfactants (MBAS) SM5540C Plastic/Glass ≤6°C 48 Hours Total Organic Carbon (TOC)

SM5310B,C,D 9060 Glass pH<2 H2SO4 or HCl,

≤6°C

28 Days Total Organic Halogen (TOX)

SM5320 9020/9021 Glass (No headspace) pH<2 H2SO4, ≤6°C

14 Days Turbidity 180.1 SM2130B Plastic/Glass ≤6°C 48 Hours

2

Methods 9315 and 9320 both state that if samples are unpreserved, the samples should be brought to the lab within 5 days of collection, preserved in the lab, and then allowed to sit for a minimum of 16 hours before sample preparation/analysis.

RADCHEM PARAMETERS

2 Methods 9315 and 9320 both state that if samples are unpreserved, the samples should be brought to the lab within 5 days of collection, preserved in the lab, and then allowed to sit for a minimum of 16 hours before sample preparation/analysis.


P&IDS DRAWINGS RELATED

SOPs/PROCEDURES/ WORK PLANS

SOP-SA-01 Soil and Water Sample Packaging and Shipping.

TOOLS Preservatives, sample container, ice, and cooler. FORMS/CHECKLIST

SOP-SA-03A; FIELD QUALITY CONTROL

SAMPLES FOR WATER SAMPLING


PURPOSE This SOP describes the preparation and collection frequency of field quality control (QC) blanks and duplicate samples from water media.



TASK INSTRUCTIONS Field Quality Control At least one set of field QC samples will be prepared for each sampling event or as

detailed in the project specific SAP or QAPP. QA/QC samples will be collected at a frequency of 1:20 or as detailed in the project specific SAP or QAPP. If the number of field QC samples taken is not equal to an integer multiple of the interval, the next higher multiple will be used. For example, if a frequency of 1:20 is indicated and 28 samples are taken, two QC samples will be prepared. All field QC samples shall be shipped with field samples to the contract laboratory as per SOP-SA-01 Soil and Water Sample Packaging and Shipping.

Field Blank or Bottle Blank

A minimum of one field bottle blank is required for every 20 natural samples. A bottle blank is a sample bottle containing di-ionized or analyte free water and preservatives and is prepared in the field. A sample bottle is randomly chosen from each lot of bottles received by the contract laboratory or supplier and di-ionized or analyte free water (depending on the analysis requested) is poured directly into the sample bottle while in the field, preserved, and shipped to the laboratory with the field samples. The field blank must be prepared in the field to evaluate the potential for contamination of a sample by site contaminants from sources not associated with the sample collected (e.g., air-borne dust). The appropriate sample number shall be placed on the bottle and recorded in the project logbook as a bottle blank.

Trip Blank One trip blank is required per sampling event when Volatile Organic Compound (VOC) samples are collected. Trip blanks are used to determine if samples were contaminated during storage and/or transportation back to the laboratory. A trip blank is only required for VOC




sampling. A trip blank is prepared for field personnel by the contract laboratory staff prior to the sampling event and is shipped and stored in the same cooler with the investigative VOC samples throughout the sampling event. At no time after their preparation are trip blanks to be opened before they reach the laboratory. Trip blanks should be kept on ice in the cooler, along with the VOC samples during the entire sampling run. They must be stored in an iced cooler from the time of collection, while they are in the sampling vehicle, until they arrive at the laboratory.

Equipment, Cross Contamination, or Rinsate Blank

A minimum of one equipment blank is required for every 20 natural samples. Equipment blanks are collected after the completion of decontamination of sampling equipment and prior to sampling. An equipment blank is prepared by running distilled, de-ionized or analyte free water through or over the cleaned sampling equipment and adding the appropriate chemical preservatives. Equipment blanks are generally prepared in the field. One equipment blank must be prepared for each type of preservative and for any filtered samples. Equipment blanks will assess the adequacy of the decontamination process, as well as, the potential contamination of samples by the containers, preservatives and filters. The appropriate sample number shall be placed on the bottle and recorded in the project logbook as equipment blank.

Field Duplicate A minimum of one duplicate is required for every 20 natural samples. A field duplicate is defined as a second sample, from the same location, collected in immediate succession, using identical techniques. This applies to all routine surface and groundwater collection procedures, including in-stream grab samples, bucket grab samples (e.g., from bridges), pumps, and other water sampling devices. Duplicate samples are sealed, handled, stored, shipped, and analyzed in the same manner as the primary sample. Duplicates should be submitted as “blind” meaning that the duplicate sample is given another name so it is not identified with the primary sample. Field duplicate assess sampling precision.

Temperature Blank One temperature blank is required for each cooler shipped. A temperature blank is a vial of water that accompanies the samples that will be opened and tested upon arrival at the laboratory to ensure that the temperature of the contents of the sampling shipping container was within the required 4°C ± 2°.



DRAWINGS RELATED

SOPs/PROCEDURES/ WORK PLANS


TOOLS Preservatives, sample glass bottles, ice, and cooler.




FORMS/CHECKLIST

SOP-SA-03B; PREPARATION OF

EQUIPMENT RINSATE BLANKS FOR SUBMERSIBLE PUMPS


PURPOSE This SOP describes the preparation and collection frequency of field quality control (QC) Equipment Cross Contamination or Rinsate Blanks from a submersible pump.



TASK INSTRUCTIONS Notes: Equipment blanks, also known as rinsate blanks, are collected periodically after completing decontamination of sampling equipment and prior to resuming sampling. Equipment blanks assess the adequacy of the decontamination process and the potential contamination of samples by the containers, preservatives, and filters. Consequently, an equipment blank may be made of a single or multiple sample containers that represent the natural sampling process. A minimum of one equipment blank is required for every 20 natural samples, regardless of the pump type used. Blanks are collected by running de-ionized or analyte free water through or over the cleaned sampling equipment and adding the appropriate chemical preservative. Field equipment rinsates should be collected in an environment free from dust and automobile exhaust. A separate blank must be collected for each type of preservative (e.g., HCl, HNO3, H2SO4, NaOH, etc.) used and each sample preparation method (e.g., unfiltered or filtered) used. If more than one type of pump is used for sampling (e.g., peristaltic pump, 12 volt submersible pump, Grunfoss Redi-Flo II pump, etc.), equipment blanks should be collected from the pump type used to collect the majority of samples, unless project-specific requirements differ. The following examples demonstrate how the number of equipment blanks may be determined.

Example #1: A project requires 14 samples to be collected using a peristaltic pump and 5 samples to be collected using a 12 volt submersible pump. There are no project-specific equipment blank requirements. Only 1 equipment blank is necessary because less than 20 natural samples will be collected. The equipment blank should be collected from the peristaltic pump because it was used to collect a majority of the natural samples.

Example #2: A project requires 23 samples to be collected using a 12 volt submersible pump, 5 samples to be collected using a Grunfoss Redi-Flow II pump, and 19 samples to be collected using a peristaltic pump. There are no project-specific equipment blank requirements. A minimum of 3 equipment blanks must be collected because the total number of natural samples is greater than 40. To evaluate potential cross contamination from each piece of sampling equipment, 1equipment blank should be collected from each of the 3 pumps.

Prior to starting the fieldwork, personnel should review the anticipated sampling conditions (e.g., well

SOP-SA-03B; PREPARATION OF

EQUIPMENT RINSATE BLANKS FOR SUBMERSIBLE PUMPS


diameter, depth to water, historic contamination levels, etc.) to determine the likely number of equipment blanks. However, once in the field, personnel should be aware of conditions that may require adjustments to the number of equipment blanks (e.g., inaccurate well construction details, changes in water level, historic contamination, etc.).

1. Label blank container.

Label sample containers with the appropriate sample number as designated in the Sampling and Analysis Plan (SAP) or Quality Assurance Project Plan (QAPP). Place clear tape over the sample label. All sample containers collected for a natural sample should be duplicated for an equipment blank.

2. Blank container preparation.

Prepare the equipment blank container by removing the covering and rinsing with de-ionized (DI) water. Before a sampling event where more than one or two wells will be sampled, a new container for collecting equipment blanks should be prepared by triple rinsing with DI water and covering with foil or plastic. The container should be tall enough to submerge the pump and have a wide enough mouth that additional water can easily be added.

3. Remove pump.

Don a new pair of nitrile gloves and remove a decontaminated pump from its storage container making sure that the attached tubing (if appropriate) and pump do not contact any other surface (i.e., the ground). If needed attach a short piece of tubing to the pump.

4. Fill rinsate container.

Place the pump in the container dedicated for equipment blanks. A fresh jug of DI water should be opened and poured into the container to cover the pump.

5. Purge and collect samples.

Turn the pump on and continue to pour DI water into the container. Purge a minimum of 4 gallons through the pump as this simulates the purging done when sampling a well. Once an appropriate volume of water has been discharged from the pump, fill sample containers in the same order and method that they are filled when collecting a natural sample. If filtered samples are collected for field samples a filter should be inserted into the discharge tube after all non-filtered samples have been collected and the appropriate sample containers should be filled.

6. Record in logbook.

The sample number and a description of the collection process should be recorded in the project logbook. The sample should be clearly identified in the logbook as an equipment blank.

7. Place on ice. The sample containers should be placed in a cooler on ice as soon as possible after collection.

8. Empty and cover rinsate container.

Empty water out of dedicated equipment rinstate container and cover the container to avoid inadvertently contaminating the interior prior to the next blank sample.



DRAWINGS


WORK PLANS


TOOLS Preservatives, sample glass bottles, ice, and cooler. FORMS/CHECKLIST

SOP-SA-04; CHAIN OF CUSTODY FORMS

FOR ENVIRONMENTAL SAMPLES


PURPOSE This SOP establishes the requirements for documenting and maintaining environmental sample chain of custody from point of origin to receipt of sample at the analytical laboratory. This procedure shall apply to all types of air, soil, water, sediment, biological, and/or core samples collected in environmental investigations by the Contractor. It is applicable from the time of sample acquisition until custody of the sample is transferred to an analytical laboratory.


DEFINITIONS Chain of Custody: is an unbroken trail of accountability that ensures the physical security of samples, data, and records. Custody refers to the physical responsibility for sample integrity, handling, and/or transportation. Custody responsibilities are effectively met, if the samples are:

In the responsible individual's physical possession; In the responsible individual's visual range after having taken possession; Secured by the responsible individual so that no tampering can occur; or Secured or locked by the responsible individual in an area in which access is

restricted to authorized personnel only.


TASK INSTRUCTIONS Project Manager’s Responsibilities

The Project Manager is responsible for overall management of environmental sampling activities, designating sampling responsibilities to qualified personnel, and reviewing any changes to the sampling plan.

Field Team Leader’s Responsibilities

The Project Manager may act as the Field Team Leader or may choose to appoint a Field Team Leader. The Field Team Leader is responsible for general supervision of field sampling activities and ensuring proper storage/transportation of samples from the field to the analytical laboratory. Chain of Custody forms will be reviewed for accuracy and completeness to preserve sample integrity from collection to receipt by an analytical lab by the Field Team Leader. The review of Chain of Custody forms may be delegated to qualified personnel.




The Field Team Leader is responsible for sample custody until the sample has been properly relinquished as documented on the chain of custody form.

Field Sampler’s Responsibilities

The Field Sampler is responsible for sample acquisition in compliance with technical procedures, initiating the Chain of Custody, and checking sample integrity and documentation prior to transfer. Field samplers are also responsible for initial transfer of samples consisting of physical transfer of samples directly to the internal laboratory or transferred to a shipping carrier, (e.g., United Parcel Service or Federal Express) for delivery.

Laboratory Technician’s Responsibilities

The receiving Laboratory Technician is responsible for inspection of transferred samples to ensure proper labeling and satisfactory sample condition. Unacceptable samples will be identified and segregated. The Laboratory Project Manager will be notified. The Laboratory Technician will review the Chain of Custody for completeness and file as part of the project’s permanent record.

Samples Handling and Chain of Custody Forms

All samples shall be collected and handled in accordance with SOP-SA-01 Soil and Water Sample Packaging and Shipping and SOP-SA-02 Sample Preservation and Containerization for Aqueous Samples, or methods described in the Sampling and Analysis Plan (SAP) or work plan. Samples will be transported in insulated coolers with ice (‘blue ice’ is acceptable) as necessary to maintain temperature at 4 C+/- 2 C until receipt by the analytical laboratory. The Field Team Leader or designated Field Sampler shall initiate the Chain of Custody form for the initial transfer of samples. A Chain of Custody form will be completed and accompany every sample. The form includes the following information:

Project code; Project name; Samplers signature; Sample identification; Date sampled; Time sampled; Analysis requested; Remarks; Relinquishing signature, data, and time; and Receiving signature, date, and time.

The Field Sampler relinquishing custody and the responsible individual accepting custody shall sign, date, and note the time of transfer on the Chain of Custody form. Note: If the transporter is not an employee of the Contractor, the Field Sampler may




identify the carrier and reference the bill of lading number in lieu of the transporter's signature. One copy of the Chain of Custody form shall be filed as a temporary record of sample transfer by the Field Sampler. The original form shall accompany the samples and shall be returned to the Contractor as part of the contracted laboratory Quality Assurance/Quality Control (QA/QC) requirements. The original form will be filed as part of the project’s permanent records. The Project Manager (or designee) shall track the Chain of Custody to ensure timely receipt of samples by an analytical laboratory.



DRAWINGS


WORK PLANS

SOP-SA-01 Soil and Water Sample Packaging and Shipping and SOP-SA-02 Sample Preservation and Containerization for Aqueous Samples.

TOOLS Seals and labels; chain of custody forms; chain of custody seals (provided by contracted laboratory); packing and shipping materials; and cooler and ice.

FORMS/CHECKLIST Chain of Custody Forms.

SOP-SA-05;

PROJECT DOCUMENTATION


PURPOSE This SOP establishes the requirements for documenting and maintaining field logbooks and photographs. These procedures shall apply to all types of air, soil, water, sediment, biological, and/or core samples collected in environmental investigation by the Contractor. These procedures apply from the time field work begins until site activities are completed.



TASK INSTRUCTIONS 1. Logbooks. A designated field logbook will be used for each field project. If requested by the

Project Manager, use a separate field logbook for each field task within a larger project. Label each logbook with the project name, dates that it covers, and logbook number. Use a waterproof marker, such as a Sharpie©, to write down the information. The logbooks will be bound and have consecutively numbered pages. The information recorded in these logbooks shall be written in ink. Begin a new page for each days notes. Write on every line of the logbook. If a blank space is necessary for clarity, such as a change of subject, skip one line before beginning the new subject. Do not skip any pages or parts of pages unless a day’s activity ends in the middle of a page. Draw a diagonal line on any blank spaces of four lines or more to prevent unauthorized entries. The author will initial and date entries at the end of each day. All corrections will consist of a single line-out deletion in ink, followed by the author’s initials and the date. Information not related to the project should not be entered in the logbook. The language used in the logbook should be factual and objective. These bound logbooks shall include the following entries: 1. A description of the field task.

2. Time and date fieldwork started. 3. Location and/or a description of the work areas including sketches, if needed,

any maps or references needed to identify locations, and sketches of construction activities. If the location has been documented in the logbook during/prior visits, only changes in conditions should be noted.

4. Names and company affiliations of field personnel.

SOP-SA-05;



5. Name, company affiliation or address, and phone number of any field contacts or official site visitors.

6. Meteorological conditions at the beginning of fieldwork and any ensuing changes in these conditions.

7. Details of the fieldwork performed and reference to field data sheets, if used.

8. Deviation from the task-specific Sampling and Analysis Plan (SAP), Work Plan (WP), or Standard Operating Procedures (SOP).

9. All field measurements made.

10. Any field laboratory analytical results.

11. Personnel and equipment decontamination procedures, if appropriate. For any field sampling work, the following entries should be made: 1. Sample location and number.

2. Sample type and amount collected.

3. Date and time of sample collection.

4. Type of sample preservation.

5. Split samples taken by other parties. Note the type of sample, sample location,

time/date, name of person for whom the split was collected, that person’s company, and any other pertinent information.

6. Sampling method, particularly any deviations from the SOP.

7. Documentation or reference of preparation procedures for reagents or supplies that will become an integral part of the sample, if available. This information may not be available for water or soil sampling bottles that come preserved from the laboratory or for preservatives provided by the laboratory. Bottle blanks will need to be used to evaluate the provided reagents.

8. The laboratory where the samples will be sent.

No bound field logbooks will be destroyed or thrown away even if they are illegible or contain inaccuracies that require a replacement document.

2. Photographs. Take photographs of field activities using a digital camera. Photographs should include a scale in the picture when practical. Telephoto or wide-angle shots will not be used, since they cannot be used in enforcement meetings. The following items shall be recorded in the bound field logbook or on a field data sheet for each photograph taken:

SOP-SA-05;



1. The photographer’s name, the date, the time of the photograph, and the general

direction faced.

2. A brief description of the subject and the fieldwork portrayed in the picture.

3. Sequential number of the photograph. An electronic copy and/or a hard copy of the photographs shall be placed in task files in the field office after each day of field activities. Supporting documentation from the bound field logbooks or field data sheets shall be photocopied and placed in the task files to accompany the photographs once the field activities are complete.



DRAWINGS


WORK PLANS

TOOLS Field logbook, Sharpie©, black pen, digital camera, and field data sheets. FORMS/CHECKLIST

SOP-SW-01; SURFACE WATER/STREAM

SAMPLING


PURPOSE To provide standard instructions for the collection of aqueous samples from stream channels and drainage ditches.


WORK INSTRUCTIONS The following instructions are intended to provide sufficient guidance to perform the task in a safe, accurate, and reliable manner. Should these instructions present information that is inaccurate or unsafe, operations personnel must bring the issue to the attention of the Project Manager and the appropriate revisions made. All work carried under this SOP will be consistent with procedures and policies described in the appropriate Operation, Maintenance, and Monitoring (O&M) Plan (where applicable), appropriate Site Specific Health and Safety Plan (SSHASP), and Contractor’s Corporate Health and Safety Plan (HASP).

TASK INSTRUCTIONS Note The samples collected will be composite or grab samples depending upon the

sample site. Always collect samples from downstream to upstream locations and stand downstream of the sample bottles to avoid stream bed solids. If it is determined that the sampling water is highly polluted, an alternative method using a dipper or pump will be chosen. Wear gloves for all surface water sampling.

1. Label sample bottles and record sampling information.

Label the sample bottles with the appropriate sample number. Carefully and clearly address all the required categories and parameters. Place clear tape over the label. Record sampling information in the logbook or field data sheets and on the chain-of-custody form.

2. Rinse sampling equipment.

If the sample bottle was not received from the laboratory with the appropriate preservative, rinse the clean sample bottle (for unfiltered samples and inorganic analyses) three times with the water to be sampled. If collecting a composite sample from multiple stream segments, also rinse a decontaminated sampling bucket three times. If a water thief is to be used to collect water, it must also be rinsed three times.

3. Collect the sample.

Collect a grab or composite sample as specified in the Sampling and Analysis Plan (SAP) or Work Plan. In general, if the channel width is less than 5 feet across, collect grab samples from the center of the channel. If the channel width is greater than 5 feet, divide the channel into 5-foot sections and collect a composite sample at the center of each section to obtain a channel-integrated sample. If needed, a clean water thief may be used to collect the water and the water then transferred to the sampling containers or mixing bucket. In some cases, because of

SOP-SW-01; SURFACE WATER/STREAM

SAMPLING


safety considerations (e.g., fast water, deep water, entrapment hazards, freezing water, etc.), the grab sample will be collected from the stream bank. Submerse the sampling containers in the water, mouth pointing upstream and below the water surface. If it is necessary to stand in the stream, always collect sample upstream from the sampler’s location, facing upstream. Samples shall be collected from the approximate midpoint between the stream bed and the stream surface. Take care not to collect any stream bed solids. If the sample bottle was received from the laboratory with preservatives, be careful not to overfill the bottle and lose the preservative. A peristaltic pump may also be used to collect a sample. Hold the new disposable tubing under the water surface and turn the pump ON.

4. Add required preservatives.

If collecting a grab sample, fill the sample bottle and add required preservatives (if needed) according to SOP-SA-02 Sample Preservation and Containerization for Aqueous Samples. Secure the bottle cap tightly. If collecting a composite sample, pour the filled container into the bucket and then take the additional grabs in each of the remaining channel sections. Collect an adequate volume of water to fill all of the required bottles. Stir or swirl the contents of the bucket gently and fill each of the sample bottles for that particular sample set. If needed, add required preservatives according to SOP-SA-02 Sample Preservation and Containerization for Aqueous Samples.







WORK PLANS

SOP-SA-02 Sample Preservation and Containerization for Aqueous Samples.

TOOLS Sample bottles, cooler, and ice. Sampling bucket to collect samples from multiple stream segments. If needed: peristaltic pump and water thief. Field logbook or field data sheets and chain-of-custody forms.

FORMS/CHECKLIST

SOP-SW-02; FIELD SAMPLE FILTRATION


PURPOSE To provide standard instructions for conducting field filtration of water.



TASK INSTRUCTIONS Field Sample Filtration Notes The general procedures listed below are applicable for field filtration of water

samples for subsequent analysis of dissolved analytes. Refer to the following SOPs for the sampling setup in which filtering will occur: SOP-GW-02 Sampling with A Bailer SOP-GW-10 Purging And Sampling with A 12-Volt Submersible Pump SOP-GW-10A Purging And Sampling with A Low Flow Submersible Pump SOP-GW-10B Purging And Sampling with Grunfoss Redi-Flow Submersible Pump SOP-GW-10C Purging And Sampling with A Peristaltic Pump SOP-GW-13 Sampling Groundwater From A Tap

Field Filtering When Sampling With A Bailer

Notes: Prior to the sample event include an extra 1 liter sample container for each sample site on the laboratory bottle order. If necessary a 1-liter sample container can be decontaminated as describer in SOP-DE-02 Equipment Decontamination – Inorganic Contaminants. This is not recommended as there is a potential for introducing contamination. A new disposable filter is to be used for each sampling site. A Peristaltic Pump will be used for filtering the sample. Order Peristaltic Pump tubing: approximately 18-inches of silicon tubing and 12-inches of polyethylene tubing per sampling site.

1. Setup

Follow the procedures as outlined in SOP-GW-02 Sampling with A Bailer through the step for collecting samples.

2. Sample for filtering

While filling sample containers, also fill the extra 1- liter unpreserved sample container, this water will be used for filtering.



Install new tubing in the Peristaltic Pump. Insert an in-line high capacity (0.45 µm) disposable filter on the tubing. Make sure that the filter is inserted so that the flow arrow is pointed toward the discharge end of the tubing. Start the pump and let a small amount of water flow through the filter before filling the sample container. Hold the filter at an angle to ensure no unfiltered water from the tubing leaks into the sample container and only the filtered water enterers the sample container. If water stops discharging from filter replace filter with a new filter. If one of the sample containers (unpreserved) for the actual sample was used in lieu of an extra container to collect the water for filtering, refill the container after filtration is completed. Follow the SOP-SA-02 Sample Preservation and Containerization for Aqueous Samples to complete sample collection. If extremely turbid water is encountered place an in-line high capacity (10 µm) disposable filter before the in-line high capacity (0.45 µm) disposable filter.



4. Dispose of used bailer, tubing, filters and extra 1 liter sample container.

Bailer, tubing, filters and the extra 1 liter sample container used in the well sampling will be disposed of in accordance with SOP-DE-03 Investigation Derived Waste Handling.

Filtering Sample with 12-Volt Submersible Pump, Low Flow Submersible Pump and Grunfoss Redi-Flo II Submersible Pump

Note: A new disposable filter is to be used for each sampling site.

1. Setup

Follow the procedures as outlined in the appropriate SOP listed above through the step for collecting samples.


After filling the unfiltered sample containers as detailed in SOP-SA-02 Sample Preservation and Containerization for Aqueous Samples insert an in-line high capacity (0.45 µm) disposable filter in the discharge end of the tubing. Make sure that the filter is inserted so that the flow arrow is pointed toward the discharge end of the tubing. Let a small amount of water flow through the filter before filling the sample container. Hold the filter at an angle to ensure no unfiltered water from the tubing leaks into the sample container and only the filtered water enterers the sample container. If water stops discharging from filter replace filter with a new filter. If one of the sample containers (unpreserved) for the actual sample was used in lieu of an extra container to collect the water for filtering, refill the container after filtration is completed. Follow the SOP-SA-02 Sample Preservation and Containerization for Aqueous Samples to complete sample collection. If extremely turbid water is encountered place an in-line high capacity (10 µm)



disposable filter before the in-line high capacity (0.45 µm) disposable filter.



4. Dispose of used disposable tubing and filters.

Dispose of tubing and filters used in the well sampling in accordance with SOP-DE-03 Investigation Derived Waste Handling.

Filtering Sample with Peristaltic Pump

Notes: A new disposable filter is to be used for each sampling site.

1. Setup

Follow the procedure for pump setup and purging as outlined in the SOP-GW-10C Purging And Sampling with A Peristaltic Pump through the step to collect samples.


After filling the unfiltered sample containers as detailed in SOP-SA-02 Sample Preservation and Containerization for Aqueous Samples place an in-line high capacity (0.45 µm) disposable filter on the discharge end of the tubing. Make sure that the filter is inserted so that the flow arrow is pointed toward the discharge end of the tubing. Let a small amount of water flow through the filter before filling the sample container. Hold the filter at an angle to ensure no unfiltered water from the tubing leaks into the sample container and only the filtered water enterers the sample container. If water stops discharging from filter replace filter with a new filter. If one of the sample containers (unpreserved) for the actual sample was used in lieu of an extra container to collect the water for filtering, refill the container after filtration is completed. Follow the SOP-SA-02 Sample Preservation and Containerization for Aqueous Samples to complete sample collection. If extremely turbid water is encountered place an in-line high capacity (10 µm) disposable filter before the in-line high capacity (0.45 µm) disposable filter.



4. Dispose of used disposable tubing and filters.

Dispose of tubing and filters used in the well sampling in accordance with SOP-DE-03 Investigation Derived Waste Handling.

Filtering Sample from a Tap

Notes: Prior to the sample event include an extra 1 liter sample container per sample site on the laboratory bottle order. If necessary a 1-liter sample container can be decontaminated as describer in SOP-



DE-02 Equipment Decontamination – Inorganic Contaminants. This is not recommended as there is a potential for introducing contamination. A new disposable filter is to be used for each sampling site. A Peristaltic Pump will be used for filtering the sample. Order Peristaltic Pump tubing: approximately 18-inches of silicon tubing and 12-inches of polyethylene tubing per sampling site.

1. Setup

Follow the procedure for setup and purging as outlined in the SOP-GW-13 Sampling Groundwater From A Tap through the step for collecting samples.


While filling sample containers, also fill the extra 1- liter unpreserved sample container, this water will be used for filtering. Install new tubing in the Peristaltic Pump. Insert an in-line high capacity (0.45 µm) disposable filter on the tubing. Make sure that the filter is inserted so that the flow arrow is pointed toward the discharge end of the tubing. Start the pump and let a small amount of water flow through the filter before filling the sample container. Hold the filter at an angle to ensure no unfiltered water from the tubing leaks into the sample container and only the filtered water enterers the sample container. If water stops discharging from filter replace filter with a new filter. If one of the sample containers (unpreserved) for the actual sample was used in lieu of an extra container to collect the water for filtering, refill the container after filtration is completed. Follow the SOP-SA-02 Sample Preservation and Containerization for Aqueous Samples to complete sample collection. If extremely turbid water is encountered place an in-line high capacity (10 µm) disposable filter before the in-line high capacity (0.45 µm) disposable filter.



4. Disposable tubing, filters and if used extra 1 liter sample container

Disposable tubing, filters and the extra 1 liter sample container will be disposed of in accordance with SOP-DE-03 Investigation Derived Waste Handling.





WORK PLANS

SOP-GW-02 Sampling with A Bailer SOP-GW-10 Purging And Sampling with A 12-Volt Submersible Pump



SOP-GW-10A Purging And Sampling with A Low Flow Submersible Pump SOP-GW-10B Purging And Sampling with Grunfoss Redi-Flow Submersible Pump SOP-GW-10C Purging And Sampling with A Peristaltic Pump SOP-GW-13 Sampling Groundwater From A Tap SOP-DE-02 Equipment Decontamination – Inorganic Contaminants SOP-SA-02 Sample Preservation and Containerization for Aqueous Samples SOP-SA-01 Soil and Water Sample Packaging and Shipping SOP-DE-03 Investigation Derived Waste Handling

TOOLS Bailer, filter, tubing, pump, sample collection tools, cooler, sample bottles, petri dish, preservatives, distilled/deionized water, and desiccators.

FORMS/CHECKLIST

SOP-SW-03; TEMPORARY INSTALLATION OF FLUMES

FOR FLOW MEASUREMENT AND SURFACE WATER SAMPLING


PURPOSE To provide standard instructions for temporary installation of flumes for flow measurement and surface water sampling.



TASK INSTRUCTIONS Notes: Flumes are fixed hydraulic structures developed to measure surface waters and

irrigation flow. The flumes discussed in this SOP are custom built 60-degree trapezoidal flumes fitted with a staff gage marked in 100ths of a foot and in centimeters by Plasti-Fab Inc. The walls are ¼-inch thick with a polyester gel coating, and are equipped with side cavities with locking clips for transducer (level logger) installation. Trapezoidal flumes were originally developed to measure flows in irrigation channels. The principal advantages of trapezoidal flumes are their ability to measure a wide range of flows and also maintain good accuracy at low flows (Adkins, 2006). This SOP discusses a method to temporarily install flumes in ephemeral streams or very shallow streams to provide a method of measuring flow. There are two potential types of sites where a flume will need to be installed. The first is in ephemeral streams with no flow at the time of installation. The second installation will be in streams that have limited flow and the water is not deep enough to measure flow by other methods. Before going to install a flume, collect the proper tools for installation which should include at a minimum the flume, a shovel, empty sand bags (will fill on site), sledge hammer, a t- post, a level, transducer (optional), string for securing the transducer to the flume and a chain to secure the flume to the T-post. In most situations, if installing a flume at a site with no flow, the intention is to measure flow events (i.e., runoff, storms, irrigation runoff etc.). Installing a transducer in the flume will insure that flow events are measured. Review SOP-GW-15 Continuous GW Level Monitoring on programming and installation of transducers. If needed a barometer will also need to be installed. If there are other transducers in the area, check with that project manager to synchronize interval logging with their barometer. When installing flumes in streams with flow, the staff gage on the inside of the flume will be used for flow calculations.

1. Finding Suitable Installation Site

After arriving at the installation site, a suitable location for the flume must be identified. A flume should be located in a straight section of the open channel, without bends if possible. Any flow entering the flume should be non-turbulent. A slope of 1 percent or less is recommended upstream of the flume entrance area but




slopes up to 2 percent are acceptable. The flume should be installed in an area that has an elevation change which allows the water to flow through the flume and past the transducer and out the flume in a free flow condition (no ponding). Flumes should be placed in a narrowing portion of the stream bed to force channel flow through the flume. If this is not possible, temporary wing walls or baffles can be built on site, from native materials or from brought in man-made materials.

2. Installing Flume

The following are the steps for Installing the Flume:

1. Using the shovel, fill sandbags from sediment in the stream bed several yards downstream of the installation point or from adjacent areas outside of the channel.

2. At the chosen location, install flumes by minor hand excavation into the

stream channel, and then anchor them in place with sandbags and/or large rocks. Excavate the channel so that the upstream entrance of the flume can be buried at the lowest point in the channel (channel invert). The downstream outlet of the flume should be buried at a slightly lower elevation to ensure flow through the flume and to prevent any pooling of water. Using a level make sure that the top of the flume is level in both longitudinal and transverse directions, to ensure even flow past the transducer. If installing in a flowing channel make sure that all the water at the installation point is flowing through the flume.

3. Once the flume is situated in the channel, sandbags, large rocks or man-

made materials can be placed to anchor the flume in place and guide flow through the flume.

4. Place a T-post in the ground adjacent to the flume and secure the flume to the T-post. This is a precaution in case an unexpectedly high flow occurs. Securing the flume will prevent the flume from washing downstream or if it is buried in sediment during the event it can be located and reinstalled.

If the flume is installed with a slight slope, as determined by the level, an adjustment of the zero level on the staff gage may need to be made so that it is at the same elevation as the flume throat.

A DTEC sampler can be installed at the outlet of the flume to collect water if required in the SAP. Record all installation information in the field logbook, including the initial staff gage reading if appropriate. Examples of temporary flume installations with the trapezoidal Plasti-Fab flumes are shown below:




3. Site Visits and

Data Collection

Periodic site visits should occur to check the status of the flume. At each site visit any accumulated sediment, either water-borne or wind borne should be removed




from the flume. If any disturbance of the flume or the installed temporary structures has occurred, these should be repaired and the flume level should be checked and adjusted. If needed the zero level on the staff gage may need to be readjusted. During the site visit transducer readings can be downloaded as described in SOP-GW-15 and the staff gage reading should be recorded.

Flows through the flume can be determined by using the barometrically compensated transducer elevation data or the staff gage readings for the time period of interest. For storm event flows, the maximum elevation reading from the transducer during the potential storm event time period can be used in calculations. Flow is calculated using an equation provided by the manufacturer. The equation used for calculating the flow in the Plasti-Fab trapezoidal flumes below is:

Q = 1.55H2.58 where Q = cubic feet per second (cfs) and H = head in feet (compensated levelogger elevation or calculated elevation using staff gage readings).

Flows for overtopped flumes can be estimated by using the above equation and using the maximum pressure transducer reading recorded during the storm event. These flows should be flagged as “exceeded flume capacity”.





WORK PLANS

SOP-GW-15 Continuous GW Level Monitoring

TOOLS Flume, shovel, empty sand bags (will fill on site), sledge hammer, t- post, level, transducer (optional), string for securing the transducer to the flume and a chain to secure the flume to the T-post.

FORMS/CHECKLIST

SOP-SW-04; SAMPLING SURFACE WATER WITH THE

SCIENCEWARE 8 LITER CHURN SPLITTER


PURPOSE To provide standard instructions for sampling surface water with the scienceware 8 liter churn splitter.



TASK INSTRUCTIONS Notes: This Standard Operating Procedure (SOP) will be used in conjunction with SOP-

SW-01 SOP for Surface Water/Stream Sampling. This SOP details the use of the Scienceware 8 Liter Churn Sample Splitter (churn splitter) when collecting an equal width integrated channel sample. An equal width integrated channel sample is one in which the stream channel is divided into a number of equal-width increments. A composite sample is then collected by lowering and raising a collection bottle through the water column at the center of each increment. Each location in the channel cross section where water is collected is referred to as a subsample location. Subsamples are combined in the churn splitter mixed and then dispensed into required sample containers.

1. Sampling Preparation

When ordering bottles prior to the sampling event, ensure an additional 1-liter bottle is ordered for each sample location. This additional bottle will be used as the sample collection bottle. If prior knowledge of the sampling locations indicates that stream width at any location is greater than 35 feet wide, an extra 500 mL bottle should be ordered instead of a 1-liter bottle. Ensure that the churn splitter is clean and has been stored in a plastic bag for transport. If cleaning is required, see Cleaning the Scienceware 8 Liter Churn Splitter, below.

2. Selecting a Sampling Location

A sample location should be chosen where sampling personnel can safely enter the stream. If that is not an option an alternate method (e.g., such as placing the collection bottle in a water thief) can be used to sample. In addition, the sampling should take into account whether or not stream flow (discharge) measurements are to be taken. Stream flow measurements require a static stream section with constant, uniform flow and where dimensions are unlikely to change over the monitoring period. A static stream section is usually found on a straight stream reach at the downstream end of a riffle. Stream flow will be measured as described in SOP-WFM-05 Stream Flow Measurement Using a Marsh McBirney. Determine a path for personnel to traverse the stream so that they remain downstream of the collection points and limit the amount of disturbance to the stream bottom. The footing and speed of the current should be evaluated to ensure




that a safe path is selected.

3. Sampling with the Scienceware 8 Liter Churn Sample Splitter

Once an appropriate sampling location has been identified personnel set up the churn splitter and prepare the sample site. The procedure is outlined below. 1. Measure the width of the stream at the sampling location. Securely fasten a cloth

measuring tape across the stream, using stakes. Record the width of the stream on the field data sheet or in the field logbook.

2. Divide the stream into appropriate intervals and determine the number and

distance for subsample locations, if required. If the stream channel width is less than 5 feet across, collect a grab sample from the center of the channel. If the channel width is greater than 5 feet across, a subsample should be collected at the mid-point of each 5 foot section (modified Equal Width Increment Method). These subsamples from each section will be combined to obtain a channel-integrated composite sample. Examples to determine subsample locations are shown below.

a. The stream channel is 3 feet wide; a grab sample will be collected at

the mid-point of the channel (1.5 feet).

b. The stream channel is 8 feet wide; two subsamples will be collected and combined to generate a composite sample. Subsamples will be collected at the 2’ and 6’ measurement.

c. The stream channel is 15 feet wide, three subsamples will be

collected and combined to generate is composite sample. Subsamples will be collected at the 2.5’, 7.5’ and 12.5’ measurement.

3. Label sample bottles with the appropriate information as described in the SAP or WP. Based on the number and size of sample containers required for the location, determine the total volume. Add a minimum of 10% to this calculated volume to cover filter losses and spillage. The maximum capacity for the churn splitter is 7.5 liters. If the volume required is significantly less than 7.5 liters, up to an additional 4 liters should be collected.

4. Using the volume from Step 3 determine the volume of water that will need to

be collected at each subsample point along the stream transit. For example, if 4 liters will be required and there are 4 subsample locations in the transit, 1 liter would be collected at each location. The collection bottle must be filled the same number of times at each subsample location. If there are only 2 subsample locations, and 4 liters are required. The collection bottle would be filled twice at each subsample location.

5. Fill the churn splitter approximately 1/3 full with the stream water and

thoroughly rinse the churn splitter by swirling it and emptying the water out through the spigot. Repeat an additional 2 times. Make sure that the water is collected and released downstream of the actual sample location to avoid any




disturbance of the location. 6. Enter the stream downstream of the sample location, walk up to the appropriate

subsample location and begin collecting the sample. Use only one collection bottle per sample location in order to minimize sediment loss while transferring samples from the bottle to the churn splitter. Each time the bottle is filled and poured in to the splitter, the succeeding sample will wash any sediment remaining in the bottle from the previous subsample into the splitter. The collection bottle should be filled at each of the designated subsample locations and emptied into the churn splitter. Unless specified in the SAP, collect water from just above the stream bed to the water surface at each subsample location. The collection bottle should be raised and lowered fast enough to fill, but not overfill, the bottle. Remember to keep the bottle mouth pointed into the flow. Alternatively, the capped collection bottle can be lowered to the approximate midpoint between the stream bed and the water surface. Orient the bottle mouth upstream and remove the cap to begin sampling. Continue to fill and empty the collection bottle until all subsample locations have been sampled.

7. When the required volume has been collected, the splitter can be moved to a

processing area or the sample can be processed in place. In either case, make sure that the splitter is on a level area and that the largest volume sample bottle will fit under the spigot.

8. Place all sample containers within easy reach and begin stirring, once started,

stirring should be continuous. The manufacturer recommends that the sample be stirred at a uniform rate of approximately 9 inches per second by raising and lowering the churn paddle. As the volume in the tank decreases, the up and down motion should increase so that the churning velocity of the water stays consistent. The disc should touch the bottom of the tank on every down stroke but should not break the water surface on the up stroke. Personnel may want to practice with tap water prior to the sampling event to become familiar with this action.

It is imperative that the churning velocity remains within the appropriate range. If the stroke length and/or disc velocity is increased beyond the recommended rate, there may be a sudden change in sound and/or the effort required for churning. This may indicate the introduction of excessive air into the mixture. The introduction of excessive air into the sample is undesirable because it may change the dissolved gasses, bicarbonate, pH and other characteristics. Likewise, inadequate stirring may result in non-representative samples.

The sample in the churn splitter should be stirred at the uniform churning rate for about 10 strokes prior to filling the first sample container. This will insure the desired stirring rate of 9 inches per second can be achieved and the uniform distribution of suspended sediments. The churning must be continuous until all sample containers have been filled. If a break is required, the stirring rate must be re-established before filling any additional containers.

9. Open the spigot and begin sampling. The spigot should always be operated in




the FULL OPEN position. The sample container with the largest volume should be filled first. When all of the sample containers have been filled, return the unused portion of water to the stream. Clean all parts of the churn splitter thoroughly.

4. Cleaning the Scienceware 8 Liter Churn Sample Splitter

Once sampling is complete at a location, the churn splitter needs to be decontaminated prior to use at the next sample location.

1. Rinse the churn splitter with tap or de-ionized (DI) water to remove any remaining sediment.

2. Fill the churn splitter with soapy water. A very small amount of liquinox or alconox in DI water is sufficient. Allow it to soak for at least 10 minutes per manufacturer’s directions.

3. Scrub the inside of the churn splitter with a non-metallic brush. Run the soapy

water out through the spigot. 4. Rinse well with DI water, running the water out through the spigot. Repeat this

step at least two more times. 5. If required in the SAP or WP, prior to the DI rinses, a dilute rinse of all surfaces

with nitric acid or appropriate solvent (methanol) should be performed. 6. Place the cleaned churn splitter in a plastic bag for transport and/or storage.





WORK PLANS

SOP-SW-01 SOP for Surface Water/Stream Sampling SOP-WFM-05 Stream Flow Measurement Using a Marsh McBirney

TOOLS Scienceware 8 Liter Churn Sample Splitter (churn splitter), tap or de-ionized (DI) water, plastic bag, non-metallic brush, sample bottles, cooler, ice, cloth measuring tape, stakes, field data sheet or in the field logbook, liquinox or alconox, Optional: nitric acid or appropriate solvent (methanol)

FORMS/CHECKLIST

SOP-WFM-01; FIELD MEASUREMENT

OF PH IN WATER


PURPOSE To provide standard instructions for field measurement of pH in water.



TASK INSTRUCTIONS 1. Prepare the pH

meter. There are different brands and models of pH field measurement meters. All units, in general, should have automatic temperature correction (ATC) capabilities. Prior to using a pH meter, verify that it has the ATC function. User manuals for each meter are available and the specific directions for calibrating and measuring pH with that meter should be followed.

Calibrate pH meter in the field at the beginning of each day and if a standard check is out of calibration. Record the calibration information in the field logbook.

1. For a new probe, prepare the pH probe according to the directions in the electrode user guide.

2. Connect the probe to the appropriate connection on the meter.

3. Turn the meter on and make sure it is in the pH measurement mode. Calibrate instrument as described in the meter specific operating manual.

2. Calibrate the meter.

The following is a general summary for instrument calibration: 1. Rinse the ATC pH probe in de-ionized water. 2. Turn on meter and immerse the ATC pH probe in a pH 7 buffer solution.

Calibrate meter to pH 7 allowing enough time for meter to stabilize. 3. Rinse ATC pH probe with de-ionized water. 4. Immerse ATC pH probe in a pH 4 buffer solution. Calibrate meter to pH 4

allowing enough time for meter to stabilize. 5. Rinse pH and temperature probe with de-ionized water. 6. Immerse ATC pH probe in a pH 10 buffer solution. Calibrate meter to pH 10


OF PH IN WATER


allowing enough time for meter to stabilize. 7. Record the slope reading in the field logbook. 8. Recheck meter calibrations with the pH 4, pH 7 and pH 10 calibration solutions.

Repeat the calibration process (steps 2-4), if values for any of the final pH check is more than 0.1 units from the appropriate value.

3. Take field

measurements. The following is a general summary for field measurement of pH:

1. Rinse beaker with sample water three times.

2. Rinse ATC pH probe with de-ionized water.

3. Fill beaker with sample water.

4. Turn on meter and immerse ATC pH probe in sample water. Stir sample for

thorough mixing. Read and record pH to the nearest 0.01 unit once pH reading has stabilized.

5. Rinse electrodes with de-ionized water and store in carrying case.

Note: pH may also be measured by placing the probe directly into the water body being tested. The probe must be moved slowly in a circular motion when measuring stagnant water.

Important information about meter.

1. Store meter in case during transport.

2. Check batteries before taking meter into the field. Carry spare batteries and de-ionized water for rinsing probe.

3. Inspect probe for damage or dirt.

4. Dust and wipe the meter with a damp cloth. If necessary, warm water or mild

water based detergent can be used to clean the case. Immediately remove any spilled substance from the meter using the proper cleaning procedure for the type of spill.

5. If meter readings are erratic, replace the probe. If readings continue to be erratic,

return the meter to factory for repair.





SOP-DE-02 Equipment Decontamination


OF PH IN WATER


WORK PLANS

TOOLS pH field measurement meters, spare batteries for the pH field measurement meters, de-ionized water, pH 7 buffer solution, pH 4 buffer solution, pH 10 buffer solution, beaker, and field logbook.

FORMS/CHECKLIST


OF OXYGEN REDUCTION POTENTIAL IN WATER


PURPOSE To provide standard instructions for field measurements of oxygen reduction potential in water.



TASK INSTRUCTIONS Important information about meter’s calibration.

There are different brands and models of oxygen reduction potential (ORP) field measurement meters. All units, in general, should have automatic temperature correction (ATC) capabilities. Prior to using an ORP meter, check that it does have the ATC function. User manuals for each meter are available and the specific directions for calibrating and measuring ORP with that meter should be followed. Measure the raw millivolt (mV) values of an electrode in the mV mode. Calibrate the relative millivolt (RmV) values of a redox electrode for oxidation reduction potential (ORP) measurements in the relative mV/ORP mode. Note: the mV measurements are raw readings and cannot be calibrated. Use the relative mV mode to calibrate mV measurements. The relative mV mode can be used to calibrate the ORP electrode so the electrode reads the EHmV values in samples. When an ORP electrode is calibrated to read EHmV values, the resulting sample reading can be compared among multiple meters and electrode systems. The Contractor may use Thermo Scientific ORION 3 Star or 5 Star Portable Meters set to the millivolt (mV) mode for ORP readings. An Orion 9179BNMD epoxy low maintenance ORP/Automatic Temperature Compensating (ATC) Triode is attached to the meter. The Orion Star meters can perform an automatic ORP calibration adjusted for temperature. Listed below is the general calibration procedure. Refer to the meter specific operating manual for detailed calibration instructions.

1. Prepare electrode. 1. Remove the protective shipping cap from the sensing element and save the cap for storage.

2. Clean any salt deposits from the exterior of the electrode by rinsing with distilled water.

3. Shake the electrode downward (similar to a clinical thermometer) to remove air

bubbles. 4. Connect the electrode to the meter.




2. Connect the electrode to the meter.

1. Insert the ORP connector (large diameter) in the pH or BNC electrode input jack on the meter and the reference electrode connector (small diameter) into the reference electrode input jack.

3. Calibrate the

meter. All field meters must be calibrated prior to use. Calibration shall be performed at a minimum of once per day for each day of instrument use. Calibration shall be performed prior to the first measurements of the day. All calibration results should be recorded in the field logbook.

1. Set the meter to the relative millivolt (RmV) mode referring to the specific

meter’s user guide for detailed instructions.

2. Rinse the electrode with de-ionized or distilled water and place the ORP electrode in ORP standard, Orion 967901. Always use fresh ORP standard for calibrations. Empty the ORP calibration container in the Contractor’s Calibration Kit, rinse the bottle with fresh ORP solution, empty and then pour a sufficient amount of the calibration fluid into the bottle to cover the bottom of the electrode.

3. Wait for the RmV icon to quit flashing. 4. The Orion Star meters will automatically calculate the EHmV. Small

adjustments may be required to the meter to achieve the EHmV value of the ORP standard at the measured temperature. Information provided in the Thermo Orion User Guide for Redox/ORP Electrodes or Table 1 attached can be used as a reference for the appropriate reading. Adjust the meter referring to the meter user’s guide for detailed instructions on adjusting the reading.

5. Press the measure symbol to end the calibration. The milllivolt offset will be

displayed and the meter will proceed to the measurement mode. 6. Record the calibration information in the logbook.

4. Conduct field measurements.

Field ORP measurements for surface water may be made by direct submersion of the instrument probe into the sample stream. If flow is turbulent or shallow, or if direct immersion of the probe would risk damaging the probe, a grab sample can be collected and immediate measurement of the grab sample conducted. Field ORP measurements of groundwater may be made by inserting the probe into a flow through device or by collection of a grab sample and immediate analysis of the grab sample in the field. Specific requirements may be listed in the Sampling and Analysis Plan (SAP) or work plan. Field ORP is measured in units of mV (millivolts) on all Contractor’s meters. Refer to the meter specific operating manual for measurement instructions. Listed below are general measurement instructions:




1. Rinse the electrode with distilled or de-ionized water. Shake off any excess water and blot the electrode dry with lint-free tissue.

2. Check and make sure that the meter is measuring in mVs. 3. Place the electrode directly into the water to be measured. If the probe cannot be

placed directly into the water being measured, rinse a decontaminated beaker with sample water three times. Fill the beaker with the water to be measured.

4. Continuously stir or move the probe through the sample at a rate of about one

foot per second. 5. If the meter is in the continuous measurement mode, it will start reading

immediately and continuously update the display. The mV icon will flash until the reading is stable.

6. Read and record the result in the field logbook or on a field data sheet. 7. Remove the electrode from the sample, rinse it with distilled or de-ionized

water, and blot it dry before inserting the probe into the storage sleeve.

Important information about the meter.



3. Inspect probe for damage or dirt. 4. Dust and wipe the meter with a damp cloth. If necessary, warm water or mild


5. If meter readings are erratic, replace the probe. If measurement readings

continue to be erratic, return the meter to factory for repair.





WORK PLANS

TOOLS Oxygen reduction potential field measurement meters, ORP standard solution, calibration kit, spare batteries for the meters, distilled water or de-ionized water, lint-free tissue, beaker, and field logbook or field data sheet.




FORMS/CHECKLIST

Table 1 – Page 1




Table 1 – Page 2


OF SPECIFIC CONDUCTANCE


PURPOSE To provide standard instructions for field measurements of specific conductance.



TASK INSTRUCTIONS Important information about the meter.

There are different brands and models of specific conductance (SC) field measurement meters. All the units, in general, should have automatic temperature correction (ATC) capabilities. Prior to using a SC meter check that it does have the ATC function. User manuals for each meter are available and the specific directions for calibrating and measuring SC with that meter should be followed. The following is a general summary for field measurement of SC.


All field meters must be calibrated prior to use. Calibration shall be performed at a minimum of once per day for each day of instrument use. Calibration shall be performed prior to the first measurements of the day. Refer to the meter specific operating manual for calibration instructions. Listed below are general calibration requirements:

1. For a new probe, prepare the SC probe according to the directions in the

electrode user guide.

2. Connect the probe to the appropriate connection on the meter.

3. Turn the meter on and make sure it is in the conductivity measurement mode. Calibrate instrument as described in the meter specific operating manual. Unless specified in the Sampling and Analysis Plan (SAP) or work plan, one conductivity standard is used for calibration. Unless directed otherwise, use the 1413 micromhos/centimeter (µs/cm) calibration standard present in all of the calibration cases. Make sure that the calibration standard in the case is fresh. The container of calibration standard should be emptied, rinsed with new calibration standard and filled prior to a field sampling event. Replace batteries and try fresh calibration solutions if meter does not calibrate properly.

4. Record the calibration results in the field logbook. If the meter displays an

average calculated cell constant, record this in the field logbook.

5. Once the SC meter is in measure mode, measure the calibration standard and record this result and the measurement temperature in the field logbook.




6. Re-measure the calibration fluid at the end of the day and note any drift. Record

the information in the field logbook.

2. Conduct field measurements.

Field conductivity measurements for surface water may be made by direct submersion of the instrument probe into the sample stream. When flow is turbulent or shallow, or when direct immersion of the probe would risk damaging the probe, measurements may be made by collection of a grab sample and immediate analysis of the grab sample in the field. Field SC measurements of groundwater may be made by inserting the probe into a flow through device or by collection of a grab sample and immediate analysis of the grab sample in the field. Specific requirements may be listed in the SAP or work plan.

Field SC is measured in units of μS/cm (micromhos/centimeter) or mS/cm (millihos/centimeters) on most all meters. Refer to the meter specific operating manual for measurement instructions. Listed below are general measurement instructions:

1. If the probe cannot be placed directly into the water being measured, rinse the

decontaminated beaker with sample water three times.

2. Fill the beaker with the water to be measured.

3. With the meter in measurement mode, rinse the conductivity cell with distilled water, blot dry with a lint-free tissue and place the cell into the water being measured.

4. Submerge conductivity probe in sample so that flow cell holes are immersed and

wait for the readings to stabilize.

5. Read and record the SC result in the field logbook or on a field data sheet making sure that the correct units are recorded, either μS/cm or mS/cm. Record the sample temperature to the nearest 0.1 C from the conductivity meter after temperature has equilibrated.

6. Repeat the above steps for all samples.

7. When all samples have been measured, store the electrode according to their

specific user guides.

Important information about the meter.



3. Inspect probe for damage or dirt. 4. Dust and wipe the meter with a damp cloth. If necessary, warm water or mild











WORK PLANS

TOOLS Specific conductance field measurement meter, calibration standard solution, calibration kit, spare batteries for the meter, distilled water or de-ionized water, lint-free tissue, beaker, and field logbook or field data sheet.

FORMS/CHECKLIST


OF WATER TEMPERATURE


PURPOSE To provide standard instructions for field measurement of water temperature.



TASK INSTRUCTIONS Note: A pH field measurement meter should be used for measuring temperature.

1. Prepare the pH meter for measuring water temperature.

There are different brands and models of pH field measurement meters. All units, in general, should have automatic temperature correction (ATC) capabilities. Prior to using a pH meter, verify that it has the ATC function. User manuals for each meter are available and the specific directions for calibrating and measuring pH with that meter should be followed. Calibrate pH meter in the field at the beginning of each day and if a standard check is out of calibration. Record the calibration information in the field logbook. 1. For a new probe, prepare the pH probe according to the directions in the

electrode user guide. 2. Connect the probe to the appropriate connection on the meter. 3. Turn the meter on and make sure it is in the pH measurement mode. Calibrate

instrument as described in the meter specific operating manual.


The following is a general summary for instrument calibration: 1. Rinse the ATC pH probe in de-ionized water. 2. Turn on meter and immerse the ATC pH probe in a pH 7 buffer solution.

Calibrate meter to pH 7 allowing enough time for meter to stabilize. 3. Rinse ATC pH probe with de-ionized water. 4. Immerse ATC pH probe in a pH 4 buffer solution. Calibrate meter to pH 4

allowing enough time for meter to stabilize. 5. Rinse pH and temperature probe with de-ionized water. 6. Immerse ATC pH probe in a pH 10 buffer solution. Calibrate meter to pH 10

allowing enough time for meter to stabilize.




7. Record the slope reading in the field logbook. 8. Recheck meter calibrations with the pH 4, pH 7 and pH 10 calibration solutions.

Repeat the calibration process (steps 2-4), if values for any of the final pH check is more than 0.1 units from the appropriate value. Record pH and temperature calibration recheck values in logbook.

3. Take field

measurements. The following is a general summary for field measurement of pH and temperature:

1. Rinse beaker with sample water three times.

2. Rinse ATC pH probe with de-ionized water.

3. Fill beaker with sample water.

4. Turn on meter and immerse ATC pH probe in sample water. Stir sample for

thorough mixing. Read and record temperature to the nearest 0.1 unit once pH and temperature readings have stabilized.

5. Rinse electrodes with de-ionized water and store in carrying case.

Note: Temperature may also be measured by placing the probe directly into the water body being tested. The probe must be moved slowly in a circular motion when measuring stagnant water.

Important information about meter.



3. Inspect probe for damage or dirt.

4. Dust and wipe the meter with a damp cloth. If necessary, warm water or mild








SOP-DE-02 Equipment Decontamination




WORK PLANS

TOOLS pH field measurement meters, spare batteries for the pH field measurement meters, de-ionized water, pH 7 buffer solution, pH 4 buffer solution, pH 10 buffer solution, beaker, and field logbook.

FORMS/CHECKLIST

SOP WFM-05; STREAM FLOW MEASUREMENT WITH

MARSH MCBIRNEY FLOW METER

STATUS: IN PROGRESS DATE ISSUED: 04/30/13 REVISION: 0 PAGE 1 of 3

PURPOSE This SOP provides instructions for streamflow measurements with Marsh McBirney flow meters.


WORK INSTRUCTIONS The following instructions are intended to provide sufficient guidance to perform the task in a safe, accurate, and reliable manner. Should these instructions present information that is inaccurate or unsafe, operations personnel must bring the issue to the attention of the Project Manager and the appropriate revisions made. All work carried out under this SOP will be consistent with procedures and polices described in the applicable Site Specific Safety and Health plan and the

Contractor’s Corporate Health and Safety Plan (HASP). TASK INSTRUCTIONS

Streamflow Measurement with Marsh McBirney

Flow Meter

Measurement of discharge will be accomplished by the USGS velocity - area method utilizing a Marsh McBirney meter. Locations for the discharge gauging stations will be based on the physical characteristics of the stream reach. Discharge measurement requires a stream section with consistently uniform flow and a static stream bed where dimensions are unlikely to change over the monitoring period. A static stream section is usually found on a straight stream reach at the downstream end of a riffle. For shallow streams with depths less than 2.5 feet, the best velocity - area method is the six-tenths' method. This method measures current velocity at a depth six-tenths of the total depth below the water surface. If depths are greater than 2.5 feet, measurements should occur at two-tenths and eight-tenths below the surface and the results are averaged for the discharge at the gauging station. The procedure is as follows:

1. Assemble the equipment per the manufacturer's instructions.

2. Select a stream section where flows are mostly parallel to the banks, there are no sharp turns in the flow direction, and the bottom is reasonably smooth. The section can be smoothed by reshaping the edges, removing rocks from the bottom, and removing branches, weeds, or grasses. Do not alter the bank or stream bed once measurements begin.

3. Set a cloth tape across the section, perpendicular to the flow. Anchor both ends securely to stakes or other fixed objects.

4. Determine the measurement interval size necessary so that no interval has greater than 5% of the flow. Generally 20 to 25 intervals are adequate depending on the variability and complexity of the stream channel. Measurement intervals in slower sections can be further apart, while measurement intervals in faster or




deeper sections should be closer together.

5. Turn on the flow meter. Check the data collection interval per the manufacturer’s instruction. Begin measurements at either the left or right bank looking upstream. Note which bank the initial point is located in either the logbook or the field data sheet. The initial point is generally the tape reading at the water line and has no depth or velocity to measure. Water depth is determined by reading the markings on the wading rod; read depths while ignoring the "pile-up" effect on the upstream portion of the wading rod. This can be accomplished by drawing a line from the undisturbed portion of the stream in front of the wading rod to the wading rod and reading the markings. Record the depth for each interval on the field data sheet or in the logbook.

6. On the marked wading rod, set the probe for the appropriate depth (6/10s method for streams less than 2.5 feet deep or dual depths; 2/10 and 8/10, for streams greater than 2.5 feet) (see operators manual for instructions on setting the probe depth). Care must be taken to keep the bulb pointed directly into the flow and to keep the rod in a vertical position. Flow at each station should be measured for 30 seconds. Flow can be measured for longer intervals and will result in more accurate results. Record this information in the logbook or on the field data sheet. Continue across the stream measuring at the predetermined interval.

7. Record station, depth and average velocity on the stream flow field data sheet or in the log book. Calculate the approximate stream flow for each gauging interval using the following:

Discharge = area X average velocity, where area is the depth of the segment by the width of the interval measured and the average velocity is either the velocity measured at 6/10ths or the average of the measurement from the 2/10th and 8/10s depths.

Total flow for the stream would be the sum of discharge from each gauging interval.

An example of a completed field data sheet is attached, as well as a blank copy of the field form (Open Channel Profiling Form) and the EXCEL spreadsheet for entering the flow measurements for the final calculations. When calculating the flow or entering it into the computer the first gauging interval measured will be ½ the width of the second measured interval and the final interval measured will be ½ the width of the next to last interval.

Note: very small flows (not exceeding 50 gpm) or streams to shallow to measure with the flow meter may be measured using the bucket and stopwatch or float and stopwatch methods.




Personnel Decontamination

1. All personnel must go through decontamination procedures whenever leaving a contaminated area. Decontamination procedures should be used in conjunction with methods to prevent contamination including minimizing contact with wastes and maximizing worker protection. Personnel must follow PTS-SOP-DE-01 Personnel Decontamination Procedures.


P&IDS

DRAWINGS SAP with site location and sample locations.


WORK PLANS

Related SOPs: PTS-SOP-DE-01 Personnel Decontamination Procedures.

TOOLS Marsh McBirney current meter, tag line or cloth tape, and field logbook or field data sheet. Bucket and stopwatch for very slow flows.

FORMS/CHECKLIST

SOP-WFM-07; FIELD MEASUREMENT OF DISSOLVED

OXYGEN


PURPOSE To provide standard instructions for field measurements of dissolved oxygen.



TASK INSTRUCTIONS Note There are several brands and models of dissolved oxygen (DO) field measurement

meters. All the units have automatic barometric pressure and salinity content compensation. User manuals for each meter are available and the specific directions for calibrating and measuring DO with that meter should be followed. The following is a general summary for field measurement of DO.


All field meters must be calibrated prior to use. Calibration shall be performed at a minimum of once per day for each day of instrument use. Calibration shall be performed prior to the first measurements of the day. Refer to the meter specific operating manual for calibration instructions. Listed below are general calibration requirements:

1. Inspect DO meter and probe for damage. If one of the YSI DO meters is to be

used, inspect the probe for sufficient electrolyte and to determine if the oxygen sensor membrane is in good condition. Replace membrane, if torn or wrinkled. Inspect for air bubbles beneath the membrane. If bubbles are present, remove membrane and add electrolyte solution. Replace membrane so that air bubbles are absent. If the Thermo Scientific DO meters are used, check to make sure the RDO Optical Dissolved Oxygen probe has not exceeded its lifespan.

2. Turn the meter on and if needed place the meter in the DO measurement mode. Calibrate instrument as described in the meter specific operating manual. Unless specified in the Sampling and Analysis Plan (SAP) or work plan, calibration should be conducted in the % saturation mode. Replace batteries and clean probe, if meter does not calibrate properly.

3. An air calibration is performed in water saturated air using the

calibration/storage sleeve. To begin, check the sponge in the calibration sleeve and moisten the sponge with distilled water, if needed. Place 3-6 drops of water on the sponge and then allow any excess water to drain out of the chamber. The wet sponge creates a 100% water saturated air environment for the probe. This environment is ideal for DO calibration and for storage of the probe during transport and non-use.


OXYGEN


4. Allow the probe and calibration standard (water saturated air) to reach

equilibrium.

5. Calibrate the meter according to manufacturer's instructions. To accurately calibrate the YSI DO meters you will need to know the following information:

The approximate salinity of the water you will be analyzing. Fresh water has

a salinity of approximately zero. Seawater has a salinity of approximately 35 parts per thousand (ppt).

For calibration in % saturation mode, the approximate altitude (in feet) of the region where you are located is required. This information can be obtained over the internet or from a topographic map.

6. Record the % saturation number displayed at the end of the automatic

calibration.

2. Take measurements.

Field DO measurements for surface water may be made by direct submersion of the instrument probe into the sample stream. If flow is turbulent or shallow, or if direct immersion of the probe would risk damaging the probe, a grab sample can be collected and immediate measurement of the grab sample conducted. Field DO measurements of groundwater may be made by inserting the probe into a flow through device or by collection of a grab sample and immediate analysis of the grab sample in the field. Specific requirements may be listed in the SAP or work plan. The site-specific document may list the units that DO should be measured in (e.g., % saturation or mg/L). Refer to the meter-specific operating manual for measurement instructions. Listed below are general measurement instructions:

1. If the probe cannot be placed directly into the water being measured, rinse the

decontaminated beaker with sample water three times.

2. Fill the beaker with the water to be measured.

3. Continuously stir or move the probe through the sample at a rate of about one foot per second.

4. Allow temperature and dissolved oxygen readings to stabilize.

5. Read and record the DO result in the field logbook or on a field data sheet

making sure that the correct units are recorded (either % Sat or mg/L). Record the sample temperature to the nearest 0.1ºC from a pH meter, if available, after the temperature has equilibrated.

6. Spray the probe with de-ionized water and wipe clean before reinserting to

calibration/storage sleeve.

7. Repeat the above steps for all samples.


OXYGEN


8. When all samples have been measured, store the electrode according to their specific user guides.

3. Maintenance

of equipment. 1. Store meter in case during transport.

2. Check batteries before taking meter into the field. Carry spare batteries and de-

ionized water for rinsing probe. 3. Inspect probe for damage or dirt.

4. Dust and wipe the meter with a damp cloth. If necessary, use warm water or

mild water based detergent to clean the case. Immediately remove any spilled substance from the meter using the proper cleaning procedure for the type of spill.

5. If meter readings are erratic, replace the probe. If measurement readings

continue to be erratic, return the meter to factory for repair.





WORK PLANS

TOOLS Dissolved oxygen field measurement meter, de-ionized water, distilled water, decontaminated beaker, field logbook or field data sheet, and spare batteries for meter.

FORMS/CHECKLIST

SOP-WFM-08;

FIELD TURBIDITY MEASUREMENT


PURPOSE To provide standard instructions for field turbidity measurements.



TASK INSTRUCTIONS Note The turbidity of the water pumped during well development and sampling or surface

water testing will be measured using a portable turbidimeter. Record the general sampling information in the bound logbook, field data sheets or the well development data form, as appropriate. The turbidity measurement data for groundwater sampling will include, at a minimum, the well number, date and time, volume of water pumped, and the Nephelometric Turbidity Units (NTU) reading.

Equipment Description

A HACH Model Portable Turbidity Meter (HACH Turbidimeter) operates on the nephelometric principle of turbidity measurement and meets EPA Method 180.1. The meter measures turbidity directly in NTU on a precalibrated meter scale. Calibration of the meter is based on an accepted primary standard of turbidity measurement and will be completed per the manufacturer’s guidance.

1. Calibrate instrument.

All field meters must be calibrated prior to use. Perform calibration at a minimum of once per day for each day of instrument use. Perform calibration prior to the first measurements of the day. The HACH Turbidimeter calibration is accompanied with three standards provided in the meter kit by the manufacturer. 1. Place the meter on a flat steady surface. Do not hold the meter during operation.

Turn on the meter and let it warm up. 2. Start the calibration process by pushing the “Calibration” key to enter the

calibration mode and follow the instructions on the display. 3. Insert the calibration sample cell marked 20 NTU in the instrument cell

compartment, close the lid and press “Read”. Note: Before inserting the calibration cell, make sure that the sample cell is clean. Wipe the sample cell thoroughly with a lint free cloth. If needed, oil the sample cell with silicone oil. To ensure that the standard solutions are well-mixed, gently invert each standard before inserting into the meter. Insert so that the diamond or orientation mark aligns with the raised orientation mark in front of the cell compartment.

SOP-WFM-08;



4. Record the result in the logbook. 5. Repeat steps 3 and 4 with the 100 NTU and 800 NTU calibration cells. Clean

and gently invert each calibration cell prior to inserting in the meter. 6. Push “Done” to review the calibration details and record in logbook. 7. Push “Store” to save results. 8. The meter automatically goes into the “Verify Calibration” mode once the

calibration sequence is complete. Insert the 20.0 NTU Verification Standard and close the lid.

9. Push “Read.” The display shows “Stabilizing” and then shows the result and

tolerance range. Record this information in the field logbook. 10. Push “Done” to return to the reading display. Repeat the calibration verification

if the verification failed. These steps may vary from different models and manufactures. Always refer to manufacture’s user manual.

2. Verify Standards

Verify manufacture’s standards are reading accurately and record in logbook. The HACH Turbidimeter calibration is accompanied with four standards provided in the meter kit by the manufacturer: <0.1, 20, 100 and 800 NTU. HACH’s accuracy is +/-2% of the reading plus stray light from 0-1,000 NTU (FTU). If turbidity meter is not a HACH Turbidimeter verify accuracy with manufacture’s user manual. To verify the standards repeat steps 3 and 4 above with each of the four provided standards. Clean and gently invert each calibration cell prior to inserting in the meter.

3. Collect Samples.

The HACH Turbidimeter requires collection of a sample for subsequent turbidity measurements. The sample may be collected using any clean container including a sample cell. Rinse sample cells three times with the water to be measured prior to filling the cell for measurement. Collect samples for field measurement purposes by direct submersion of the sample container into the flow whenever possible. For surface water, always collect samples upstream of sampling personnel and equipment, and with the sample container pointed upstream when the container is opened for sample collection. Take care not to sample water downstream of areas where sediments have been disturbed in any manner by field personnel. Collect samples from a location where the sample stream visually appears to be completely mixed. Ideally, this is at the center of the flow cross-section, but site conditions do not always allow this. The location should preferably be accessible by

SOP-WFM-08;



direct reach, or in the case of a receiving water body, via wading. Caution is required when wading, as flowing water provides more force than visually anticipated. If the center of the flow cannot be sampled by direct reach or by wading into the flow, use a sampling pole or other sampling device to reach the sampling location. Such devices typically involve a means to extend the reach of the sampler, with the sample bottle attached to the end of the device for filling at the desired location. For groundwater, fill the sample cells with sample water directly from the pump tubing during purging activities. Rinse the sample cell three times with purge water prior to sample collection.

4. Take turbidity measurements.

Always cap the sample cell prior to placing in the cell compartment to prevent spillage of the sample into the instrument. Use clean sample cells in good condition. Dirty, scratched or damaged cells can cause inaccurate readings. Make sure that cold samples do not “fog” the sample cell. 1. Collect a representative sample in a clean container. Fill a sample cell to the

line (about 15 milliliter). Take care to handle the sample cell by the top. Cap the cell.

2. Wipe the cell with a soft, lint-free cloth to remove water spots and fingerprints. 3. Apply a thin film of silicone oil (provided in meter kit), if needed. Wipe with

soft cloth (provided in meter kit) to obtain an even film over the entire surface. 4. Push the “Power” key to turn on the meter. Make sure that the meter is placed

on a level, stationary surface during the measurement. Do not hold the meter in the hand during measurement.

5. Gently invert the sample cell to ensure mixing. Insert the sample cell in the

instrument cell compartment so the diamond or orientation mark aligns with the raised orientation mark in front of the cell compartment. Close the lid.

6. Push the “Read” key. The display shows “Stabilizing” then displays the

turbidity in NTU (FNU). 7. Record the value in the field logbook or on the field data form. These steps may vary for different models and manufactures. Always refer to the Turbidmeter manufacture’s user manual. Repeat sample collection and measurement process as required in the sampling and analysis plan, work plan or the specific SOP. After use, rinse the sample cells with di-ionized water. Store the sample cells with caps on to prevent cells from drying. Do not air-dry the sample cells after use.

SOP-WFM-08;



5. Store sample cells.

To properly store the sample cells: 1. Fill the sample cells with di-ionized water. 2. Cap and store the sample cells. 3. Wipe the outside of the sample cells dry with a soft cloth.





WORK PLANS

TOOLS Turbidimeter and meter kit; bound logbook, field data sheets or well development data form; clear containers for sample collection; sampling pole or other sampling device (if the center of the flow cannot be sampled by direct reach or by wading into the flow); and de-ionized water.

FORMS/CHECKLIST

SOP-WFM-09; BUCKET AND STOPWATCH

METHOD FOR MEASURING FLOW


PURPOSE This document describes general and specific procedures, methods and considerations to be used and observed when conducting discharge measurement during field investigations.



TASK INSTRUCTIONS Field Measuring Flow

Note The general procedure listed below is applicable for lower flow volume. The main limitation is that the discharge must fall from a hose, pipe, or from a drop in a channel in such a way that the collection container can be placed underneath to capture all the discharge.

1. Locate the measurement area.

Locate the measurement area and determine what size container would be most appropriate for measuring the flow. If discharge occurs via a channel, then a temporary dam may need to be placed across the channel with the discharge directed through a single outlet.

2. Place collection container directly under the discharge.

Place collection container directly under the discharge. All discharge should flow into the collection container. (Note: measurement lines on the container may need to be measured and clearly marked ahead of time.)

3. Time discharge with stopwatch.

Time discharge with stopwatch. Time how long it takes to fill the container or to the desired measurement line marked on container. Record time in logbook.

4. Repeat Repeat steps 2 and 3 two more times to obtain a three point average.

5. Calculate discharge.

Calculate discharge by following Example 1 calculation.




Example 1 Calculation: Calculating Discharge A 5-gallon bucket is placed under a discharging hose. The bucket fills in 25 seconds, 28 seconds and 24 seconds. Calculate average time:

Add the three recorded times together and divide by three to obtain the average fill time.

25 28 24

325.7

Convert average time in seconds to minutes:

Divide average time by 60 seconds per minute to obtain minutes.

25.7seconds

60seconds/minute0.43

Calculate the discharge:

Divide the volume of the bucket (gallons) by the average time to fill the bucket (minutes). 5gallons

0.43 mintues11.6

Source: Estimating Discharge and Stream Flows A Guide for Sand and Gravel Operators, July 2005 Field Measuring Flow (alternative for low flow)

Note The general procedure listed below is applicable for low flow volume. The main limitation is that the discharge must fall from a hose, pipe, or from a drop in a channel in such a way that the collection container can be placed underneath to capture all the discharge.

1. Locate the measurement area.

Locate the measurement area and determine what size container would be most appropriate for measuring the flow. If discharge occurs via a channel, then a temporary dam may need to be placed across the channel with the discharge directed through a single outlet.

2. Place collection container directly under the discharge.

Place collection container directly under the discharge. All discharge should flow into the collection container. (Note: measurement lines on the container may need to be measured and clearly marked ahead of time.)

3. Time discharge with stopwatch.

Time discharge with stopwatch for 1 minute. Record volume in logbook.

4. Repeat Repeat steps 2 and 3 two more times to obtain a three point average.

5. Calculate discharge.

Calculate discharge by following Example 2 calculation.




Example 2 Calculation: Calculating Discharge A 1-liter beaker is placed under a discharging hose. The beaker fills to 55 milliliters and 60 milliliters and 58 milliliters in the 1 minute. Calculate average volume:

Add the three recorded volumes together and divide by three to obtain the average volume.

55 60 58

357.7

Convert average volume in milliliters to liters:

Divide average volume by 100 milliliters per liter to obtain liters.

57.7milliliters

100milliliters/liter0.58

Calculate the discharge:

Divide the average volume of the beaker (liters) by the time (minute). 0.581 mintue

0.58


P&IDS



WORK PLANS

TOOLS A variety of different sized containers based on expected flow, beakers up to 1 liter, buckets up to 5-gallons,(with volume marked), stopwatch, logbook and pen.

FORMS/CHECKLIST

Appendix A2

Laboratory Standard Operating Procedures

Pace Analytical Services, Inc. 1700 Elm Street SE, Suite 200 Minneapolis, MN 55414

www.pacelabs.com

Phone: 612-607-1700 Fax: 612-607-6444

STANDARD OPERATING PROCEDURE INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION SPECTROSCOPY

Reference Methods: EPA 6010B, 6010C, and EPA 200.7

Local SOP Number: S-MN-I-313-rev.25 Effective Date: Date of Final Signature

Supersedes: S-MN-I-313-rev.24

APPROVALS

PERIODIC REVIEW

SIGNATURES BELOW INDICATE NO CHANGES HAVE BEEN MADE SINCE PREVIOUS APPROVAL.

Signature Title Date



© 2002 – 2014 Pace Analytical Services, Inc. This Standard Operating Procedure may not be reproduced, in part or in full, without written consent of Pace Analytical Services, Inc. Whether distributed internally or as a “courtesy copy” to clients or regulatory agencies, this document is considered confidential and proprietary information. Any printed documents in use within a Pace Analytical Services, Inc. laboratory have been reviewed and approved by the persons listed on the cover page. They can only be deemed official if proper signatures are present.

This is COPY# 18 Distributed on 20Jan2015 by SDP and is CONTROLLED or X UNCONTROLLED

S-MN-I-313-rev.25

TABLE OF CONTENTS

SECTION PAGE 1. Purpose/Identification of Method ............................................................................................. 3

2. Summary of Method ................................................................................................................... 3

3. Scope and Application ................................................................................................................ 3

4. Applicable Matrices .................................................................................................................... 3

5. Limits of Detection and Quantitation ....................................................................................... 3

6. Interferences ................................................................................................................................ 3

7. Sample Collection, Preservation, Shipment and Storage ........................................................ 4

8. Definitions .................................................................................................................................... 4

9. Equipment and Supplies (Including Computer Hardware and Software) ........................... 4

10. Reagents and Standards ............................................................................................................. 5

11. Calibration and Standardization............................................................................................... 5

12. Procedure ..................................................................................................................................... 7

13. Quality Control ........................................................................................................................... 9

14. Data Analysis and Calculations ............................................................................................... 10

15. Data Assessment and Acceptance Criteria for Quality Control Measures ......................... 10

16. Corrective Actions for Out-of-Control Data .......................................................................... 10

17. Contingencies for Handling Out-of-Control or Unacceptable Data .................................... 11

18. Method Performance ................................................................................................................ 11

19. Method Modifications .............................................................................................................. 11

20. Instrument/Equipment Maintenance ...................................................................................... 11

21. Troubleshooting ........................................................................................................................ 11

22. Safety .......................................................................................................................................... 11

23. Waste Management .................................................................................................................. 11

24. Pollution Prevention ................................................................................................................. 12

25. References .................................................................................................................................. 12

26. Tables, Diagrams, Flowcharts, and Validation Data ............................................................. 12

27. Revisions .................................................................................................................................... 12

Inductively Coupled Plasma Atomic Emission Spectroscopy Pace Analytical Services, Inc. Effective Date: Upon Final Signature S-MN-I-313-rev.25 Page: 3 of 19

1. Purpose/Identification of Method

1.1. The purpose of this SOP is to establish a procedure for the determination of metals by inductively coupled plasma atomic emissions spectroscopy (ICP-AES) as delineated in EPA Method 6010B, 6010C or 200.7.

2. Summary of Method

2.1. Prior to analysis, samples must be solubilized or digested using appropriate sample preparation methods.

2.2. This method describes the determination of elements by ICP-AES. The method measures element-emitted light by optical spectrometry. Samples are nebulized and the resulting aerosol is transported to the plasma torch. Element-specific atomic-line emission spectra are produced by a radio-frequency inductively coupled plasma. The spectra are dispersed by a grating spectrometer, and the intensities of the lines are monitored by a charge coupled device detector.

2.3. Background correction may be required. Background is measured adjacent to analyte lines on samples during analysis. The position selected for the background-intensity measurement, on either or both sides of the analytical line, will be determined by the complexity of the spectrum adjacent to the analyte line. The position used should be free of spectral interference and reflect the same change in background intensity as occurs at the analyte wavelength measured. Background correction is not required in cases of line broadening where a background correction measurement would actually degrade the analytical result. The possibility of additional interferences should also be recognized and appropriate corrections made as necessary.

3. Scope and Application

3.1. Personnel: The policies and procedures contained in this SOP are applicable to all personnel involved in the analytical method or non-analytical process.

3.2. Parameters: This SOP applies to the elements listed in Attachment I.

4. Applicable Matrices

4.1. This SOP is applicable to ground water, aqueous samples, leachates, industrial wastes, soils, sludges, sediments, and other solid wastes.

5. Limits of Detection and Quantitation

5.1. The reporting limit (LOQ) for all analytes is listed in Attachment I. All current MDLs are listed in the LIMS and are available by request from the Quality Manager.

6. Interferences

6.1. Spectral Interferences are caused by background emission from continuous or recombination phenomena, stray light from the line emission of high concentration elements, overlap of a spectral line from another element, or unresolved overlap of molecular band spectra.

6.1.1. Spectral overlap can be compensated by computer-correcting the raw data after monitoring and measuring the interfering element. Unresolved overlap requires selection of an alternate wavelength. Background contribution and stray light can usually be compensated for by a background correction adjacent to the analyte line. Interelement correction factors are used on the simultaneous ICP.

6.2. Physical Interferences are effects associated with the sample nebulization and transport processes. Changes in viscosity and surface tension can cause significant inaccuracies, especially in samples containing high dissolved solids or high acid concentrations. If physical interferences are present, they must be reduced by diluting the sample, by using a peristaltic pump, by using an internal


standard, or by using a high solids nebulizer. Another problem that can occur with high dissolved solids is salt buildup at the tip of the nebulizer, affecting aerosol flow rate and causing instrument drift.

6.3. Chemical interferences include molecular compound formation, ionization effects and solute vaporization effects. Normally, these effects are not significant with the ICP technique, but if observed, can be minimized by careful selection of operating conditions (incident power, observation position, and so forth), but buffering the sample, by matrix matching, and by standard addition procedures.

6.4. Memory interferences result when analytes in a previous sample contribute to the signals measured in the new sample. Memory effects can result from sample deposition on the uptake tubing to the nebulizer and from buildup of sample material in the plasma torch and spray chamber.

6.5. Users are advised that high salt concentrations can cause analyte signal suppressions and confuse interference tests.

7. Sample Collection, Preservation, Shipment and Storage

7.1. Table 7.1 – Sample Collection, Preservation, Shipment and Storage

Sample type Collection per sample Preservation Storage Hold time Liquid Glass containers. Collect

dissolved metal samples and filter immediately through a 0.45-micron filter on-site by the sampler before adding preservative. If samples are filtered at the laboratory, use a polyethylene or glass container and preserve after filtration with HNO3.

Preserve immediately with HNO3

to bring the pH to <2

For samples received with a pH>2, additional nitric acid must be added upon receipt to dissolve the metals that may have adhered to the sample container. Sample receiving adds the additional acid, labels the samples with the amount of acid added, the lot number of the acid, date, time and initials of person that added the acid. The samples must not be analyzed for 24 hours from acid addition per the Method Update Rules.

Store total and dissolved metal samples at room temperature.

The maximum sample holding time for metals is 6 months from sample collection.

Solid

Glass or polyethylene container

N/A Above freezing but below 6oC.

The maximum sample holding time for metals is 6 months from sample collection.

8. Definitions

8.1. Definitions of terms found in this SOP are described in the Pace Analytical Services Quality Manual, Glossary Section.

9. Equipment and Supplies (Including Computer Hardware and Software)

9.1. Table 9.1 – Equipment and Supplies

Supply Description Vendor/Item #/Description Perkin Elmer Optima 4300 (or equivalent) Desktop computer and printer Perkin Elmer AS 93 Plus Autosampler


Peristaltic pump and Fisherbrand pump tubing, or equivalent.

Refrigerated Circulator Argon gas supply high-purity grade, 99.99% House Argon Mechanical pipettes, and metals-free disposable pipet tips

Glassware Class A volumetric flasks, graduated cylinders and funnels (glass or metals-free class B plastic).

Disposable digestion cups 50 mL Epic Pro Data reporting software See master list for current version LimsLink Data transmission software See master list for current version WinLab 32 ICP Continuous Automated Analysis Control See master list for current version

10. Reagents and Standards

10.1. Table 10.1 – Reagents and Standards

Reagent/Standard Concentration/Description Requirements/Vendor/Item # De-ionized Water ASTM Type II House DI water Concentrated Hydrochloric acid (HCl) Trace Metals grade Fisher Concentrated Nitric Acid (HNO3) Trace Metals grade Fisher Calibration Standard Stock Solutions Custom blend Spex Certiprep or equivalent Initial Calibration Verification (ICV) Stock Standard solutions

Custom blend. Must be separate stock from the calibration standards.

CPI or equivalent

Profiling Solution Manganese, at a concentration of 1 mg/L or 10 mg/L, is used to profile the system

Internal Standards (optional) Scandium (1 mg/L) or Yttrium (5 mg/L) may be used as an internal standard

10.2. Table 10.2 - Working Standard Dilutions and Concentrations

10.2.1. See Attachment VII – ICP Standard Prep Log 8632

11. Calibration and Standardization

11.1. Table 11.1 – Calibration and Standardization

Calibration Metric Parameter/Frequency Criteria Comments Initial Calibration (ICAL)

Instruments must be calibrated at a minimum once every 24 hours or prior to use. The instrument standardization

date and time must be included in the raw data. See Attachment VI for an example

run sequence. A calibration curve must

consist of a blank and at least one calibration standard

Linear regression:

r ≥ 0.995 for 6010B, 200.7

r ≥ 0.998 for 6010C

If not met, remake standards and recalibrate and verify before sample analysis.

Second Source Verification Standard (ICV)

Immediately after the calibration standards have

been analyzed, the accuracy of the initial calibration shall be verified and documented for every analyte by the analysis of an ICV Solution(s) at each

± 10% for method 6010B and 6010C or ± 5% for method 200.7

The RSD of the standards must be

below 5% for 6010 and 3% for 200.7 W of the replicate readings.

Review the standard preparation. Remake the

standard accordingly if that is the cause. Re-inject the ICV one more time, if it

fails stop all analysis. Perform all necessary


wavelength used for analysis.

The Initial Calibration Verification (ICV) Solution(s)

should be obtained from a different source than the

calibration standards.

instrument maintenance and recalibrate the instrument.

Only two injections are allowed back to back, then

the system must be recalibrated.

Continuing Calibration Verification (CCV)

To ensure calibration accuracy during each analytical run, a

CCV standard must be analyzed after every 10

samples and at the end of the run for each wavelength. The ICV solution can be utilized

as the CCV.

For method 6010B, 6010C and 200.7, the CCV must be within ± 10% of the true value. The RSD of the standards must be below

5% for 6010 and 3% for 200.7 W of the replicate readings.

If the requirements for continuing calibration are not met, review for preparation error or instrument malfunction. A CCV may be repeated, but a second failure requires the system to be recalibrated prior to further analysis.

If the samples bracketed are non-detect and the CCV is biased high, data may be reported as there is no impact from the high bias. If the samples associated are non-detect and the only detections are associated with the batch QC (LCS/MS) but the QC is within limits, the data can be reported. The QC should be flagged indicating that there was bias but that there was no impact to the associated samples.

If the CCVs are biased low, reanalyze any samples impacted since the last

passing CCV. 6010B/200.7 - Contract Required Detection Limit Sample (CRDL)

The CRDL must be analyzed at the beginning of each run for every analyte of interest. The CRDL is at or below the

RL.

± 40% (or specified by the client) . The system must be stopped. Perform any

necessary maintenance and recalibrate accordingly.

6010C – Low Level Initial/Continuing Calibration Verification (LLICV/LLCCV)

The LLICV must be analyzed following the ICV at a

concentration at or below the RL. Additionally, a LLCCV (may be the same solution as the LLICV) must be analyzed at a frequency of once at the end of each analytical batch, preferably every 10 samples

following the CCV to minimize sample re-runs.

± 30% . The system must be stopped. Perform any

necessary maintenance and recalibrate accordingly.

Initial Calibration Blank (ICB)

An ICB must be analyzed immediately following ICV

All elements of interest must be evaluated to the method detection

limit. Depending on the data

. If an analyte of interest is greater than the RL, the

sample concentration must


for each element of interest. quality objective of the associated

projects, a blank with detections less than the RL may be considered acceptable

be greater than 10 times the blank concentration or the

element cannot be reported. If associated projects are evaluated to the method detection limits per data

quality objects, the detections must be

evaluated for data impact and the system evaluated for necessary corrective actions.

Continuing Calibration Blank (CCB)

A CCB must be analyzed, for each element of interest after

every CCV within the analytical run and after the

final CCV.

All elements of interest must be evaluated to the method detection

limit. Depending on the data quality objective of the associated projects, a blank with detections

less than the RL may be considered acceptable.

If an analyte of interest is greater than the RL, the

sample concentration must be greater than 10 times the blank concentration or the

element cannot be reported. If associated projects are evaluated to the method detection limits per data

quality objects, the detections must be

evaluated for data impact and the system evaluated for necessary corrective actions.

Interelement Correction Standard A (ICSA)

A solution containing high concentrations of Al, Ca Fe and Mg is analyzed at the

beginning of each sample run sequence

Acceptance criteria for the spiked interferent elements are ± 20%

and ± 2X the RL for target analytes.

If the ICSA fails criteria, stop analysis. Review the

standard preparation, remake accordingly.

Perform any necessary maintenance and recalibrate

prior to sample analysis.

Additional corrective actions may be required for client specific QAPP and Technical Specifications

Interelement Correction Standard AB (ICSAB)

A solution containing high concentrations of Al, Ca, Fe

and Mg and low to mid-range concentrations of the target

analytes is analyzed following the ICSA

This is required by certain clients. It is not a method requirement and need be analyzed only for clients specifying this in the QAPP

The acceptance criteria are ± 20%.

If the ICSAB fails criteria, stop analysis. Review the

standard preparation, remake accordingly.

Perform any necessary maintenance and recalibrate

prior to sample analysis.

Additional corrective actions may be required for client specific QAPP and Technical Specifications

12. Procedure

12.1. Instrument Set up and Operation

12.1.1. Perform the daily maintenance if needed (change pump tubing, fill rinse solution container, drain waste container, etc.) and record in the daily maintenance log.

12.1.2. Start the ICP and let it warm up.


12.1.2.1. Check the gas supply.

12.1.2.2. Confirm the water circulator/chiller is on.

12.1.2.3. Turn on the computer.

12.1.2.4. Double click on the Optima (WinLab32) program icon. Open the workspace that has the method to run: it will open as well.

12.1.2.5. Click on the plasma icon.

12.1.2.6. Click on the startup/shutdown button.

12.1.2.7. The software will go through several steps until the argon is ignited. Check to be sure the gas flow and pump speed are correct. If not, make changes and click on Apply

12.1.2.8. Close the window.

12.1.3. Create an auto sampler file and pour samples into the corresponding location in the auto sampler tray.

12.1.3.1. Open sample information table by clicking on the button for Sample Info.

12.1.3.2. Click on New/File.

12.1.3.3. Enter in the batch ID, the name of the analyst and standard log numbers. Go down to the table and type in the samples to be analyzed.

12.1.3.4. Click on File Save As and type Date for the data file (which is usually the same as the batch ID).

12.1.3.5. Click on Setup and click on Open to choose which results data set to use. Choose or type in the data set, click OK.

12.1.3.6. Click on Analyze tab. Click on rebuilt list or reset sequence buttons to put the sample information into the analyze window.

12.1.3.7. Print the Sample Info page to get the run log.

12.1.4. Pour the standards and start the calibration of the instrument.

12.1.5. Monitor all initial QC checks. If initial QC fails, make instrument modifications and recalibrate. If checks pass criteria, continue with sample analysis.

12.1.6. During the sample analysis or after the analysis is completed, transfer valid data into LIMS system.

12.1.7. In LIMS system enter any dilutions and any required footnotes. Print validation lists and complete checklist. Turn data in for validation.

12.1.8. ICP Routine Maintenance:

12.1.8.1. Change pump tubing if there is visible wear or flat spots.

12.1.8.2. Change filters as needed.

12.1.8.3. Clean optic window as needed.

12.1.8.4. Empty the waste container as needed.

12.1.8.5. Replace the torch as needed.

12.1.8.6. Clean injector as needed.

12.2. Sample Analysis

12.2.1. Load samples and batch QC into designated autosampler locations making sure the correct spot is used.

12.2.2. Start analytical procedure.

12.2.3. Monitor results and standard recoveries for problems.

12.2.4. At the end of the analytical run, perform the manual shut down.

12.2.4.1. If the analysis extends past working hours, set the instrument up for auto shutdown.

12.3. Daily File


12.3.1. Gather daily printouts.

12.3.2. Print out instrument raw data.

12.3.3. Include calibration summaries and runlogs.

12.3.4. Update and include necessary standard prep logs.

12.3.5. Label the daily file folder with date and instrument information.

13. Quality Control

13.1. Table 13.1 – Quality Control

QC Sample Components Frequency Acceptance Criteria Corrective Action Method Blank (MB)

DI water for liquid samples Resin beads for solid samples

Prepared and analyzed with each group of samples digested. For 6010C - Carried through the appropriate steps of the analytical process. These steps may include, but are not limited to, prefiltering, digestion, dilution, filtering and analysis.

< absolute value of the reporting limit (RL)

For 6010C - If the method blank does not contain target analytes at a level that interferes with project-specific DQOs, then the method blank would be considered acceptable.

If the concentration in the MB is greater than the RL, samples associated with that MB must be re-prepared, unless the samples are non-detect or greater than 10X the blank contamination. When reporting data with a hit in the MB, all samples affected will be footnoted with the appropriate flag to document contamination in the blank.


DI water for liquids and resin beads for solids, spiked with analytes of interest at same level as MS/MSD

Prepared and analyzed for every batch of 20 or less samples digested

80-120% for 6010B and 6010C

85-115% for 200.7

If the percent recovery for the LCS falls outside the control limits of 80-120% for 6010B and 6010C or 85-115% for 200.7, the analyses should be terminated, the problem corrected, and the samples associated with that LCS re-analyzed. If reanalysis of the samples fail, the samples affected by the failing LCS elements need to be re-digested and re-analyzed. EXCEPTION: if LCS fails high and samples are ND the data may be reported with appropriate qualification.


The spike is added to a well-mixed aliquot of a selected sample before the digestion (i.e., prior to the addition of other reagents).

One MS/MSD per batch. If >10 samples for 200.7, an additional MS is required. Clients may have requirements that create a higher frequency of MS/MSD samples.

75-125% for 6010B and 6010C

70-130% for 200.7

% RPD: 20% for

6010B/C; 20% for 200.7

If the percent recovery for the MS and MSD fall outside the control limits, the results are flagged that they are outside acceptance criteria along with the parent sample. If the RPD exceeds the acceptance criteria, the MSD sample and associated parent sample need to be flagged. For Minnesota Admin Contract clients – all MS/MSD failures require reanalysis of the MS/MSD and the original sample. If it is still out of control, investigate and document the


cause in the associated narrative as well as qualifying appropriately.


Spike is added to the native QC sample at the same concentration as the MS but at the instrument.

Required if reporting by 6010C and MS/MSD fail outside 75-125% and if the PDS also fails then a 5x dilution is made of the PDS.

75-125% for 6010B and 80-120% for 6010C

If PDS fails data is qualified

Internal Standard

The same concentration should be used for standards and samples throughout the entire analytical run.

Introduced automatically with every sample.

70-130% of its true concentration

If the recovery is outside the criteria, sample is reanalyzed at a 5X dilution.

13.2. If matrix interference is suspected, a serial dilution may be performed. One serial dilution test may be performed per batch of twenty samples per client contractual requirements. An analysis of a 1:5 dilution should agree within ± 10% of the original result. Additional dilutions may be required.

13.3. When reviewing total and dissolved metals, an RPD of ≤ 20% is considered to be within experimental error.

14. Data Analysis and Calculations

14.1. The percent recovery of the spike is calculated from the following equation:

14.2. The relative percent difference between the MS/MSD can be calculated as follows:

RPD = │(S-D) │ X (100) (S+D)/2

15. Data Assessment and Acceptance Criteria for Quality Control Measures

15.1. See tables in section 11 and 13.

16. Corrective Actions for Out-of-Control Data

16.1. See tables in section 11 and 13.

% Recovery = (SSR-SR) X 100 ST

Where: SSR = Spike sample result, ug/L or mg/kg dry SR = Sample result, ug/L or mg/kg dry ST = Spike target, ug/L or mg/kg dry

Where: RPD = Relative Percent Difference S = Original Spiked Sample Value, ug/L or mg/kg dry D = Second Spiked Sample Value, ug/L or mg/kg dry


17. Contingencies for Handling Out-of-Control or Unacceptable Data

17.1. If not specifically listed in the tables in section 11 or 13, the contingencies are as follows. If there is no additional sample volume to perform re-analyses, all data will be reported as final with applicable qualifiers. If necessary, an official case narrative will be prepared by the Quality Manager or Project Manager.

18. Method Performance

18.1. All applicable personnel must read and understand this SOP with documentation of SOP review maintained in their training files.

18.2. Method Detection Limit (MDL) Study: An MDL study must be conducted annually (per the method) per S-MN-Q-269 – Determination of Limit of Detection and Limit of Quantitation (or equivalent replacement) for each matrix per instrument.

18.3. Instrument Detection Limit (IDL) Study: An IDL study must be conducted quarterly per S-MN-Q-269 – Determination of Limit of Detection and Limit of Quantitation (or equivalent replacement).

18.4. Demonstration of Capability (DOC): Every analyst who performs this method must first document acceptable accuracy and precision by passing a demonstration of capability study (DOC) per S-ALL-Q-020 - Training Procedures (or equivalent replacement).

18.5. Periodic performance evaluation (PE) samples are analyzed to demonstrate continuing competence per SOP S-MN-Q-258 – Proficiency Testing Program (or equivalent replacement). Results are stored in the QA office.

19. Method Modifications

19.1. Not applicable for this SOP.

20. Instrument/Equipment Maintenance

20.1. All maintenance activities are listed daily in maintenance logs that are assigned to each separate instrument.

21. Troubleshooting

21.1. Not applicable for this SOP.

22. Safety

22.1. Standards and Reagents: The toxicity and carcinogenicity of standards and reagents used in this method have not been fully defined. Each chemical compound should be treated as a potential health hazard. Reduce exposure by the use of gloves, lab coats and safety glasses. Material Safety Data Sheets (MSDSs) are on file in the laboratory and available to all personnel. Standard solutions should be prepared in a hood whenever possible.

22.2. Samples: Take precautions when handling samples. Samples should always be treated as potentially hazardous “unknowns”. The use of personal protective equipment (gloves, lab coats and safety glasses) is required when handling samples. In the event a sample container must be opened, it is recommended to perform this in a hood whenever possible.

23. Waste Management

23.1. Procedures for handling waste generated during this analysis are addressed in S-MN-S-003 - Waste Handling and Management (or equivalent replacement).


23.2. In order to minimize the amount of waste generated during this procedure, analyst should prepare

reagents in an amount which may be used in a reasonable amount of time (e.g., before a reagent expires).

24. Pollution Prevention

24.1. The company wide Chemical Hygiene and Safety Manual contains information on pollution prevention.

25. References

25.1. Pace Quality Assurance Manual- most current version.

25.2. National Environmental Laboratory Accreditation Conference (NELAC), Chapter 5, “Quality Systems”- most current version.

25.3. The NELAC Institute (TNI); Volume 1, Module 2, “Quality Systems”- most current version.

25.4. Test Methods for Evaluating Water and Solid Waste, SW-846 3rd Edition, Final Update III, Method 6010B.

25.5. Test Methods for Evaluating Water and Solid Waste, SW-846, Method 6010C Update IV, Feb. 2007.

25.6. Perkin Elmer Hardware Guide 1997.

25.7. Perkin Software Guide 2000.

25.8. Method 200.7 Revision 4.4, Determination of Metals and Trace Elements in Water and Wastes by Inductively Coupled Plasma-atomic Emission Spectrometry

25.9. Test Methods for Evaluating Solid Waste Physical/Chemical Methods, SW-846, Third Edition. Method 3050B

26. Tables, Diagrams, Flowcharts, and Validation Data

26.1. Attachment I - Target Analyte List and Reporting Limits (PRL)

26.2. Attachment II - Trace-ICP Working Calibration Standard

26.3. Attachment III - Trace-ICP Calibration Verification Standard

26.4. Attachment IV - ICSA

26.5. Attachment V - Trace CRDL #2

26.6. Attachment VI - Sample Run Sequence

26.7. Attachment VII – ICP Standards Prep Log 8632

27. Revisions

Document Number Reason for Change Date

S-MN-I-313-rev.24

Implemented new corp SOP format 18.3 – added 26.1-26.6 – changed “table” to “attachment” Added – attachment VII 01Aug2013

S-MN-I-313-rev.25

1.1/2.2 – added ‘AES’ to ICP 2.2 – edited Table 7.1 – updated sample type Table 9.1/10.1/11.1/13.1 – updated Added and changed method criteria (RPD) to 20% Added PDS criteria and frequency Removed DoD reference from section 25 30Apr2014


ATTACHMENT I – Target Analyte List and Reporting Limits (PRL)

Element Wavelength 1(nm) Water PRL (ug/L) Soil PRL (mg/kg) Aluminum 396 200 10 Antimony 217 20 1.0 Arsenic 193 20 1.0 Barium 233 10 0.50 Beryllium 313 5.0 0.25 Boron 249 150 7.5 Cadmium 228 3.0 0.15 Calcium 317 500 25 Chromium 267 10 0.50 Cobalt 228 10 0.50 Copper 327 10 0.50 Iron 238 50 2.5 Lead 220 10 1.0 Magnesium 279 500 25 Manganese 257 5.0 0.25 Molybdenum 202 15 0.75 Nickel 231 20 1.0 Potassium 766 2500 125 Selenium 196 20 0.75 Silver 328 10 0.50 Sodium 589 1000 50 Thallium 190 20 1.0 Tin 189 75 3.75 Titanium 334 25 1.25 Vanadium 290 15 0.75 Zinc 206 20 1.0 Hardness N/A 3300 134

1The wavelengths listed are recommended because of their sensitivity and overall acceptance. Other wavelengths may be substituted when using a sequential instrument if they can provide the needed sensitivity and are treated with the same corrective techniques for spectral interference.


ATTACHMENT II – Trace-ICP Working Calibration Standard

Element Stock Conc.

(mg/L) Aliquot

(mL)

Final Volume

(mL)

Cal STD Final Conc. (mg/L)

Ag 100 1.0 50 2 Al 2,000 0.5 50 20 As 200 1.0 50 4 Ba 200 1.0 50 4 Be 200 1.0 50 4 Ca 2000 0.5 50 20 Cd 200 1.0 50 4 Co 200 1.0 50 4 Cr 200 1.0 50 4 Cu 200 1.0 50 4 Fe 2000 0.5 50 20 K 2000 0.5 50 20

Mg 2000 0.5 50 20 Mn 200 1.0 50 4 Na 2000 0.5 50 20 Ni 200 1.0 50 4 Pb 200 1.0 50 4 Sb 200 1.0 50 4 Se 200 1.0 50 4 Tl 200 1.0 50 4 V 200 1.0 50 4 Zn 200 1.0 50 4 Mo 200 1.0 50 4 B 200 1.0 50 4

Sn 200 1.0 50 4 Ti 200 1.0 50 4


ATTACHMENT III – Trace-ICP Calibration Verification Standard

Element Stock Conc.

(mg/L) Aliquot in

(mL)

Final Volume

(mL)

Final Conc. (mg/L)

Ag 50 1.0 50 1 Al 1000 0.5 50 10 As 100 1.0 50 2 Ba 100 1.0 50 2 Be 100 1.0 50 2 Ca 1000 0.5 50 10 Cd 100 1.0 50 2 Co 100 1.0 50 2 Cr 100 1.0 50 2 Cu 100 1.0 50 2 Fe 1000 0.5 50 10 K 1000 0.5 50 10

Mg 1000 0.5 50 10 Mn 100 1.0 50 2 Na 1000 0.5 50 10

Ni 100 1.0 50 2 Pb 100 1.0 50 2 Sb 100 1.0 50 2 Se 100 1.0 50 2 Tl 100 1.0 50 2 V 100 1.0 50 2 Zn 100 1.0 50 2 Mo 100 1.0 50 2 B 100 1.0 50 2

Sn 100 1.0 50 2 Ti 100 1.0 50 2


ATTACHMENT IV – ICSA

Element Stock Conc.

(mg/L) Aliquot in

(mL)

Final Volume

(mL)

Final Conc. (mg/L)

Al 10000 2.5 1000 25 Ca 10000 50 1000 500 Fe 10000 7.5 1000 75 Mg 10000 15 1000 150


ATTACHMENT V – Trace CRDL2

Element Stock Conc.

(mg/L) Aliquot in

(mL)

Final Volume

(mL) Final Conc.

(mg/L)

Ag 5 1.0 1000 0.005

Al 100 1.0 1000 0.100 As 5 1.0 1000 0.005 Ba 1.5 1.0 1000 0.0015 Be 5 1.0 1000 0.005 Ca 250 1.0 1000 0.250 Cd 0.5 1.0 1000 0.0005 Co 10 1.0 1000 0.010 Cr 10 1.0 1000 0.010 Cu 5 1.0 1000 0.005 Fe 50 1.0 1000 0.050 K 250 1.0 1000 0.250

Mg 250 1.0 1000 0.250 Mn 5 1.0 1000 0.005 Na 1000 1.0 1000 1.0

Ni 20 1.0 1000 0.020 Pb 3 1.0 1000 0.003 Sb 5 1.0 1000 0.005 Se 5 1.0 1000 0.005 Tl 10 1.0 1000 0.010 V 15 1.0 1000 0.015 Zn 20 1.0 1000 0.020 Mo 15 1.0 1000 0.015 B 75 1.0 1000 0.075

Sn 35 1.0 1000 0.035 Ti 10 1.0 1000 0.010

The CRDL standard is prepared by diluting the CRDL2 standard by a factor of 2.


ATTACHMENT VI – Sample Run Sequence

1. Calibration Blank 2. Calibration Standard 3. ICV 4. LLICV (6010C) 5. ICB 6. CRDL (6010B and 200.7) 8. CRDL2 (6010B and 200.7) 9. ICSA 10. ICSAB 11. CCV 12. LLCCV (6010C) 13. CCB 14. SAMPLE 1 15. SAMPLE 2 16. SAMPLE 3 17. SAMPLE 4 18. SAMPLE 5 19. SAMPLE 6 20. SAMPLE 7 21. SAMPLE 8 22. SAMPLE 9 23. SAMPLE 10 24. CCV 25. CCB 26. CRDL (project specific) 27. CRDL2 (project specific) 28. ICSA (project specific) 34. ICSAB (project specific) 35. CCV 36. CCB


ATTACHMENT VII - ICP Standards Prep Log 8632

Pace Analytical Services, Inc. 1700 Elm Street, Suite 200

Minneapolis, MN 55414

Phone: 612.607.1700 Fax: 612.607.6444

STANDARD OPERATING PROCEDURE ALKALINITY, TITRIMETRIC (AUTOMATED TITRATION TECHNIQUE)

Reference Methods: SM 2320B

Local SOP Number: S-MN-I-365 Rev.16 Effective Date: Date of Final Signature

Supersedes: S-MN-I-365 Rev.15

APPROVALS

PERIODIC REVIEW







S-MN-I-365 Rev.16

TABLE OF CONTENTS

SECTION PAGE

1. PURPOSE/IDENTIFICATION OF METHOD ................................................................................................. 3

2. SUMMARY OF METHOD .............................................................................................................................. 3

3. SCOPE AND APPLICATION .......................................................................................................................... 3

4. APPLICABLE MATRICES .............................................................................................................................. 3

5. LIMITS OF DETECTION AND QUANTITATION ........................................................................................ 3

6. INTERFERENCES ........................................................................................................................................... 3

7. SAMPLE COLLECTION, PRESERVATION, SHIPMENT AND STORAGE ............................................... 3

8. DEFINITIONS .................................................................................................................................................. 3

9. EQUIPMENT AND SUPPLIES (INCLUDING COMPUTER HARDWARE AND SOFTWARE) ............... 4

10. REAGENTS AND STANDARDS .................................................................................................................... 4

11. CALIBRATION AND STANDARDIZATION ................................................................................................ 5

12. PROCEDURE ................................................................................................................................................... 6

13. QUALITY CONTROL ...................................................................................................................................... 6

14. DATA ANALYSIS AND CALCULATIONS .................................................................................................. 8

15. DATA ASSESSMENT AND ACCEPTANCE CRITERIA FOR QUALITY CONTROL MEASURES ........ 9

16. CORRECTIVE ACTIONS FOR OUT-OF-CONTROL DATA ....................................................................... 9

17. CONTINGENCIES FOR HANDLING OUT-OF-CONTROL OR UNACCEPTABLE DATA ...................... 9

18. METHOD PERFORMANCE ............................................................................................................................ 9

19. METHOD MODIFICATIONS .......................................................................................................................... 9

20. INSTRUMENT/EQUIPMENT MAINTENANCE ........................................................................................... 9

21. TROUBLESHOOTING .................................................................................................................................... 9

22. SAFETY ............................................................................................................................................................ 9

23. WASTE MANAGEMENT .............................................................................................................................. 10

24. POLLUTION PREVENTION ......................................................................................................................... 10

25. REFERENCES ................................................................................................................................................ 10

26. TABLES, DIAGRAMS, FLOWCHARTS, AND VALIDATION DATA ..................................................... 10

27. REVISIONS .................................................................................................................................................... 10

Pace Analytical Services, Inc. Alkalinity, Titrimetric Date: Upon Final Signature S-MN-I-365 Rev.16 Page 3 of 13

1. PURPOSE/IDENTIFICATION OF METHOD

1.1. The purpose of this SOP is to determine the alkalinity, i.e. the acid-neutralizing capacity of potable and surface waters, domestic and industrial wastewaters, and saline waters as delineated in Standard Methods 2320B. Alkalinity may be reported as total alkalinity or individually as bicarbonate, carbonate, or hydroxide.

2. SUMMARY OF METHOD

2.1. The sample is titrated to an electrometrically determined endpoint of pH 8.3 then to pH 4.5 in succession with an acid reagent.

3. SCOPE AND APPLICATION

3.1. Personnel: The policies and procedure contained in this SOP are applicable to all personnel involved in the analytical method or non-analytical process.

3.2. Parameters: This method is applicable to waters or wastes with alkalinity in ranges from 5 mg/L to approximately 1,000 mg/L.

4. APPLICABLE MATRICES

4.1. This SOP is applicable to water and wastewater.

5. LIMITS OF DETECTION AND QUANTITATION

5.1. The reporting limit is 5 mg/L using a 25 mL sample volume.

6. INTERFERENCES

6.1. Soaps, oily matter, suspended solids, or precipitates may coat the glass electrode and cause a sluggish response. Allow additional time between titrant additions to let the electrode come to equilibrium or clean the electrodes occasionally. Do not filter, dilute, concentrate, or alter the sample.

7. SAMPLE COLLECTION, PRESERVATION, SHIPMENT AND STORAGE

7.1. Sample Collection Table 1

Sample Type Collection per Sample Preservation Storage Hold Time

Aqueous

Collect samples in glass or polyethylene bottles.

For analysis use the Pace General (GN)

bottle (or equivalent)

Not required Above freezing

≤6°C Max hold time is

14 days

8. DEFINITIONS



9. EQUIPMENT AND SUPPLIES (INCLUDING COMPUTER HARDWARE AND SOFTWARE)

9.1. Equipment and Supplies

Supply Description Vendor/ Item # pH Meter General laboratory equipment Scientific Instruments IQ 180 GLP

Steel Electrode General laboratory equipment Fisher part # 13-620-285, or equivalent

Miscellaneous Glassware Various class A volumetric flasks and pipettes Class A 50 mL burette Non-class A beakers, 150 mL to 250 mL Watch glass

Fisher Scientific or equivalent

10 L Nalgene Bottle with Dispenser

For storing and delivering titer (see 10.2.1.) Fisher part # 02-963-2A

Magnetic Stir Plate and Magnetic Stir Bars

General laboratory equipment Fisher Scientific or equivalent

778 Autotitrator system with 888 Titrando Dosing unit (10WET6)

Includes mechanical burette, pH electrode, 1 L amber glass container for titer, Tiamo software

Metrohm

814 Autotitrator system with 905 Titrando Dosing unit (10WT63)

Includes mechanical burette, pH electrode, 1 L amber glass container for titer, Tiamo software

Metrohm

Hot plate General laboratory equipment Fisher Scientific or equivalent replacement

Analytical Balance Capable of reading to 0.0001 g Sartorius RC 210P or equivalent

Laboratory Information System (LIMS)

Laboratory Information System (LIMS) – data reporting software

Horizon, see master software list for current version

10. REAGENTS AND STANDARDS

10.1. Reagents and Standards

Reagent/Standard Concentration/ Description Requirements/ Vendor/ Item # De-ionized (DI) Water N/A Verify daily that pH and specific

conductivity are within acceptable limits and record in the electronic prep log.

Hydrochloric Acid (HCl) Concentrated. Store at room temperature. Expires per manufacturer’s specifications.

Fisher part #

Sodium Carbonate (Na2CO3), Anhydrous

Powder. Store at room temperature. Expires per manufacturer’s specifications.

Fisher part # S263-500

Sodium Carbonate (Na2CO3) Solution

0.05N. For use in standardizing titer. Purchase premade. Store at room temperature. Expires per manufacturer’s specifications.

Fisher part # 7185-32

pH 4.00 ± 0.01 Buffer Used for calibration of the pH electrode. Store at room temperature. Expires as

SCP Science part # 250-204-503 or equivalent


specified by manufacturer.

pH 7.00 ± 0.01 Buffer Used for calibration of the pH electrode. Store at room temperature. Expires as specified by manufacturer.


pH 10.00 ± 0.01 Buffer Used for calibration of the pH electrode. Store at room temperature. Expires as specified by manufacturer.


pH 5.00 ± 0.01 Buffer Used to verify calibration of the pH electrode before sample analysis. Store at room temperature. Expires as specified by manufacturer.

Fisher part # SB102-1 or equivalent

10.2. 1.0N HCl Stock Solution. Add 83 mL of concentrated HCl to a 1000 mL volumetric flask containing 800 mL DI water. Dilute to mark, mix thoroughly, cool in fume hood and transfer to 1 L amber glass container. Expires in 12 months.

10.2.1. 0.02N HCl Solution (Titer). Add 40 mL of 1.0N stock to 2000 mL volumetric flask containing approximately 1500 mL DI water. Dilute to mark, mix thoroughly, cool in fume hood and transfer to a 10 L Nalgene plastic dispenser. Expires in three months. Standardize this solution per section 11.2.

10.3. Stock LCS/ICV/CCV Standard: 10,000 mg CaCO3/L as Na2CO3. Dry ~200 g of anhydrous Na2CO3 at 180ºC for at least four hours. Dissolve 10.6 g of Na2CO3 in a 1000 mL volumetric flask containing about 900 mL of DI water. Dilute to the mark and mix thoroughly. Transfer to a plastic bottle, cap tightly and store at room temperature. Expires in six months.

11. CALIBRATION AND STANDARDIZATION

11.1. Calibration

11.1.1. Before beginning analysis, the pH probe used with the autotitrator must be calibrated daily to three points: 4.00, 7.00 and 10.00. The acceptance criteria for the slope is 96-106% per manufacturer guidelines. Print this information from the database and include with the respective batch paperwork.

11.1.2. Immediately after calibration a pH calibration check must be performed using the pH 5.00 buffer. The acceptance criteria for this check is ± 0.10 pH units. If outside the acceptance criteria, the pH probe must be recalibrated and the pH 5.00 buffer check must be reanalyzed. Print this information from the database and include with the respective batch paperwork.

11.2. Standardization

11.2.1. 0.02N HCl solution must be standardized prior to any analysis.

11.2.1.1. In a beaker, add 15 mL 0.05 N NaCO3 solution and approximately 22 mL DI water.

11.2.1.2. Fill a burette with the 0.02N HCl solution to be standardized.

11.2.1.3. Titrate potentiometrically to a pH of about 5.0.

11.2.1.4. Lift out the electrode and rinse into the beaker.

11.2.1.5. Boil contents of the beaker for 3-5 minutes under a watch glass, cool to room temperature. Rinse watch glass into the beaker.

11.2.1.6. Finish titrating to a pH of 4.5, and calculate the normality using the formula below:

Normality of 0.02N HCl, N = A x B C

Where A = Normality of NaCO3 B = mL of NaCO3 solution used for titration


C = mL HCl used

11.2.1.7. Record in the Normality of Titer in calibration program

12. PROCEDURE

12.1. Batch Samples

12.1.1. Batches include up to 20 samples, a method blank (MB), laboratory control spike (LCS), laboratory control spike duplicate (LCSD) and a matrix spike/matrix spike duplicate for every 10 samples (MS/MSD).

12.1.2. See Attachment II for an example of a sample sequence.


12.2.1. Measure the sample with a 50 mL class A graduated cylinder and transfer it to a 50-mL sample vessel. The recommended sample volume is 25 mL, less may be used when required.

12.2.2. Add a magnetic stir bar to each sample vessel. Mixing of the sample is controlled by the automated process.

12.2.3. Fill the 1L titer container with the standardized 0.02 N HCl.

12.2.4. The pH of the sample is measured. The values are recorded into the instrument’s database.

12.2.4.1. If the initial pH is greater than 8.3, titrate the sample to pH 8.3 and record the volume of the titrant, then continue titration to pH 4.5 and record the volume of the titrant.

12.2.4.2. If the initial pH is less than 8.3 but greater than 4.5, titrate the sample to pH 4.5 and record the volume of the titrant.

12.2.4.3. If the pH is less than or equal to 4.5, alkalinity is not present.

12.2.5. If the total alkalinity of the sample is less than 20 mg/L, it must be re-analyzed using the instrument’s low level method. The low level method uses the titrant to reduce the sample to a pH of 4.5 without measuring the volume. It then titrates to a pH of 4.2, records the volume and uses it for the total alkalinity concentration.

12.2.5.1. Titrate all method blanks, initial calibration blanks and continuing calibration blanks using the low level method.

12.3. Exporting Data

12.3.1. Select samples from the database to be exported. Send the results to the folder “Alkalinity Data Field”, found on the desktop.

12.3.2. After the files are sent to the desktop folder, rename file: AlkBatch#20010 MM/DD/YY.xls

12.3.3. Transfer the data to its respective folder (10WET6 or 10WT63) in J:\Share\LAB\Wet Chem\

12.3.4. Upload to LIMSLINK. Send to 10WET6 or 10WT63 data file.

12.4. Calculations

12.4.1. Refer to section 14.

13. QUALITY CONTROL

13.1. Quality Control Table 1

QC Sample Components Frequency Acceptance Criteria Corrective Action

pH Calibration Check

pH 5.0 Buffer Immediately after calibration of the pH probe

±0.10 pH units If the acceptance criterion is not met, terminate analysis, correct the problem, recalibrate and attempt a new pH calibration check


Initial Calibration Verification (ICV) / Continuing Calibration Verification (CCV) / Laboratory Control Spike (LCS) / Laboratory Control Spike Duplicate (LCSD)

Prepare by pipetting 0.1 mL of the 10,000mg/L stock standard into 25 mL of DI water. The true value is 40 mg/L

An ICV must be conducted immediately after pH calibration check (pH 5.0 Buffer) A CCV standard must be analyzed and reported every ten samples and at the end of the analytical run to ensure calibration accuracy An LCS and LCSD must each be analyzed once per batch

90-110% of the true value 20% RPD for LCS/LCSD

If acceptance criteria are not met for the ICV, LCS or LCSD, a single reanalysis of the respective failing QC is allowed. If the reanalysis is outside the acceptance criteria, the analysis must be terminated, the problem corrected, the instrument recalibrated, and the calibration reverified. If the deviation of the CCV is greater than ±10%, the analysis must be stopped and the problem corrected. All samples analyzed since the last compliant CCV must be reanalyzed

Method Blank (MB) /Initial Calibration Blank (ICB) and Continuing Calibration Blank (CCB)

DI water A calibration blank must be analyzed immediately after every ICV and CCV A method blank must be analyzed once per batch

The ICB and CCB's must be less than the reporting limit unless otherwise specified by the client or QAPP

If acceptance criterion is not met for the ICB/CCB/MB, a single reanalysis of the respective failing QC is allowed. If the reanalysis is outside the acceptance criteria, the analysis must be terminated, the problem corrected, the instrument recalibrated and the calibration reverified. A failing ICB/CCB/MB may be accepted if the affected sample results are non-detect or at least 10 times greater than the failing result. Batch data must be qualified accordingly.

Matrix Spike (MS) and Matrix Spike Duplicate (MSD)

The spike is added to the sample by pipetting 0.1 mL of the 10000 ppm stock standard solution directly into the sample. The value of spike added to a 25 mL sample in this manner is 40 mg/L. The spike sample analysis is designed to provide information about the effect of the sample matrix on the measurement

The spikes are performed at a minimum frequency of 10%. Samples identified as field blanks cannot be used for spike sample analysis

The recovery must be within 80-120% of the true value 20% RPD for the MS/MSD

If acceptance criteria are not met for the MS/MSD, batch data may be qualified as long as the LCS/LCSD are within their respective acceptance criteria For Minnesota Admin Contract clients – all MS/MSD failures require reanalysis of the MS/MSD and the original sample. If it is still out of control, investigate and document the cause in the associated narrative as well as qualifying appropriately.


procedures.

14. DATA ANALYSIS AND CALCULATIONS

14.1. Phenolphthalein alkalinity (pH 8.3)

mg CaCo3/L = (A x N x 50000) ÷ V Where A = mL standard acid titrant to pH 8.3 N = Normality of standard acid titrant V = Volume of sample analyzed

14.2. Total alkalinity (pH 4.5)

mg CaCO3/L = A x N x 50000 V Where A = mL standard acid titrant to pH 4.5 N = Normality of standard acid titrant V = Volume of sample analyzed

14.3. Bicarbonate, carbonate, and hydroxide alkalinity values may also be calculated using the data obtained from the titration and the following table.

Hydroxide Carbonate Bicarbonate Alkalinity Alkalinity Concentration as CaCO3 as CaCO3 as CaCO3

P=0 0 0 T P<.5 T 0 2P T-2P P=.5 T 0 2P 0 P>.5 T 2P-T 2(T-P) 0

P=T T 0 0 P =Phenolphthalein alkalinity T =Total alkalinity

14.4. Spike Sample Analysis (MS) Recovery is calculated as follows:

% Recovery = (SSR - SR) x 100 SA

Where SSR = Spike sample result, mg/L SR = Sample result, mg/L* SA = Spike added, mg/L

*If the sample concentration is less than the MDL, use SR = 0 for the purpose of calculating spike recovery.

14.5. Duplicate Spike Sample Analysis (MSD) or Duplicate Sample relative percent difference (RPD) is calculated as:

RPD = (S - D)(100) [S + D)/2]

Where S = Spike sample value, mg/L D = Duplicate spike sample value, mg/L


15. DATA ASSESSMENT AND ACCEPTANCE CRITERIA FOR QUALITY CONTROL MEASURES

15.1. See table in section 13.

16. CORRECTIVE ACTIONS FOR OUT-OF-CONTROL DATA


17. CONTINGENCIES FOR HANDLING OUT-OF-CONTROL OR UNACCEPTABLE DATA


18. METHOD PERFORMANCE

18.1. There are several requirements that must be met to insure that this procedure generates accurate and reliable data. A general outline of requirements has been summarized below. Further specifications may be found in the Laboratory Quality Manual and specific Standard Operating Procedures.

18.1.1. The analyst must read and understand this procedure with written documentation maintained in his/her training file, which is maintained in the Quality Assurance Office.

18.1.2. An initial demonstration of capability (IDC) must be performed per SOP S-ALL-Q-020 (or equivalent replacement). A record of the IDC will be maintained in his/her file with written authorization from the Laboratory Manager and Quality Manager.

18.1.3. An annual minimum detection limit (MDL) study, following S-MN-Q-269 (or equivalent replacement), will be completed for this method and whenever there is a major change in personnel or equipment. Results of these studies are maintained in the Quality Assurance department.

18.1.4. Periodic performance evaluation (PE) samples are analyzed to demonstrate continuing competence per SOP S-MN-Q-258 (or equivalent replacement).

19. METHOD MODIFICATIONS

19.1. The lab utilizes a sample volume of 25 mL instead of 100 to 200 mL as described in the method for the potentiometric titration of low alkalinity (SM 2320B section 4d).

20. INSTRUMENT/EQUIPMENT MAINTENANCE

20.1. Please refer to the instrument manual provided by Metrohm for maintenance procedures performed by the lab.


21. TROUBLESHOOTING

21.1. Not applicable to this SOP.

22. SAFETY

22.1. 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 and exposure should be as low as reasonably achievable. Cautions are included for known extremely hazardous materials.

22.2. Each laboratory is responsible for maintaining a current awareness file of OSHA regulations regarding the safe handling of the chemicals specified in this method.


22.3. A reference file of MSDS is maintained by the lab and available to all personnel to review at any time

needed.

22.4. The toxicity or condition of samples analyzed by this method is unknown. Therefore, always wear appropriate personal protective equipment to control exposure to hazards.

23. WASTE MANAGEMENT

23.1. The quantity of chemicals purchased is based on expected usage during its shelf life and disposal cost of unused material. Actual reagent preparation volumes reflect anticipated usage and reagent stability.

23.2. The Environmental Protection Agency (USEPA) requires that laboratory waste management practice be conducted consistent with all applicable rules and regulations. Excess reagents, samples and method process wastes are characterized and disposed of in an acceptable manner. For further information on waste management consult S-MN-S-003 – Waste Handling and the Chemical Hygiene Plan (or equivalent replacement).

24. POLLUTION PREVENTION


25. REFERENCES

25.1. Standard Methods for the Examination of Water and Wastewater, Online Edition, Method 2320B, 1997.




26. TABLES, DIAGRAMS, FLOWCHARTS, AND VALIDATION DATA

26.1. Attachment I – Alkalinity Bench Sheet (example)

26.2. Attachment II – Alkalinity Sample Sequence (example)

27. REVISIONS


S-MN-I-365 Rev.14

Reformatted to new SOP layout according to SOT-ALL-Q-001 3.2 – added “to approximately” 9.1 – added unit # 9.2 – added 9.15 – removed flashdrive and added software 10.2 – changed plastic to amber glass 11 – updated entire calibration section 12 – moved standardization section to calibration section 12.3.4.3 – added “or equal to” Table 13 acceptance criteria for ICB/CCB – changed “MDL” to “reporting limit” and added “unless otherwise specified by the client or QAPP

07Jan2013


S-MN-I-365 Rev.15

Removed DoD reference from section 25 Attachment I – updated 9.1-9.15.3 reformatted to table 9.1 10.1—added reagents and standards table 10.1 – 10.3- updated 11.2-section updated

06Feb2014

S-MN-I-365 Rev.16 12.2.5 – added 19.1 – added modification Attachment II - updated

28Mar2014


ATTACHMENT I – Alkalinity Spreadsheet (example)


ATTACHMENT II – Alkalinity Sample Sequence (example)


www.pacelabs.com

Phone: 612-607-1700 Fax: 612-607-6444

STANDARD OPERATING PROCEDURE

METALS ANALYSIS BY ICP/MS Reference Methods: EPA Methods 6020/6020A/200.8


Supersedes: S-MN-I-492-Rev.22

PERIODIC REVIEW






This is COPY# 6 Distributed on 20Jan2015 by SDP and is CONTROLLED or X

UNCONTROLLED

S-MN-I-492-rev.22

TABLE OF CONTENTS

SECTION PAGE 1. Purpose/Identification of Method ............................................................................................ 3

2. Summary of Method .................................................................................................................. 3

3. Scope and Application ............................................................................................................... 3

4. Applicable Matrices ................................................................................................................... 4

5. Limits of Detection and Quantitation ...................................................................................... 4

6. Interferences ............................................................................................................................... 4

7. Sample Collection, Preservation, Shipment and Storage ....................................................... 6

8. Definitions ................................................................................................................................... 6

9. Equipment and Supplies (Including Computer Hardware and Software) .......................... 6

10. Reagents and Standards .......................................................................................................... 7

11. Calibration and Standardization ............................................................................................ 8

12. Procedure ................................................................................................................................ 12

13. Quality Control ...................................................................................................................... 13

14. Data Analysis and Calculations ............................................................................................ 15

15. Data Assessment and Acceptance Criteria for Quality Control Measures ...................... 16

16. Corrective Actions for Out-of-Control Data ....................................................................... 16

17. Contingencies for Handling Out-of-Control or Unacceptable Data ................................. 16

18. Method Performance ............................................................................................................. 16

19. Method Modifications ........................................................................................................... 16

20. Instrument/Equipment Maintenance ................................................................................... 17

21. Troubleshooting ..................................................................................................................... 18

22. Safety ....................................................................................................................................... 18

23. Waste Management ............................................................................................................... 18

24. Pollution Prevention .............................................................................................................. 18

25. References ............................................................................................................................... 18

26. Tables, Diagrams, Flowcharts, and Validation Data .......................................................... 19

27. Revisions ................................................................................................................................. 19

ICP-MS Method 6020/6020A/200.8 Pace Analytical Services, Inc. Effective Date: Upon Final Signature S-MN-I-492-Rev.22 Page: 3 of 25


1.1. This Standard Operating Procedure provides a detailed description based on EPA Methods 200.8, 6020 and 6020A for analysis determining dissolved and total recoverable metals by Inductively Coupled Plasma – Mass Spectrometry (ICP-MS) in environmental samples.


2.1. An aliquot of a well-mixed, homogeneous sample is accurately measured for sample processing. For total recoverable analysis of solids and liquids or dissolved liquid analysis requiring digestion, analytes are first solubilized by gently refluxing with nitric and hydrochloric acids. After cooling, the sample is brought to volume, mixed and allowed to settle overnight prior to analysis. For the determination of dissolved analytes in a filtered aqueous sample by 200.8, or for the “direct analysis” total recoverable determination of analytes in drinking water by 200.8 where sample turbidity is < 1 NTU, the sample is made ready for analysis by the appropriate addition of nitric acid, and then mixed and allowed to set for the required time prior to analysis.

2.2. The method describes the determination of trace elements in aqueous solutions by ICP-MS. Sample solutions are introduced by pneumatic nebulization into a plasma, in which desolvation, atomization and ionization occurs. Ions are extracted from the plasma through a differentially pumped vacuum interface and separated on the basis of their mass-to-charge ratio by a quadrupole mass spectrometer. The ions transmitted through the quadrupole are detected by an electron multiplier. Ion intensities at each mass are recorded and compared to those obtained from external calibration standards to generate concentration values for the samples. Results are corrected for instrument drift and matrix effects using internal standards. Additional corrections are applied as necessary to correct for isobaric and poly atomic elemental interferences (Section 6).


3.1. Personnel: The policies and procedures contained in this SOP are applicable to all personnel involved in the analytical method.

3.2. Parameters: This SOP applies to the determination of dissolved and total recoverable elements by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) in environmental samples.

3.3. This SOP is applicable to the determination of the following elements, at a minimum:

Analyte Registry Number (CAS #) Aluminum (Al) 7429-90-5 Antimony (Sb) 7440-36-0 Arsenic (As) 7440-38-2 Barium (Ba) 7440-39-3 Beryllium (Be) 7440-41-7 Bismuth (Bi) 7440-69-9 Boron (B) 7440-42-8 Cadmium (Cd) 7440-43-9 Calcium (Ca) 7740-70-2 Cesium (Cs) 7440-46-2 Cerium (Ce) 7440-45-1 Chromium (Cr) 7440-47-3 Cobalt (Co) 7440-48-4 Copper (Cu) 7440-50-8 Iron (Fe) 7439-86-6 Iridium (Ir) 7439-88-5 Lanthanum (La) 7439-91-1


Lead (Pb) 7439-92-1 Lithium (Li) 7439-93-2 Magnesium (Mg) 7439-95-4 Manganese (Mn) 7439-96-5 Mercury (Hg) 7439-97-6 Molybdenum (Mo) 7439-98-7 Neodymium (Nd) 7440-00-8 Nickel (Ni) 7440-02-0 Palladium (Pd) 7440-05-3 Platinum (Pt) 7440-06-4 Potassium (K) 7440-70-2 Rhenium (Re) 7440-15-5 Rhodium (Rh) 7440-16-6 Rubidium (Rb) 7440-17-7 Selenium (Se) 7782-49-2 Silicon (Si) 7740-21-3 Silver (Ag) 7440-22-4 Sodium (Na) 7740-23-5 Strontium (Sr) 7440-24-6 Thallium (Tl) 7440-28-0 Tin (Sn) 7440-31-5 Titanium (Ti) 7440-32-6 Vanadium (V) 7440-62-2 Zinc (Zn) 7440-66-6


4.1. This SOP is applicable to ground, surface, drinking, and storm runoff water samples; industrial, domestic waste waters and solids.

4.2. Dissolved elements are determined after suitable filtration and acid preservation. In order to reduce potential interferences, dissolved solids should not exceed 0.2 % (w/v).

4.3. Where this method is approved for the determination of metal and metalloid contaminants in drinking water, samples are analyzed directly by pneumatic nebulization without acid digestion if the samples have been properly acid-preserved and have turbidity of < 1 NTU at the time of analysis, this total recoverable determination procedure is referred to as “direct analysis”. Direct Analysis is only applicable to samples being analyzed by 200.8.

4.4. For the determination of total recoverable analytes in aqueous samples containing particulate and suspended solids a digestion step is required prior to analysis.


5.1. The reporting limit (LOQ) for all analytes ranges from 0.08 to 53.5 ug/L for waters and 0.08 to 50 mg/Kg for soils depending on the element for this method. All current method detection limits (MDLs) and LOQs are listed in the LIMS and are available by request from the Quality Manager.

6. Interferences

6.1. Isobaric Elemental Interferences – Isobaric elemental interferences result when isotopes of different elements have the same nominal mass-to-charge ratio and cannot be resolved with the instrument’s spectrometer. One way to solve this problem is to measure a different isotope for which there is no interference. Alternatively, one can monitor another isotope of the element and subtract an appropriate amount from the element being analyzed, using known isotope ratio information. Corrections for most of the common elemental interferences are programmed into the software.


6.1.1. All analytes listed in section 2.1 have at least one isotope free of isobaric elemental

interference. Of the analytical isotopes recommended for use with this method (Table III), only molybdenum-98 (ruthenium) and selenium-82 (krypton) have isobaric elemental interferences. If alternative analytical isotopes having higher natural abundance are selected in order to achieve greater sensitivity, an isobaric interference may occur. All data obtained under such conditions must be corrected by measuring the signal from another isotope of the interfering element and subtracting the appropriate signal ratio from the isotope of interest. A record of this correction process should be included with the report of the data. Such corrections will only be as accurate as the accuracy of the isotope ratio used in the elemental equation for data calculations. Relevant isotope ratios should be established prior to the application of any corrections.

6.2. Abundance Sensitivity Interference – Abundance sensitivity interference refers to the degree of peak overlap that can occur between adjacent peaks. Interference can occur when the shoulder of a large peak significantly overlaps the peak of a neighboring minor peak, thereby contributing to its intensity. The potential for these interferences should be recognized and the spectrometer resolution adjusted to minimize them.

6.3. Isobaric Polyatomic Interference – Isobaric polyatomic interferences result when ions containing more than one atom have the same nominal mass-to-charge ratio as an analyte of interest and cannot be resolved by the instrument’s spectrometer. Examples include ArCl (mass 75) which interferes with As, ClO+ (mass 51) which interferes with V and must be corrected by measuring ClO+ at mass 53. These interferences are highly dependent on the matrix of the samples and day-to-day plasma conditions, so correction factors must be determined on the day of analysis. When possible, one should choose an interference-free isotope to measure.

6.4. Physical Interferences – Physical interferences result from the physical processes associated with the transport of sample to the plasma, sample behavior within the plasma, and transmission through the interface region between the plasma and the mass spectrometer. Viscosity and surface tension differences can affect results, as can deposits on the sampler and skimmer cones caused by large quantities of dissolved solids in the sample. The interferences can be compensated for by the use of internal standards that approximate the analytical behavior of the elements being determined. Additionally, it is recommended that dissolved solids in samples be kept below 0.2% (w/v).

6.5. Memory Interference – Memory interferences are related to sample transport and result when there is carryover from one sample to the next. Sample carryover can result from sample disposition on the sample and the skimmer cones and from incomplete rinsing of the sample solution from the plasma torch and the spray chamber between samples. These memory effects are dependent upon both the analyte being measured and sample matrix and can be minimized through the use of suitable rinse times.

6.5.1. The rinse times necessary for a particular analyte should be estimated prior to analysis. This may be achieved by aspirating a standard containing the analyte at a concentration ten times the LDR for the normal sample analysis period, followed by analysis of the rinse blank at designated intervals. The length of time required to reduce the analyte signal to less than ten times the method detection limit should be noted. The minimum rinse time between samples should be set to this time. Memory interferences may also be assessed within an analytical run by using three or more replicate integrations for data acquisition. If the integrated signal values drop consecutively, the analyst should check for the possibility of a memory effect. If the analyte concentration in the previous sample is high enough to suspect analyte carryover, the sample should be re-analyzed after a long rinse period.

6.6. Silver is only slightly soluble in the presence of chloride unless there is a sufficient chloride concentration to form the soluble chloride complex. Therefore, low recoveries of silver may occur in samples, fortified sample matrices and even fortified blanks if determined as a dissolved analyte or by “direct analysis” where the sample has not been processed using the total recoverable mixed acid digestion. For this reason samples are digested prior to the determination of silver. The total


recoverable sample digestion procedure is suitable for the determination of silver in aqueous samples containing concentrations up to 0.1 mg/L. For the analysis of wastewater samples containing higher concentrations of silver, succeeding smaller volumes of well mixed sample aliquots must be prepared until the analysis solution contains < 0.1 mg/L silver.

6.7. The total recoverable sample digestion procedure given in this method will solubilize and hold in solution only minimal concentrations of barium in the presence of free sulfate. For the analysis of barium in samples having varying and unknown concentrations of sulfate, analysis should be completed as soon as possible after sample preparation.


7.1. Table 7.1 Collection, Preservation and Storage.

Sample type Collection per sample Preservation Storage Hold time Aqueous Plastic or glass, 250 mL

minimum. Acidified with nitric acid to pH<2; if received unpreserved at 1.5 mL nitric fore each liter received. Mix and confirm that the pH has been adjusted to <2 and allow the samples to sit for 24 hours prior to analysis.

<6°C if shared with mercury analysis; otherwise ambient if preserved properly with nitric acid

Must be prepped and analyzed within 180 days of collection for all other metals than mercury.

Solid 8 oz glass jar None <6°C, but above freezing

Must be prepped and analyzed within 180 days of collection.

8. Definitions



9.1. Table 9.1 Equipment and Supplies.

Supply Description Vendor/ Item # / Description ICPMS (Inductively Coupled Plasma Mass Spectrometer)

Cetac ASX-530 Autosampler, Niagra valve system and PC3 spray chamber chiller/valve system. Toshiba 1600 EP recirculating chiller or equivalent. Toshiba UPS system

Thermo Fisher Scientific XSeries 2 ICP-MS Agilent 7700 series ICPMS

Argon gas High purity grade, 99.99% Praxair or equivalent replacement Collision Gas High purity 7%H/93% He mix

Ultra high purity He, Ultra high purity H2

Praxair (Oxygen Services) or equivalent replacement

Autosampler tubes 15 mL metals free autosampler tubes Mold Pro, MP100 or equivalent replacement

Rough pump oil CMP-19 Fisher Scientific or equivalent replacement

Peristaltic pump tubing Various sizes Fisher Scientific or equivalent replacement

Analytical Balance With the capability to measure to 0.1 mg Sartorius BP 110S, A&D EK-610i, A&D FX1200, or Sartoriius LC612S-00MS or equivalent replacement

Mechanical pipettors Capable of delivering volumes ranging from 10 to 5000 μL, and associated metal –free disposable pipet tips

Eppendorf, Fisher brand or equivalent replacement


Glassware Class A volumetric flasks, graduated cylinders,

funnels (glass and/or metal-free plastic Fisher Scientific or equivalent replacement

Digestion cups 50 mL disposable digestion cups Environmental Express SC475or equivalent replacement

Narrow mouth storage bottles

FEP (fluorinated ethylene propylene) with screw top closure, 135 mL to 1 L capacity

C&G Containers or equivalent replacement

Data Reporting Software

Horizon (also referenced Epic Pro)

Data Uploading Software

Pace internal software used to transfer data from the instrument to the LIMS

Limslink

Instrument software PlasmaLab ICPMS software Thermo Fisher


10.1. Table 10.1 Reagents and Standards.

Reagent/Standard Concentration/ Description Requirements/ Vendor/ Item # Hydrochloric acid (HCl) Trace metals grade or better Fisher Scientific, A-508-P212 or

equivalent replacement

Nitric Acid (HNO3) Trace metals grade or better Fisher Scientific, A-509-P212 or equivalent replacement

Deionized water (DI) Reagent grade (DI) water – (18 MOhm resistivity)

Barnstead Epure System or equivalent replacement

2% (v/v) Nitric Acid/1% (v/v) Hydrochloric Acid Solution

Used for instrument blanks, standards and dilutions. Prepared in 1 L increments utilizing a volumetric flask and transferring into a C&G narrow mouth storage bottle. This is measured by mixing 20 mL of HNO3 trace metals grade acid and 10 mL of HCl trace metals grade acid and DI H2O, and bringing to volume of 1 L.

n/a

Calibration Stock Standard solutions

Custom blend of elements. See Attachment II for the standard preparation information

Spex Certiprep, XFSPA-221-250, XFSPA-656-250, XFSPA-220-250 or equivalent replacement

Initial Calibration Verification (ICV) Stock Standard solutions

Custom blend from of elements from a different source than the Calibration Stock Standard Solutions. See Attachment II for standard preparation information

Inorganic Ventures, XFSMN-26-250A, XFSMN-27-250A, XFSMN-28-250A; Peak Performance, Hg: 4400-1000331 or equivalent replacement

Internal Standard Stock Solution

Can be a purchased multi-element blend or single element standards to be mixed prior to use.

Peak Performance, In: S4400-1000241, Sc: S4400-100048, Y: S4400-1000671, Tb: S4400-1000571;Inorganic Ventures, Ge: CGGe1-1, Spex, Th: PL TH2-2y

Tuning Stock Solution Purchased multi-element standard from a qualified vendor

Claritas PPT, CL-JUNG-1

Rinse Blank 2-5% (v/v) Nitric Acid solution for rinsing between runs. Prepared in 1G increments utilizing Nalgene bottles. This is measured by mixing 76 mL of HNO3 trace metals grade acid and 38 mL of HCl trace metals grade and DI H2O, and bringing to volume of 1 G.

n/a


10.2. Working Standard Dilutions and Concentrations

Standard Standard(s)

Used

Standard(s) Amount

(mL) Diluent Solvent

Volume (mL)

Final Total Volume

(mL) Final

Concentration Standard 1

Refer to Table 10.1, See

Calibration Stock Standard

Solutions

0.250

2% Nitric/1% HCl acid solution

9.75 10 5/62.5 Standard 2 0.500 9.5 10 10/125 Standard 3 1.000 9 10 20/250 Standard 4 0.1 9.9 10 200/2500 Standard 4 0.1 9.9 10 200/2500 Standard 4 0.1 9.9 10 200 Standard 5 0.05 9.95 10 500 Standard 5 0.05 9.95 10 250/500/2500 Standard 5 0.25 9.75 10 25000

CRDL Inorganic Ventures, PACE-28

0.1 9.9 10 varied

CRDL2 Inorganic Ventures, PACE-28

0.2 9.8 10 varied

ICS-A Inorganic

Ventures 6020 ISC-OA

0.25 9.75 10 25000

ICS-AB Refer to Table

10.1 0.25 9.65 10 100/1250/26250

ICV/CCV

Inorganic Ventures, PACE-5, PACE-4B

0.2 49.8 50 80/1000

ICV/CCV

Inorganic Ventures, PACE-5, PACE-4B

0.2 49.8 50 80/1000

Hg-Intermediate Refer to 10.1

See Calibration Stock Standard

Solutions

1.000 24.0 25 40 Standard 6 0.05 9.95 10 0.2 Standard 7 0.25 9.75 10 1.00 Standard 8 0.25 4.75 5 2.00 Standard 9 0.5 4.5 5 4.00

ICV/CCV/Hg* Inorganic Venture,

CGHG1-1 0.05 24.95 25 2


11.1. Table 11.1 Calibration and Standardization.

Calibration Metric Parameter / Frequency Criteria Comments Tune Daily prior to any

calibration EPA performance report - print and file all reports, note failures and corrective actions taken. Adjust spectrometer resolution to produce a peak width of approximately 0.75 amu at 5% peak height. Adjust mass calibration if

The tune criteria must pass before instrument is calibrated and any samples are analyzed.

Follow manufacturer guidelines for troubleshooting and maintenance for tune failures. Document all maintenance performed and return to compliance.


it has shifted by more than 0.1 amu from unit mass.

Note: The tuning criteria utilized is based on the 200.8 method. The mass criteria for 200.8 (0.75 amu at 5% peak height) is more stringent than the criteria for 6020A (0.9 amu at 10% peak height) therefore applicable for both methods.

Calibration Curve Fit

Linear Regression r ≥ 0.998 Instruments are setup with the following calibration curve fit options; linear regression, linear regression through the blank, and weighted least squares. Analysis is conducted utilizing the calibration curve fit method recommended by the instrument manufacturer. If not met, remake standards and recalibrate and verify before sample analysis.

Second Source Verification Standard (ICV)

Immediately after each initial calibration

% Diff ± 10% of the true value

%RSD between multiple

integrations must be ≤ 5%

Review the standard preparation. Remake the standard accordingly if that is the cause. Re-inject the ICV one more time, if it fails stop all analysis. Perform all necessary instrument maintenance and recalibrate the instrument. Only two injections are allowed back to back, then the system must be recalibrated.

Initial Calibration Blank (ICB)

Immediately after the initial calibration verification

Evaluate the blank to the MDL depending on the data quality objective of the associated samples, a blank with detections less than the RL or have levels at least 1/10th of that in the associated samples to be acceptable. Per client QAPP/Technical Specifications the blanks may require to be evaluated and clean to the MDL or ½ RL. WIDNR and West Virginia require samples to be reported to the MDL. The blanks must be clean to the data

If there is a detection, stop analysis and determine the source of the contamination. Perform any necessary maintenance and recalibrate the instrument accordingly.


quality objectives.

Contract Required Detection Limit Sample (CRDL) or Low Level Initial/Continuing Calibration Verification (LLICV/LLCCV)

6020/200.8 - The CRDL must be analyzed at the beginning of each run for every analyte of interest.

6020A - must be analyzed at the beginning of each run, and once at the end of each analytical batch.

Per client QAPP/Technical Specifications a closing CRDL may be required every 8 hours or close of the sequence of client samples, whichever more frequent.

The CRDL/LLICV/LLCCV is at or below the RL. For 6020/200.8: The acceptance criteria are +/-40% (or specified by the client). For 6020A: The acceptance criteria are +/-30% (or specified by the client).

Evaluate standard preparation, re-prepare and analyze if suspected. Review the CRDL 2 standard for the failing elements.

-If the CRDL2 passes, report only the samples that have detections greater than that concentration.

-If the CRDL or CRDL2 are biased high, only samples that are non-detect below the reporting limit can be reported as there would be no impact from the high bias.

-If the CRDL is biased low, no data can be reported for the target elements failing criteria including J-flagged data. The system must be stopped. Perform any necessary maintenance and recalibrate accordingly.

Interference Check Solutions (ICSA/AB)

ICSA containing high concentrations of C, Cl, Al, Ca, Fe, K, Mg, Mo, Na, P, S and Ti is analyzed at the beginning of each sample run sequence after the CRDL.

ICSAB containing high concentrations of C, Cl, Al, Ca, Fe, K, Mg, Mo, Na, P, S and Ti and mid-range concentrations of the remaining analyzed elements is analyzed at the beginning of each sample run sequence following the ICSA.

6020A requires the ICSA/AB be analyzed every 12 hours thereafter.

Per client QAPP/Technical Specifications a closing sequence ICSA/AB may be required at a frequency of every 8 hours or end of sequence, whichever is more frequent.

ICSA all spiked elements are to be within 20% of the expected true value. The non-spiked elements are to be below the RL. ICSAB all spiked elements are to be within 20% of the expected true value. Client QAPPs/Technical Specifications by provided alternate criteria for non-spiked elements and must be followed accordingly.

If the ICSA or AB fail criteria, stop analysis. Review the standard preparation, remake accordingly. Perform any necessary maintenance and recalibrate prior to sample analysis.

Adjust the equations accordingly or recalibrate as needed to meet specified requirements. Note that monitoring the interference source does not necessarily require monitoring the interference itself, but that a molecular species may be monitored to indicate the presence of the interference

Exception:

If the minerals are high bias and the analytes of interest are not impacted, passing all criteria, the data may be reported.

Continuing Calibration Verification (CCV)

Prior to the analysis of any samples and after every 10 injections thereafter. Samples must

% Diff ± 10% of the true value

%RSD between multiple

If the requirements for continuing calibration are not met, review for preparation error or instrument malfunction. A CCV may be


be bracketed with a closing CCV standard.

integrations must be ≤ 5% repeated, but a second failure requires the system to be recalibrated prior to further analysis.

If the samples bracketed are non-detect and the CCV is biased high, data may be reported as there is no impact from the high bias. If the samples associated are non-detect and the only detections are associated with the batch QC (LCS/MS) but the QC is within limits, the data can be reported. The QC should be flagged indicating that there was bias but that there was no impact to the associated samples.

If the CCVs are biased low, reanalyze any samples impacted since the last passing CCV.

Continuing Calibration Blank (CCB)

Following every CCV injection

Evaluate the blank to the MDL depending on the data quality objective of the associated samples, a blank with detections less than the RL or have levels at least 1/10th of that in the associated samples to be acceptable. Per client QAPP/Technical Specifications the blanks may require to be evaluated and clean to the MDL or ½ RL. WIDNR and West Virginia require samples to be reported to the MDL. The blanks must be clean to the data quality objectives.

If there is detection, stop analysis and determine the source of the contamination. Perform any necessary maintenance and recalibrate the instrument accordingly.

Reanalyze any samples impacted since the last passing CCB.

Internal Standard Response

Monitor the signal intensity for the internal standard masses throughout the analytical run. This information is useful in detecting instrument drift, sensitivity shifts, and inherent internal standard (i.e., a natural constituent in a sample).

For method 6020, the absolute intensity of any one internal standard in the ICB/CCB and ICS (ICSA/AB) standards must not deviate more than 80-120% from its original intensity in the associated calibration blank. The absolute intensity of any one internal standard in the

If deviations greater than these are observed, flush the instrument with the rinse blank and re-analyze the calibration blank and examine the internal standard intensities with the following actions; If the intensities of the internal standards are acceptable, dilute a fresh aliquot of the sample and re-analyze. A 5X dilution or larger factor or multiple dilutions may be


samples and remaining QC must not deviate more than 30-120% from its original intensity in the associated calibration blank. For method 6020A, the intensity of the internal standards must not fall below 70% for any standard or sample. An upper limit of 125% will be applied to the internal standard recoveries for analyses. For Method 200.8 the absolute intensity of any one internal standard in the samples and QC must not deviate more than 60-125% from its original intensity in the associated calibration blank.

required to achieve acceptable results. If the internal standards are still out-of-limits, terminate the analysis and determine the cause of the drift. Routine maintenance of the sampling interface or re-tuning the mass spectrometer may be required. The system must be calibrated and any samples not bordered by acceptable ICV/CCV samples re-analyzed.

12. Procedure

12.1. Perform all initial system set up procedures

12.1.1. Check waste jug. If more than half full, empty it into the acid waste stream.

12.1.2. Check the chiller temperature and water level. Add additional water as needed to return the instrument to specification. The system will not operate if the water is too low.

12.1.3. Check rough pump oil color. It should be amber or light yellow; if it is the color of coffee it should be changed.

12.1.4. Check pressure of collision gas cylinder, change if needed.

12.1.5. Open the torch chamber and visually inspect the cones if the instrument performance is not acceptable. If there are significant deposits, remove both cones and clean or replace them.

12.1.6. Check torch position and fittings. Adjust the position of the torch accordingly, reattach the fittings as necessary.

12.1.7. Check the peristaltic pump tubing. If it has flattened or plugged, replace it.

12.1.8. Turn plasma on by switching the instrument into the operating state. Place the probes in 2% nitric acid solution and allow the instrument to warm up for 20-30 minutes.

12.1.9. Check peristaltic pump flow by monitoring bubble movement in the pump tubing. Adjust tension as needed to achieve a smooth flow.

12.1.10. Perform daily tuning and optimization of the instrument in the following order:

12.1.10.1. Torchbox alignment, if torch chamber was opened.

12.1.10.2. EPA autotune wizard.

12.1.10.3. EPA performance report, print and file all reports. Note failures and corrective actions taken.

12.1.10.4. Detector cross calibration.

12.1.10.5. CCT-KED autotune wizard.

12.1.10.6. CCT-KED performance report, print and file all reports. Note failures and corrective actions taken.

12.1.10.7. CCT autotune wizard.


12.1.10.8. CCT performance report, print and file all reports. Note failures and corrective actions

taken.

12.1.11. See Attachment I for an example of the Daily Operational Checklist Form F-MN-I-212, or equivalent replacement.

12.2. Analysis

12.2.1. General method development steps are outlined in the Training and Operations manuals from Thermo Scientific. Select masses carefully to avoid and/or minimize interferences. Make sure appropriate measures are in place to deal with interferences. Use an internal standard within 50 mass units of the analyte if possible.

12.2.2. Run analytical samples, appropriate batch and quality control samples.

12.2.3. Each sample preparation set will typically include a digestion blank, a laboratory control spike, matrix spike and sample duplicate, as defined in the Glossary Section of the PASI Quality Manual. More quality control samples may be necessary. In particular, it is suggested that the matrix spike be added in a form that tests the digestion efficiency.

12.2.4. CCV/CCB required every 10 samples using the same solution and control limits as the ICV and ICB standard and blank.

12.2.5. Review results of quality control samples for PASS/FAIL criteria.

12.2.6. Review the sample in-solution concentrations. Samples that have concentrations outside the linear range for each element will be diluted until they fall within range.

12.2.7. At the conclusion of the experiment, set the instrument to go into vacuum status. Selecting shut down will turn the vacuum off. Selecting or leaving the instrument at none will leave the plasma on.

12.3. Daily File (in hardcopy format; if electronic assembly is available the same images will be captured in pdf accordingly)

12.3.1. Gather all daily printouts.

12.3.2. Print out instrument raw data.

12.3.3. Include the calibration summaries and runlogs.

12.3.4. Update and include necessary standard preparation logbooks.

12.3.5. Label the daily folder with the date and instrument information.

13. Quality Control

13.1. Table 13.1 Quality Control and Corrective Action.


Reagent water for water samples or Teflon chips/or nonmetal containing solid matrix for soil batches

One per 20 samples

Target analytes must be less than reporting limit. If results are reported to MDL, target analytes in MB should be non-detect. WIDNR and West Virginia require samples to be reported to the MDL. The blanks must be clean to the data quality objectives.

Re-analyze associated samples. Exceptions: If sample ND, report sample without qualification; If sample result >10x MB detects, report sample as not impacted by the blank contamination; If sample result <10x MB detects and sample cannot be reanalyzed, report sample with appropriate qualifier to indicate an estimated value. Client must be alerted and authorize this condition.



DI water spiked with all target compounds or a spiked Teflon chip/or nonmetal containing matrix for soils.

One per 20 samples

6020/6020A: 80-120%

200.8: 85-115%

The analyses should be terminated, the problem corrected, and the samples associated with that LCS re-analyzed. If reanalysis of the samples fail, the samples affected by the failing LCS elements need to be re-digested and re-analyzed. Exceptions: If LCS recovery is > QC limits and these compounds are non-detect in the associated samples, the sample data may be reported with appropriate data qualifiers.

Matrix Spike (MS)

Client sample spiked with all target compounds

One per 20 samples for 6020 and 6020A One per 10 samples for 200.8

6020/6020A : 75-125%

200.8: 70-130%

If LCS and MBs are acceptable, the MS/MSD chromatogram should be reviewed and it may be reported with appropriate footnote indicating matrix interferences. Perform a PDS on any elements that failed to meet criteria. For Minnesota Admin Contract clients – all MS/MSD failures require analysis of the MS/MSD and the original sample. If it is still out of control, investigate and document the cause in the associated narrative as well as qualifying appropriately.

MSD / Duplicate

MS Duplicate OR (alternative) Sample Dup

One for every 20 samples for 6020 and 6020A.

%Diff ≤ 20% Report results with an appropriate footnote.

Serial Dilution

A 5-fold dilution of a digested sample. See section 13.1.1.

One per batch of 20 samples or less

fivefold dilution must agree within ± 10% of the original determination if analyte concentration is >50x MDL

If criteria is not met, original sample and dilution shall be reanalyzed.


An aliquot of the parent sample used for the MS, prepared at the same dilution as the parent sample. Spiked with 20 uL of 20/250 mg/L stock concentration.

One per batch if there is a MS failure.

80-120% If the element fails to meet the recovery criteria, then the dilution test on the PDS must be performed. If the dilution test fails, it is determined to be matrix interference,

Serial Dilution of Post Digestion Spike

The above PDS is diluted 1:5 and treated as a serial dilution

Required by certain client QAPPs. This is not a standard practice

fivefold dilution must agree within ± 10% of the

original determination

If this fails data is qualified


13.1.1. To prepare a 5-fold dilution: take a 1 mL aliquot from the sample and add to 4 mL of 2%

HNO3 / 1% HCl DI water diluents. Note: this is a typical process for 200.8 and 6020W. It can be replicated for the preparation of highly concentrated samples by starting with a diluted “parent” sample and then performing the stepwise dilution process.


14.1. Percent Recovery Equation:

14.2 Relative Percent Difference Calculation

RPD = │(S-D) │ X (100) (S+D)/2

14.3 Concentration Calculation for Soils

(W) x (1- (M/100)) = C

(K) x (D) x (F) = X (C x 1000)

Where: W = original sample weight (g) M = percent moisture K = on column analyte concentration (ug/L) D = digested volume (mL) F = dilution factor C = moisture corrected weight (g)

14.4 Linear Regression Equation y = mx+ b

Where: y = instrument response m = slope of calibration function x = analyte concentration (ug/L) b = blank concentration (ug/L)

14.5 The Weighted Least Squares Regression of each point (wi) is calculated as follows:

% Recovery = (SSR-SR) X 100 ST

Where: SSR = Spike sample result, μg/L or mg/kg dry SR = Sample result, μg/L or mg/kg dry ST = Spike target, μg/L or mg/kg dry

Where: RPD = Relative Percent Difference S = Original Spiked Sample Value, μg/L or mg/kg dry D = Second Spiked Sample Value, μg/L or mg/kg dry


Where: wi = weight of each point Si = standard deviation of each point n = number of point


15.1. See tables in section 11 & 13.

16. Corrective Actions for Out-Of-Control Data

16.1. See tables in section 11 % 13.

17. Contingencies for Handling Out-Of-Control or Unacceptable Data

17.1. If not specifically listed in the tables in section 11 & 13, the contingencies are as follows. If there is no additional sample volume to perform re-analyses, all data will be reported as final with applicable qualifiers. If necessary, an official case narrative will be prepared by the Quality Manager or Project Manager.



18.2. Method Detection Limit (MDL) Study: An MDL study must be conducted annually (per the method) per S-MN-Q-269, Method Detection Limit Studies for each matrix per instrument. For 200.8, a new MDL must be performed with each new analyst begins work as well.

18.3. Demonstration of Capability (DOC): Every analyst who performs this method must first document acceptable accuracy and precision by passing a demonstration of capability study (DOC) per S-ALL-Q-020, Training Procedures.

18.4. Periodic performance evaluation (PE) samples are analyzed to demonstrate continuing competence per SOP S-MN-Q-258, or equivalent replacement. Results are stored in the QA office.

18.5. An Instrument Detection Limit (IDL) Study is required quarterly. This consists of three runs on three consecutive days from the analysis of a reagent blank with seven consecutive measurements per day. The data will be maintained in the metals department.


19.1. The tuning criteria utilized is based on the 200.8 method. The mass criteria for 200.8 (0.75 amu at 5% peak height) is more stringent than the criteria for 6020A (0.9 amu at 10% peak height) therefore applicable for both methods

19.2. Sample digestates are allowed to settle overnight. If undissolved material does not settle out the sample digestate is filtered prior to analysis on the instrument. The laboratory does not centrifuge samples as suggested in the method.

19.3. Aqueous samples with less than 1%-undissolved solids are brought up to a final volume of 100 mL (no preparation step is performed at the instrument).

19.4. LRB results are not subtracted from LFB results for calculation of LFB recoveries. The level of contamination in the LRB should be minimal when compared to the LFB spiking levels.

19.5. Instruments utilize dual detector scanning, analog and pulse counting. The detector cross calibration is used to convert the data acquired using analog detector mode into the equivalent pulse counting


data. During detector cross calibration, a polynomial fit line is applied by comparing masses found on the y-axis against x-axis. External calibration is completed each day by utilizing 100/1250 ug/L solution. Internal instrument calibrations are also obtained by the instrument during pauses in operation, utilizing obtained integrated counts per second across the mass range and creating a separate polynomial fit line.

19.6. Calibration

19.6.1. Linear Regression

19.6.1.1. Utilizing a standard linear regression format (See Equation 14.4). All points of the calibration curve including the blank are plotted as regular fitted points.

19.6.2. Weighted Least Squares Regression

19.6.2.1. Utilizing Weighted Least Squares Regression in Section 14.5. When data with more than one repetition is used to create a calibration curve, weighted regression can be selected. The count error for data collected in this manner is represented as the standard deviation of the counts. Usually the count error for higher concentrations is larger than that for lower concentrations. When weighted regression is selected, lower concentrations are given more weight because it is more desirable that the curve pass through points having lower error than points having higher error.

19.7. Analyte List from Section 1.2

19.7.1. The following elements are not listed in the method 6020A recommended analyte list; bismuth, boron, lithium, molybdenum, palladium, platinum, silica, silicon, strontium, tin, titanium, and uranium-238. The accuracy and precision for the analysis of these analytes have been demonstrated in the matrices of interest, at the concentration of interest, and in the same manner as the elements recommended in the method.

19.7.2. The following elements are not listed in the method 200.8 recommended analyte list: bismuth, boron, calcium, iron, lithium, magnesium, palladium, platinum, potassium, silica, silicon, sodium, strontium, tin, and titanium. The accuracy and precision for the analysis of these analytes have been demonstrated in the matrices of interest, at the concentration of interest, and in the same manner as the elements recommended in the method


20.1. Please refer to the instrument manual for maintenance procedures performed by the lab. 20.2. Routine Maintenance (Document all routine maintenance in the Routine Maintenance Logbook at the

time of performing the maintenance) 20.2.1. Weekly Maintenance.

20.2.1.1. Replace peristaltic pump tubing for sample, internal standard and waste.

20.2.1.2. Clean spray chamber and nebulizer.

20.2.1.3. Clean and/or replace torch (optional or as needed).

20.2.1.4. Check and clean air filters id necessary.

20.2.1.5. Check multiplier voltages.

20.2.2. Monthly Maintenance 20.2.2.1. Check rotary pump oil. 20.2.2.2. Check oil mist filters. 20.2.2.3. Replace sample uptake tubing. 20.2.2.4. Check chiller water level in reservoir 20.2.2.5. Bi-Annual Maintenance 20.2.2.6. Examine lens system and clean, if necessary. 20.2.2.7. Examine penning gauge and clean, if necessary.


20.2.2.8. Change rotary pump oil (perform more frequently based on sample type and load). 20.2.2.9. Annual Maintenance 20.2.2.10. Replace worn o-rings.

21. Troubleshooting


22. Safety




23.1. Procedures for handling waste generated during this analysis are addressed in S-MN-S-003, Waste Handling, or equivalent replacement.

23.2. In order to minimize the amount of waste generated during this procedure, analyst should prepare reagents in an amount which may be used in a reasonable amount of time (e.g., before a reagent expires).



25. References




25.4. U.S. Environmental Protection Agency. Method 200.8, Determination of Trace Elements in Waters and Wastes by Inductively Coupled Plasma – Mass Spectrometer, Revision 5.4, EMMC Version, May 1994.

25.5. Fisons –VG Genesis Users Manual.

25.6. Region 9 Laboratory Standard Operating Procedure 130, Glassware Cleaning Procedures.

25.7. Region 9 Laboratory Standard Operating Procedure 462, Analysis of Total Suspended Solids By EPA Method 160.2.

25.8. U.S. Environmental Protection Agency. SW846 Method 6020, Inductively Coupled Plasma – Mass Spectrometry, Revision 0, 9/94.

25.9. U.S. Environmental Protection Agency. SW846 Method 6020A, Inductively Coupled Plasma – Mass Spectrometry, Revision 1, 92/2007.

25.10. Test Methods for Evaluating Solid Waste Physical/Chemical Methods, SW-846, Third Edition. Method 3020A.


25.11. Test Methods for Evaluating Solid Waste Physical/Chemical Methods, SW-846, Third Edition.

Method 3050B.


26.1. Attachment I – ICPMS Daily Operational Checklist

26.2. Attachment II – IS Reference ICPMS.

26.3. Attachment III - Method 6020/6020A/200.8 Analyte List and PRL

26.4. Table I – Internal Standards and Limitation of Use.

26.5. Table II – Recommended Elemental Equations for Data Calculations.

26.6. Table III – Recommended Analytical Isotopes and Additional Masses.

27. Revisions


S-MN-I-492-rev.21

2.1 – removed HCl for soil only reference 9.1 – removed ESI SC4 DX autosampler, replaced with Niagra valve system; vendor updated 9.1 – collision gas row – added ultra high purity… 10.1 – 10.2 – updated 11.1 – added RSD criteria to ICV/CCV 13.1 – Added Serial Dilution of PDS 19.5 – removed Added PDS criteria in section 13.1 table Attachment I-II updated to current revision Attachment III – standard prep log example removed Attachment IV (now III) – updated Removed DoD reference from section 25

30Apr2014

S-MN-I-492-rev.22

Table 10.2 – Changed Pace-9 to Pace-28 for CRDL/CRDL2; Changed standard amount, solvent volume and final concentration for ICV/CCV 18.2 – added MDL frequency with a new analyst per 200.8 19.7 – added section 1.2 analyte list deviation for 6020A and 200.8 Table 11.1 – added C and P in ICSA/ICSB Attachment I – corrected title

28Oct2014

S-MN-I-492-rev.23 11.1 and 13.1, added state regulation requirements for blanks for WIDNR and West Virginia

20Nov2014


Attachment I – ICPMS Daily Operational Checklist


Attachment II - IS Reference ICPMS


Attachment III: – Method 6020/6020A/200.8 Analyte List and PRL

Analyte CAS# Water

PRL (ug/L) Soil

PRL (mg/kg)

Aluminum 7429‐90‐5 10.0 10.0

Antimony 7440‐36‐0 0.5 0.5

Arsenic 7440‐38‐2 0.5 0.5

Barium 7440‐39‐3 0.3 0.3

Beryllium 7440‐41‐7 0.2 0.2

Bismuth 7440‐69‐9 0.5 0.5

Boron 7440‐42‐8 5.0 5.0

Cadmium 7440‐43‐9 0.08 0.08

Calcium 7740‐70‐2 40.0 40.0

Chromium 7440‐47‐3 0.5 0.5

Cobalt 7440‐48‐4 0.5 0.5

Copper 7440‐50‐8 1.0 1.0

Iron 7439‐86‐6 50.0 50.0

Lead 7439‐92‐1 0.1 0.1

Lithium 7439‐93‐2 0.5 0.5

Magnesium 7439‐95‐4 10.0 10.0

Manganese 7439‐96‐5 0.5 0.5

Molybdenum 7439‐98‐7 0.5 0.5

Nickel 7440‐02‐0 0.5 0.5

Palladium 7440‐05‐3 0.5 ‐

Platinum 7440‐06‐4 0.5 ‐

Potassium 7440‐70‐2 50.0 50.0

Selenium 7782‐49‐2 0.5 0.5

Silica 7631‐86‐9 53.5 53.5

Silicon 7740‐21‐3 50.0 50.0

Silver 7440‐22‐4 0.5 0.5

Sodium 7740‐23‐5 50.0 50.0

Strontium 7440‐24‐6 0.5 0.5

Thallium 7440‐28‐0 0.1 0.1

Tin 7440‐31‐5 0.5 0.5

Titanium 7440‐32‐6 1.0 1.0

Vanadium 7440‐62‐2 1.0 1.0

Zinc 7440‐66‐6 5.0 5.0

Uranium‐238 7440‐61‐1 0.5 0.5

NOTE: Reporting Limits are current at the time of issuing this SOP. For the most current reporting limits, refer to LIMS system.


Table I - Internal Standards and Limitations of Use

Internal Standard Mass Possible Limitation Lithium 6 a Scandium 45 polyatomic ion interference Yttrium 89 a, b Rhodium 103 Indium 115 isobaric interference by Sn Terbium 159 Holmium 165 Lutetium 175 Bismuth 209 a- May be present in environmental samples b- In some instruments Yttrium may form measurable amounts of YO+ (105 amu) and YOH+ (106 amu). If this

is the case, care should be taken in the use of the cadmium elemental correction equation. Internal standards recommended for use with this method are underlined.


Table II - Recommended Elemental Equations for Data Calculations

Element Elemental Equation Note Al (1.000) (27C) Sb (1.000)(123 C) As 1.000(75C)-3.1278(77C)+0.815(82C) 1 Ba 1.000(137C) Be 1.000(9C) Cd 1.000(111C) -1.073 (108C)+0.76398(106C) 2 Cr 1.000(52C) 3 Co 1.000(59C) Cu 1.000(63C) Pb 1.000(206C)+1.000 (207C)+1.000(208C) 4 Mn 1.000(55C) Mo 1.000(98C) -0.146 (99C) 5 Ni 1.000(60C) Se 1.000(82C) 6 Ag 1.000(107C) Tl 1.000(205C) Th 1.000(232C) U 1.000(238C) V 1.000(51C) -3.1081 (53C)+0.353351(52C) 7 Zn 1.000(66C) Bi 1.000(209C) Sc 1.000(45C) Tb 1.000(159C) Y 1.000(89C) Hg 1.000(202C) C Calibration blank subtracted counts at specified mass. 1 Correction equation for As taken from EPA method 6020. Isobaric correction for ArCl. 2 Correction for MoO, Sn. 3 The background for ClOH will normally be small and can be estimated from the reagent blank. 4 Allowance for isobaric variablility of lead isotopes. 5 Isobaric elemental correction for Ru. 6 Some Ar supplies contain Kr as an impurity. Se is corrected for Kr by background subtraction. 7 Correction for chloride interference with adjustment for Cr. ClO 51/53 ratio may be determined from the

reagent blank. Isobaric mass 52 must be from Cr only not ArC+.


Table III - Recommended Analytical Isotopes

Element of Interest Isotope

Aluminium 27 Antimony 121,123 Arsenic 75 Barium 135, 137 Beryllium 9 Cadmium 106, 108, 111, 114 Chromium 52, 53 Cobalt 59 Copper 65 Lead 206,207,208 Manganese 55 Mercury 202 Molybdenum 95, 97, 98 Nickel 62 Selenium 77, 82 Silver 107, 109 Thallium 203, 205 Vanadium 51 Zinc 66, 67, 68 Ruthenium 99 Palladium 105 Tin 118, 120

NOTE: Isotopes recommended for analytical determination are underlined.


www.pacelabs.com Phone: 612-607-1700 Fax: 612-607-6444

STANDARD OPERATING PROCEDURE MEASUREMENT OF SOLIDS IN WATER AND WASTEWATER

Reference Methods: SM 2540-B, -C, and –D and EPA 160.4

Local SOP Number: S-MN-I-528-Rev.12 Effective Date: Date of Final Signature

Supersedes: S-MN-I-528-Rev.11

PERIODIC REVIEW SIGNATURES BELOW INDICATE NO CHANGES HAVE BEEN MADE SINCE PREVIOUS APPROVAL.





This is COPY# 12 Distributed on 20Jan2015 by SDP and is CONTROLLED or X

UNCONTROLLED

S-MN-I-528-Rev.12

TABLE OF CONTENTS

SECTION PAGE

1. Purpose/Identification Of Method ................................................................................................. 3

2. Summary Of Method ..................................................................................................................... 3

3. Scope And Application ................................................................................................................... 3

4. Applicable Matrices ....................................................................................................................... 3

5. Limits Of Detection And Quantitation ............................................................................................ 3

6. Interferences ................................................................................................................................. 3

7. Sample Collection, Preservation, Shipment And Storage ................................................................ 4

8. Definitions ..................................................................................................................................... 4

9. Equipment And Supplies (Including Computer Hardware And Software) ........................................ 4

10. Reagents And Standards ................................................................................................................ 5

11. Calibration And Standardization .................................................................................................... 5

12. Procedure ...................................................................................................................................... 6

13. Quality Control .............................................................................................................................. 8

14. Data Analysis And Calculations ...................................................................................................... 9

15. Data Assessment And Acceptance Criteria For Quality Control Measures ..................................... 10

16. Corrective Actions For Out‐Of‐Control Data ................................................................................. 10

17. Contingencies For Handling Out‐Of‐Control Or Unacceptable Data .............................................. 10

18. Method Performance .................................................................................................................. 10

19. Method Modifications ................................................................................................................. 11

20. Instrument/Equipment Maintenance ........................................................................................... 11

21. Troubleshooting .......................................................................................................................... 11

22. Safety .......................................................................................................................................... 11

23. Waste Management .................................................................................................................... 11

24. Pollution Prevention .................................................................................................................... 11

25. References ................................................................................................................................... 11

26. Tables, Diagrams, Flowcharts, And Validation Data ...................................................................... 11

27. Revisions ..................................................................................................................................... 12

Measurement of Solids in Water and Wastewater Pace Analytical Services, Inc. Date: Upon Final Signature S-MN-I-528-Rev.12 Page: 3 of 12

1. Purpose/Identification Of Method

1.1. This Standard Operating Procedure (SOP) describes operations used to measure Total Solids (TS), Total Suspended Solids (TSS), Total Dissolved Solids (TDS), and Total Volatile Solids (TVS) in water samples, and TS and TVS on solids, based on Standard Methods 2540-B, 2540-C, and 2540-D and EPA 160.4.


2.1. Total Solids (TS) – A well-mixed sample is evaporated to dryness and the residue solids are measured gravimetrically.

2.2. Total Suspended Solids (TSS) – A well-mixed sample is filtered. The residue collected by the filter is dried and measured gravimetrically.

2.3. Total Dissolved Solids (TDS) – A well-mixed sample is filtered. The filtrate passing through the filter is evaporated to dryness and the residual solids is measured gravimetrically.

2.4. Total Volatile Solids (TVS, TVSS, or TVDS) – Residue obtained from the determination of TS, TSS, or TDS is ignited at 550 ºC in a muffle furnace. The loss of weight on ignition is reported as mg/L volatile solid (TVS if the result was obtained from ashing a TS sample, TVSS if the result was from a TSS sample, or TVDS if the result was obtain from a TDS sample).

2.5. Solid matrices are reported as a percentage for TS and TVS.


3.1. Personnel: The policies and procedures contained in this SOP are applicable to all personnel involved in the analytical method.

3.2. Parameters: This SOP applies to matter suspended or dissolved in water or wastewater.


4.1. This SOP is applicable to water samples, including drinking water, groundwater, municipal and industrial wastewater.

5. Limits Of Detection and Quantitation

5.1. The reporting limit (LOQ) for all analytes is 10 mg/L for a default volume of 100 mL. All current limits are listed in the LIMS and are available by request from the Quality Manager.

6. Interferences

6.1. Non-representative materials, e.g., leaves and sticks should be removed from the sample prior to measurement unless it is determined that their inclusion is desired. If floating oil and grease are present, the sample should be dispersed by blending prior to analysis.

6.2. Measurements are subject to negative bias for samples containing significant quantities of ammonium carbonate, volatile organics, or other volatile materials that could be lost during drying.

6.3. The residue of samples for TS and TDS that are highly mineralized, especially containing significant concentrations of calcium, magnesium, chloride, and/or sulfate may be hydroscopic and will require longer drying, desiccation, and rapid weighing.

6.4. Samples for TS and TDS containing high concentrations of bicarbonate will require careful, and possibly prolonged, drying to ensure that all bicarbonate is converted to carbonate.

6.5. The volumes of aliquots for TS and TDS should be selected to limit the total residue to 200 mg to prevent the residue from crusting over and trapping water during drying.

6.6. Samples for TSS with high TDS, such as saline waters, brines, and some wastes, may be subject to positive bias. Care must be taken to properly rinse the filter to minimize the bias.



7.1. Collection, Preservation, Storage and Holding Time Table

Sample type Collection per sample Preservation Storage Hold time Aqueous Samples are collected

in plastic bottles N/A Samples are stored

above freezing but below 6°C

Analyze as soon as possible to minimize microbiological decomposition of organic solids, holding time not to exceed 7 days from collection.

8. Definitions


9. Equipment and Supplies (Including Computer Hardware And Software)

9.1. Table 9.1 Equipment and Supplies Table

Supply Description Vendor/ Item # / Description Analytical Balance Electronic with RS-232 output, capable of

weighing 0.0001g Mettler Toledo, AB135-S

Drying Oven Capable of maintaining temperature at 103-105C for TSS, capable of holding temperature at 178-182C for TDS

VWR 1370F, Precision Scientific

Muffle Furnace Capable of maintaining temperature at 550C for volatile solids

Fisher Scientific, or equivalent

Vacuum Filtration System

Including filter holder, membrane filter funnel, vacuum flask and vacuum pump

Pall

EPIC Horizon (LIMS) Data Reporting Software See master list for current version

LIMSLink Data Transmission Software See master list for current version

Microsoft Excel Spreadsheet software See master list for current version

Dessicator General laboratory equipment Labconco

Indicating Dessicant General laboratory equipment Drierite, 23005

Non-indicating Dessicant General laboratory equipment Drierite, 13005

Ceramic Evaporating Dishes (Crucibles)

For use in TVS Fisher Scientific, or equivalent

Beaker 200 mL capacity, tall form. For use in TDS and TS.

Fisher Scientific part # 02-546B, or equivalent

Glass Fiber Filters Pre-washed and dried. For use in TDS. Environmental Express part # F92447MM

Glass Fiber Filters Pre-washed, dried, pre-weighed and barcoded. For use in TSS.

Environmental Express part # F93447MM

Wash Bottle Nalgene, one piece stem or equivalent Fisher Scientific, or equivalent

Glass Fiber Filter (TVSS) Pre-washed and dried Environmental Express part # F92447VOL

Glass Fiber Filters (Sand Filtrate)

General laboratory equipment Millipore part # AP2504700

Aluminum Dish 70 mL. Low form weighing dish, smooth. Fisher part # 08-732-103



10.1. Table 10.1 - Reagents and Standards Table

Reagent/Standard Concentration/ Description Requirements/ Vendor/ Item # De-Ionized (DI) Water Verify daily that pH and specific

conductivity are within acceptable limits.

CeLite Filter Aid TSS dry standard. Diatomaceous earth. Store at room temperature. Expires per manufacturer’s specifications or five years after opening, whichever is sooner.

Fisher part # C212-500

Sodium Chloride (NaCl) TDS dry standard. Store at room temperature. Expires per manufacturer’s specifications or five years after opening, whichever is sooner.


TS/TSS/TDS Standard Purchased premade. Store at room temperature. Expires per manufacturer’s specifications. TDS = 1000 mg/L, TSS = 100 mg/L, TS = 1100 mg/L

Environmental Express part # NS1QC1-55H

10.2. Table 10.2 - Working Standard Dilutions and Concentrations

Standard Standard(s) Used Standard(s)

Amount Solvent Solvent Volume

Final Total

Volume Final

Concentration TSS Standard CeLite Filter Aid 0.2 g DI Water ~2000 mL 2000 mL 100 mg/L TDS Standard NaCl 2 g DI Water ~2000 mL 2000 mL 1000 mg/L TSS/TDS/TS Combined Standard

CeLite Filter Aid 0.2 g DI Water ~2000 mL 2000 mL

100 mg TSS/L 1000 mg TDS/L 1100 mg TS/L NaCl 2 g

10.2.1. All standards have a six month expiration date. Store at room temperature.


11.1. Daily calibration of the balance is required following SOP S-MN-Q-264 – Support Equipment (or equivalent replacement). Record in associated balance calibration logbook. Calibration limits are found in the balance calibration logbook; if values exceed these limits, recalibrate the balance.

11.2. All balances must be certified by an outside agency on an annual basis with documentation of the calibration maintained in the QA office.

11.3. Establishing Constant Weight

11.3.1. Weigh the vessel (filter pad, beaker or crucible) and dry in an oven for 30 minutes (104 ± 1ºC for TSS filter pads and TS/TVS beakers or crucibles, 180 ± 2ºC for TDS beakers).

11.3.2. Remove from the oven and allow them to cool to room temperature in a desiccator.

11.3.2.1. If done in a room with < 20% humidity, the vessels may be allowed to cool on a benchtop for approximately 5 minutes to allow more rapid cooling.

11.3.3. Weigh the filter pad, beaker or crucible again. If the second weight is within ±0.5 mg of the first, constant weight is established and analysis is complete, otherwise repeat 11.3.1 through 11.3.3 for a third weight and, if necessary, a fourth weight.

11.3.3.1. 4% Rule (only applicable to residue, does not apply to clean vessel weights): If any weight measurement agrees within 4% of a previous weight, it is considered a constant weight and analysis is complete.

11.3.3.2. If the fourth weight is still not within ±0.5 mg, use the fourth weight and qualify the sample data as not having established constant weight.

11.3.3.3. TSS filters may be purchased pre-weighed and may be used immediately. One filter per manufacturer’s lot must be weighed to verify correctness.


11.3.3.4. All weights must be recorded and the date/time and oven temperature must be recorded in the electronic prep log.

12. Procedure

12.1. Total Solids (TS)

12.1.1. Wash beakers (or crucibles if TVS is being performed) with phosphate-free soap and warm tap water. Rinse three times or until free of soap. Rinse three times with DI water and dry at 180±2°C for at least 1 hour.

12.1.2. Assign clean, dry beakers to each sample and record the tare weight to the nearest 0.1 mg using the constant weight procedure described in section 11.3.

12.1.3. Choose a sample volume to yield a residue of at least 25 mg but less than 200 mg. If there is not a reliable indication of solids content, choose 100 mL if the sample appears clean or, as little as 10 mL if the sample appears to have solids.

12.1.4. Shake thoroughly to homogenize the sample and measure the chosen aliquot volume in a graduated cylinder and pour into the respective beaker.

12.1.5. Rinse the graduated cylinder with ~10 mL DI water and pour into the beaker. Repeat this step twice.

12.1.6. Optional: Evaporate the beakers in an oven no higher than 105ºC to complete dryness, preferably overnight.

12.1.7. Place the evaporated beakers in an oven at 104 ± 1ºC for at least 1 hour.

12.1.8. Remove the beakers from the oven and allow them to cool to room temperature in a desiccator.

12.1.8.1. If done in a room with < 20% humidity, the beakers may be allowed to cool on a benchtop for approximately 5 minutes to allow more rapid cooling.

12.1.9. After cooling to room temperature, weigh each beaker to the nearest 0.1 mg.

12.1.10. Repeat steps 12.1.5 through 12.1.8 and establish constant weight as described in section 11.3.

12.1.11. Record all weights, dates and times of oven and desiccator tracking as well as oven temperatures in the electronic prep log (F-MN-I-318 for TS, F-MN-I-375 for beaker preweights).

12.2. Total Suspended Solids (TSS) & Sand Filtrate

12.2.1. Use ProWeigh filter pads (prewashed and preweighed) from Environmental Express. Verify the weight indicated on the weigh pan or record the actual weight if it differs from the vendor indicated weight.

12.2.2. For sand filtrate, TVSS or for TSS when ProWeigh filter pads are not available, identify and wash each filter pad with three 20 mL aliquots of DI water and vacuum to dryness between each aliquot. Establish constant weight for each filter pad as described in section 11.3.

12.2.2.1. Use Millipore part # AP2504700 for sand filtrate.

12.2.2.2. Use Environmental Express part # F92447VOL for TVSS.

12.2.2.3. Use Environmental Express part # F92447MM for TSS when ProWeigh filter pads are not available.

12.2.3. Choose a sample volume to yield a residue of at least 1 mg but less than 200 mg.

12.2.3.1. For TSS low level, filter a 500 mL volume if the sample appears clean.

12.2.3.1.1. Per client request, filter a 1000 mL volume if the sample is drinking water or other very clean surface water.

12.2.3.2. For wastewaters, choose 100 mL if the sample appears clean. When filtering less than 10 mL, dilute the aliquot of sample in at least 10 mL DI water prior to filtering in order to disperse the sample on the filter pad evenly.

12.2.3.3. For sand filtrate, filter a 1000 mL volume.


12.2.4. Place a clean filter pad on the filtration manifold, handling the filter pad with forceps only. Wet the filter with a small volume of DI water to seat it. Discard the rinsates if the sample is also being analyzed for TDS.

12.2.5. Shake the sample thoroughly and measure the chosen aliquot volume using a class A graduated cylinder.

12.2.6. Filter the sample. Rinse the graduated cylinder and wash the filter three times with approximately 10 mL of DI water. Once filtration is complete, maintain the filter vacuum for about three minutes and until filter has come to complete dryness.

12.2.6.1. If the sample is also being analyzed for TDS, retain the filtrate. Transfer the filtrate to an evaporating vessel and complete the analysis for TDS as described in Section 12.3.

12.2.6.2. If total volatile suspended solids (TVSS) are also to be performed, transfer the filter pad to a ceramic evaporating dish and complete the analysis for TVSS as described in Section 12.4.

12.2.7. Remove the filter pad with the forceps and place it back into its respective aluminum pan.

12.2.8. Place the pans with filter pads onto drying racks in oven at 104±1ºC for at least 1 hour.

12.2.9. Remove the samples from the oven and place them in a desiccator to cool for at least 30 minutes.

12.2.10. After cooling to room temperature, weigh each filter pad to the nearest 0.1 mg.


12.2.12. Record all weights, dates and times of oven and desiccator tracking as well as oven temperatures in the electronic prep log (F-MN-I-325 for TSS, F-MN-I-375 for sand filter preweights).

12.3. Total Dissolved Solids (TDS)

12.3.1. Wash beakers (or crucibles if TVDS is being performed) with phosphate-free soap and warm tap water. Rinse three times or until free of soap. Rinse three times with DI water and dry at 180 ± 2°C for at least 1 hour.

12.3.2. Assign clean, dry beakers to each sample and record the tare weight to the nearest 0.1 mg using the constant weight procedure described in section 11.3.

12.3.3. Choose a sample volume to yield a residue of at least 25 mg but less than 200 mg. Choose 100 mL by default but if sample is suspected of having large amounts of TDS, proceed to 12.3.3.1 to prescreen. When filtering less than 10 mL, dilute the aliquot of sample in at least 10 mL DI water prior to filtering in order to evenly disperse the sample on the filter pad.

12.3.3.1. Prescreen samples to determine the general range of TDS using the Analog Total Dissolved Solids Meter.

12.3.3.2. Rinse the cell cup three times with the sample.

12.3.3.3. Fill the cell with the sample to at least ¼” above the upper electrode.

12.3.3.4. Press the black button and read the meter.

12.3.4. Prepare the filter system with a prewashed filter pad. If the sample will also be analyzed for TSS, use a ProWeigh filter pad and handle the filter with forceps only.

12.3.5. Wet the filter with a small volume of DI water to seat it and thoroughly rinse the vacuum flask with DI water. Discard the rinse water.

12.3.6. Shake the sample thoroughly and measure the chosen aliquot volume using a class A graduated cylinder.

12.3.7. Filter the sample. Rinse the graduated cylinder and wash the filter three times with approximately 10 mL of DI water. Once filtration is complete, maintain the filter vacuum for about three minutes.

12.3.8. Transfer the filtrate to its assigned beaker.


12.3.8.1. If the sample is also being analyzed for TSS, transfer the filter pad to its respective pan and complete the analysis for TSS as described in Section 12.2.

12.3.9. Optional: Evaporate the beakers in an oven no higher than 105ºC to complete dryness, preferably overnight.

12.3.10. Place the evaporated beakers in an oven at 180±2ºC for at least 1 hour.

12.3.11. Remove the beakers from the oven and allow them to cool to room temperature in a desiccator.

12.3.11.1. If done in a room with < 20% humidity, the beakers may be allowed to cool on a benchtop for approximately 5 minutes to allow more rapid cooling.



12.3.14. Record all weights, dates and times of oven and desiccator tracking as well as oven temperatures in the electronic prep log (F-MN-I-324 for TDS, F-MN-I-375 for beaker preweights).

12.4. Volatile Solids (TVS, TVDS, or TVSS)

12.4.1. Wash crucibles with phosphate-free soap and warm tap water. Rinse three times or until free of soap. Rinse at least three times with DI water and ignite in a muffle furnace at 550°C for 1 hour.

12.4.2. Assign crucibles to each sample and record the tare weight to the nearest 0.1 mg using the constant weight procedure described in section 11.3.

12.4.3. Obtain the dry residue from a TS, TDS, or TSS determination. Note: The residue for TS and TDS is obtained by drying the sample directly in a prepared crucible through the respective drying process for each analysis. The residue for TSS is obtained by filtering the sample on a pad suitable for volatization (see 12.2.2), dried through the same process for TSS samples and then placed in a clean aluminum dish for TVSS.

12.4.4. Place the crucibles (clean aluminum dishes with TSS filters if TVSS is being analyzed) into the muffle furnace at 550ºC for 30 minutes.

12.4.4.1. Note: 15 to 20 minute ignition times are usually required for a 200 mg residue; however, multiple samples and/or heavier residues may overtax the furnace and therefore necessitate a longer ignition time of 30 minutes.

12.4.5. Remove the crucibles from the furnace and cool for approximately 10 minutes. Place the crucibles in a desiccator to cool to room temperature.



12.4.8. Record all weights, dates and times of oven and desiccator tracking as well as oven temperatures in the electronic prep log (F-MN-I-318 for TVS, F-MN-I-375 for crucible preweights).

13. Quality Control

13.1. Table 13.1 Quality Control Table


100 mL of DI water

Once per batch of up to 20 samples. An MB is not analyzed in TVS or TVDS.

Absolute value must be less than the reporting limit. Per QAPP or client specifications, alternate criteria such as evaluating to ½ RL

Reanalyze all samples in the batch. Exception: Any samples with residues 10x the result of the method blank or non-detect may be accepted.


may apply.

Laboratory Control Sample (LCS) and Laboratory Control Sample Duplicate (LCSD)

50 mL of TSS Standard, TDS Standard or TSS/TDS/TS Combined Standard

Once per batch of up to 20 samples. An LCSD must be substituted in the event of insufficient sample volume for a duplicate sample. An LCS is not analyzed in any volatile solids analyses.

80-120% of the true value

If an LCSD is analyzed, the RPD < 10% For tests undergoing volatizing by EPA 160.4, RPD < 20%

Reanalyze all samples in the batch.

Duplicate Sample

Client-provided sample

Once every 10 samples. RPD ≤ 10% For tests undergoing volatizing by EPA 160.4, RPD < 20%

Reanalyze the parent sample in duplicate to confirm either the parent sample result or duplicate result. Exception: If the results of the sample and duplicate are less than 5x the RL, the data can be reported with the D8 qualifier and no further corrective action unless it is suspected that the data is in error for any other reason. If either the parent sample or the duplicate is below the MDL, RPD is not generated and no further action is necessary If either the parent sample or the duplicate is below the RL but above the MDL, qualify with a D8 flag.

Pad Weight Verification (not reported)

ProWeigh TSS pads

One pad per box of 100 (pre-weighed TSS pads) is weighed and the weight is logged on the certificate that is included in the box with the pad. This documentation is filed with the certificates of analysis for all materials received in the wetchem department.

± 0.0005 g of the weight specified by the manufacturer

If outside the acceptance criteria, attempt verification on a second pad in the lot. If the second is also outside the acceptance criteria, discard the lot.


14.1. See the most current Quality Manual for calculations

14.2. LCS Recovery

LCS Recovery = SSR x 100% SA

Where: SSR = Spike Sample Results SA = Spike Added from spiking mix


14.3. Relative Percent Differences (RPD)

RPDA B

A Bx

2

100

Where:

RPD = Relative Percent Difference A = % Moisture for Sample B = % Moisture for Sample Duplicate

14.4. TS, TSS and TDS

TS, TSS and TDS (mg/L) = (A-B)*1000/V

Where:

A = Weight of residue and vessel (g)

B = Tare weight of vessel (g)

V = Volume of sample aliquot (mL)

14.5. TVS, TVDS and TVSS

TVS, TVDS or TVSS (mg/L) = 100xV

BA

% TVS = (A-B)/(A) *100

Where:

A = Weight of dry sample residue and dish before ignition (mg)

B = Weight of ignited sample residue and dish (mg)

V = Volume of sample aliquot (mL)



16. Corrective Actions for Out-Of-Control Data


17. Contingencies for Handling Out-Of-Control or Unacceptable Data

17.1. If not specifically listed in the table in section 13, the contingencies are as follows. If there is no additional sample volume to perform re-analyses, all data will be reported as final with applicable qualifiers. If necessary, an official case narrative will be prepared by the Quality Manager or Project Manager.



18.2. Method Detection Limit (MDL) Study: Not applicable to this SOP.

18.3. Demonstration of Capability (DOC): Every analyst who performs this method must first document acceptable accuracy and precision by passing a demonstration of capability study (DOC) S-ALL-Q-020 (or equivalent replacement), Training Procedures.


18.4. Periodic performance evaluation (PE) samples are analyzed periodically to demonstrate continuing competence per SOP S-MN-Q-258 (or equivalent replacement). Results are stored in the Quality office.


19.1. The duplicate criteria exception of reported data outside of 10% is a modification. This is due to the fact that samples close to the reporting limit can be statistically unreliable. The 5x the RL criteria is based on the inorganic guidance provided in National Functional Guidelines.



21. Troubleshooting

21.1. Not applicable.

22. Safety




23.1. Procedures for handling waste generated during this analysis are addressed in S-MN-S-003, Waste Handling and Management, or equivalent replacement.




25. References




25.4. USEPA Methods for Chemical Analysis of Water and Wastes, EPA-600/4-79-020, Method 160.4, Issued 1971.

25.5. Methods 2540-B, 2540-C, and 2540-D, Standard Methods for Examination of Water and Wastewater, 20th Edition (1997).




27. Revisions


S-MN-I-528-rev.10

Removed reference to final blank for TSS – as not a method requirement Added 11.6 Establishing Constant Weight 12.1.3 – 12.1.5 and 12.1.9, 12.2.6.2, 12.3.6, 12.4.4 – rewording for more precise procedure 12.1.8 and 12.4.2 – changed 0.01 g to 0.0001 g Added 12.2.2.1 – 12.2.2.3 Removed 12.1.10-12.1.12, 12.2.12-12.2.14, 12.3.3, 12.3.6.2, 12.3.11-12.3.13 12.1.14, 12.2.16 and 12.3.15 moved to 14.4 as one equation 12.2.4.1-12.2.4.3 and 12.2.11, 12.3.10, 12.4.6 – edited to integrated procedure in section 11.6 12.2.10 – changed 0.01 to 0.0005g Added – 12.3.2 to refer to section 11.6 Added – “When filtering less…filter pad” in 12.3.3 Moved 12.4.8 to 14.5 13.1 table – added exception to MB corrective action; edited corrective action of LCS/LCSD and Dup for more precise procedure; added “an LCS is not analyzed…” Attachment II updated

30Oct2013

S-MN-I-528-rev.11 Removed 11.6.3 Tare weights requirement - Shifted 11.6.3.1 to 11.6.3

Added “For sample and QC residue…” in 11.6.2 22Nov2013

S-MN-I-528-rev.12

Table 9.1/10.1/10.2/13.1 – revised Table 9.1 – added ‘Aluminum dish’ 10.1 – removed and put as 10.2.1 Section 11 – revised to follow guidelines in S-MN-Q-264 Section 12 – revised the whole procedure; added the use of electronic preplog; added aluminum dish 13.2 – removed 14.5 – calculation revised 18.2 – MDL is not applicable to this SOP Removed DoD reference in section 25 25.4 – revised the year published of the reference 25.6 – removed Attachment I and II - removed

15Jul2014


www.pacelabs.com

Phone: 612-607-1700 Fax: 612-607-6444

STANDARD OPERATING PROCEDURE DETERMINATION OF INORGANIC ANIONS BY ION CHROMATOGRAPH

Reference Methods: EPA 300.0/SW-846 Method 9056A


Supersedes: S-MN-I-583-rev.03

APPROVALS

PERIODIC REVIEW







S-MN-I-583-Rev.04

TABLE OF CONTENTS

SECTION PAGE 1. Purpose/Identification of Method ............................................................................................. 3

2. Summary of Method ................................................................................................................... 3

3. Scope and Application ................................................................................................................ 3

4. Applicable Matrices .................................................................................................................... 3

5. Limits of Detection and Quantitation ....................................................................................... 3

6. Interferences ................................................................................................................................ 3

7. Sample Collection, Preservation, Shipment and Storage ........................................................ 4

8. Definitions .................................................................................................................................... 4

9. Equipment and Supplies (Including Computer Hardware and Software) ........................... 4

10. Reagents and Standards ............................................................................................................. 4

11. Calibration and Standardization............................................................................................... 7

12. Procedure ................................................................................................................................... 10

13. Quality Control ......................................................................................................................... 11

14. Data Analysis and Calculations ............................................................................................... 12

15. Data Assessment and Acceptance Criteria for Quality Control Measures ......................... 12

16. Corrective Actions for Out-of-Control Data .......................................................................... 12

17. Contingencies for Handling Out-of-Control or Unacceptable Data .................................... 12

18. Method Performance ................................................................................................................ 12

19. Method Modifications .............................................................................................................. 12

20. Instrument/Equipment Maintenance ...................................................................................... 13

21. Troubleshooting ........................................................................................................................ 13

22. Safety .......................................................................................................................................... 13

23. Waste Management .................................................................................................................. 14

24. Pollution Prevention ................................................................................................................. 14

25. References .................................................................................................................................. 14

26. Tables, Diagrams, Flowcharts, and Validation Data ............................................................. 14

27. Revisions .................................................................................................................................... 14

Inorganic Anions by Ion Chromatography Pace Analytical Services, Inc. Effective Date: Upon Final Signature S-MN-I-583-Rev.04 Page: 3 of 14


1.1. This method is used to determine the concentration of the following inorganic anions by ion chromatography: Fluoride, Chloride, Bromide, Nitrite, Nitrate, and Sulfate by EPA Method 300.0 and SW-846 Method 9056A.


2.1. Approximately 50 μL of sample is injected into an ion chromatograph system. The anions of interest are separated and measured using a system composed of a guard column, analytical column, suppressor device, and conductivity meter. Anions are identified based on their retention times as compared to known standards. Quantitation is accomplished by measuring the peak area comparing it to a calibration curve generated from known standards.


3.1. Personnel: The policies and procedures contained in this SOP are applicable to all personnel involved in the analytical method or non-analytical process.

3.2. Parameters: This SOP applies to Fluoride, Chloride, Bromide, Nitrite, Nitrate, and Sulfate.


4.1. This SOP is applicable to drinking water, surface water, mixed domestic and industrial wastewaters, groundwater, and reagent waters.


5.1. The reporting limit (LOQ) is 0.05 mg/L for Fluoride, 0.08 mg/L for Bromide, 0.10 mg/L for Nitrate and Nitrite, 1.2 mg/L for Chloride and Sulfate. All current MDLs are listed in the LIMS and are available by request from the Quality Manager.

6. Interferences

6.1. Interferences can be caused by substances with retention times that are similar to and overlap those of the anion of interest. Large concentrations of one anion can interfere with the peak resolution of an adjacent anion. Sample dilution can be used to alleviate most interference problems.

6.2. The negative peak that elutes near the fluoride peak can usually be eliminated by the optional addition of the equivalent of 0.1 mL of concentrated eluent to 5 mL of each standard or sample.

6.3. Method interferences may be caused by contaminants in the reagent water, reagents, glassware, and other sample processing apparatus that lead to discrete artifacts or to elevated baselines in ion chromatograms.

6.4. Samples must be filtered prior to injection to prevent damage to instrument columns and flow systems.

6.5. Known co-elution is caused by other small organic anions eluting in the area of fluoride causing interference.

6.6. The acetate anion elutes early during the chromatographic run, plus the retention times of the anions also seem to differ when large amounts of acetate are present. Avoid analysis of leachates (TCLP extracts), as acetic acid is used for pH adjustment.

6.7. Low molecular weight organic acids (formate, acetate, propionate, etc.) are conductive and co-elute with or near fluoride and can bias the fluoride quantitation in some drinking waters and most wastewaters.


6.8. Residual chlorine dioxide present in the sample will result in the formation of additional chlorite. If

chlorine dioxide is suspected (chlorinated drinking water supplies), then purge the sample with nitrogen for 5 minutes.


7.1. Table 7.1 – Sample Collection, Preservation, Shipment and Storage

Sample type Collection per sample Preservation Storage Hold time Aqueous Glass or plastic. A

minimum of 50 mL is required to allow for filtering and duplication.

Unpreserved Above freezing but below 6°C

Must be analyzed within 28 days from collection. If the analysis is to speculate Nitrate and Nitrite, samples must be analyzed within 48 hours of collection.

8. Definitions



9.1. Table 9.1 – Equipment and Supplies

Supply Description Vendor/Item #/Description Ion Chromatograph Metrohm 881 Compact IC Pro,

858 Professional Sample Processor, 800 Dosino for in-line and automatic dilution, A Supp 5 column and Metrohm Suppressor Module (MSM)

Metrohm, or equivalent. See Metrohm Product Catalog for respective part numbers

Sample loop 20 uL Metrohm part #6.1825.210 H2O scrubber Metrohm part # 6.2837.010 CO2 scrubber Metrohm part # 6.2837.000 Peristaltic pump tubing (sampler) Yellow-yellow (1.42 mm I.D.)

Black-black (0.76 mm I.D.) Yellow-yellow: Metrohm part # 6.1826.070 Black-black: Metrohm part # 6.1826.040

Peristaltic pump tubing (MSM) Orange-yellow (0.51 mm I.D.) Metrohm part # 6.1826.060 Ultrafiltration disks 47 mm diameter, 0.2 µm thickness Metrohm part # 6.2714.020 In-line filtration disks Metrohm part # 6.2821.130 Column: Metrosep A Supp 5 – 100/4.0 Metrohm part # 6.1006.510 Sample vials 11 mL plastic tubes Moldpro Inc. part # MP-100 MagIC Net 2.2 software Used to analyze, integrate and

export data from IC Metrohm

Data transmission software LIMSLink See master list for current version Data reporting software Horizon See master list for current version


10.1. Table 10.1 – Reagents and Standards

Reagent/Standard Concentration/Description Requirements/Vendor/Item # E-pure DI water Verify daily that pH and conductivity

are within acceptance limits Sodium Carbonate (Na2CO3)

Anhydrous. Powder. Store at room temperature. Expires per manufacturer’s specifications.


Sodium Bicarbonate Powder. Store at room temperature. Expires per Fisher part # S233-500


(NaHCO3) manufacturer’s specifications. Methanol Store at room temperature. Expires per

manufacturer’s specifications. Fisher part # A454-4

Sulfuric Acid, Optima (H2SO4)

Concentrated. Store at room temperature. Expires per manufacturer’s specifications.

Fisher part # A468-500

Oxalic Acid Dihydrate Store at room temperature. Expires per manufacturer’s specifications.

Fisher part # 423152500

Acetone Store at room temperature. Expires per manufacturer’s specifications.

Fisher part # A929-4

Ascarite Store at room temperature. Expires per manufacturer’s specifications.

Fisher part # AC208091000

Bromide Standard 1000 mg Br/L. Purchase premade. Store at room temperature. Expires per manufacturer’s specifications.

ERA part # 046 Inorganic Ventures part # ICBR1-1

Chloride Standard 1000 mg Cl/L. Purchase premade. Store at room temperature. Expires per manufacturer’s specifications.

ERA part # 988 Inorganic Ventures part # ICCL1-1

Fluoride Standard 1000 mg F/L. Purchase premade. Store at room temperature. Expires per manufacturer’s specifications.

ERA part # 989 Inorganic Ventures part # ICF1-1

Nitrate Standard 1000 mg NO2-N/L. Purchase premade. Store at room temperature. Expires per manufacturer’s specifications.

ERA part # 991 Inorganic Ventures part # ICNNO31-1

Nitrite Standard 1000 mg NO3-N/L. Purchase premade. Store at room temperature. Expires per manufacturer’s specifications.

ERA part # 990 Inorganic Ventures part # ICNNO21-1

Sulfate Standard 1000 mg SO4/L. Purchase premade. Store at room temperature. Expires per manufacturer’s specifications.

ERA part # 995 Inorganic Ventures part # ICSO41-1

A Supp 5 Eluent 20x 64 mM Sodium Carbonate, 20 mM Sodium Bicarbonate. Purchase premade or prepare as outlined in table 10.2. Store at room temperature. Expires per manufacturer’s specifications.

Metrohm part # REAIC1101

Suppressor Rinse Solution

DI water with 0.1 % methanol. Purchase premade or prepare as outlined in table 10.2. Store at room temperature. Expires per manufacturer’s specifications.

Metrohm part # REAIC1150C

Suppressor Cleaning Solution

1 M Sulfuric Acid & 0.1 Oxalic Acid in 5% Acetone. Purchase premade or prepare as outlined in table 10.2. Store at room temperature. Expires per manufacturer’s specifications.


Suppressor Regenerant Solution

0.1 M Sulfuric Acid. Purchase premade or prepare as outlined in table 10.2. Store at room temperature. Expires per manufacturer’s specifications.

Metrohm part # REAIC1160C

Calibration Solution (CAL6)

Bromide – 8.0 mg/L Chloride – 100 mg/L Fluoride – 4.0 mg/L Nitrate as N – 8.0 mg/L Nitrite as N – 8.0 mg/L Sulfate – 100 mg/L Purchase premade or prepare as outlined in table 10.2. Store at 4±2ºC. Expires per manufacturer’s specifications.


Initial & Continuing Calibration Verification (ICV/CCV) Solution

Bromide – 1.0 mg/L Chloride – 12.5 mg/L Fluoride – 1.0 mg/L Nitrate as N – 1.0 mg/L



Nitrite as N – 1.0 mg/L Sulfate – 12.5 mg/L Purchase premade or prepare as outlined in table 10.2. Store at 4±2ºC. Expires per manufacturer’s specifications.

Spiking Solution Bromide – 10.0 mg/L Chloride – 125 mg/L Fluoride – 10.0 mg/L Nitrate as N – 10.0 mg/L Nitrite as N – 10.0 mg/L Sulfate – 125 mg/L Purchase premade or prepare as outlined in table 10.2. The system automatically prepares the spike at a 10x dilution in the selected parent sample. Store at 4±2ºC. Expires per manufacturer’s specifications.

ERA part # 092 (custom standard)

10.2. Table 10.2 – Working Standards and Reagents

Note: The system can be programmed to automatically make the necessary dilutions.

Solution Reagent(s) Used Reagent(s) Amount Solvent Final Solution

Volume Final

Concentration

A Supp 5 Eluent 20x Na2CO3 6.78 g

DI Water 1000 mL 64 mM Na2CO3 20 mM NaHCO3 NaHCO3 1.68 g

Suppressor Rinse Solution

Methanol 1 mL DI Water 1000 mL 0.1% Methanol

Suppressor Regenerant Solution H2SO4 5.3 mL DI Water 1000 mL 0.1 M H2SO4

Suppressor Cleaning Solution

H2SO4 53 mL DI Water 1000 mL

1 M H2SO4 0.1 M Oxalic Acid

5% Acetone Oxalic Acid 12.6 g

Acetone 50 mL

Calibration Solution (CAL6)

Fluoride Standard 0.1 mL

DI Water 50 mL

2.0 mg F/L 100 mg Cl/L

8.0 mg NO2-N/L 8.0 mg Br/L

8.0 mg NO3-N/L 100 mg SO4/L

Chloride Standard 5 mL

Nitrite Standard 0.4 mL

Bromide Standard 0.4 mL

Nitrate Standard 0.4 mL

Sulfate Standard 5 mL

CAL5 CAL6 5.0 mL DI Water 10 mL









0.10 mg F/L 5.0 mg Cl/L

0.40 mg NO2-N/L 0.40 mg Br/L

0.40 mg NO3-N/L 5.0 mg SO4/L

CAL2 CAL6 1.0 mL DI Water 50 mL 0.040 mg F/L 2.0 mg Cl/L


0.16 mg NO2-N/L

0.16 mg Br/L 0.16 mg NO3-N/L

2.0 mg SO4/L


0.020 mg F/L 1.0 mg Cl/L

0.080 mg NO2-N/L 0.080 mg Br/L

0.080 mg NO3-N/L 1.0 mg SO4/L

ICV/CCV Solution


DI Water 200 mL

1.0 mg F/L 12.5 mg Cl/L


1.0 mg NO3-N/L 12.5 mg SO4/L

Chloride Standard 2.5 mL Nitrite Standard 0.2 mL

Bromide Standard 0.2 mL Nitrate Standard 0.2 mL Sulfate Standard 2.5 mL

Spiking Solution


DI Water 10 mL

10.0 mg F/L 125 mg Cl/L

10.0 mg NO2-N/L 10.0 mg Br/L

10.0 mg NO3-N/L 125 mg SO4/L

Chloride Standard 1.25 mL Nitrite Standard 0.1 mL

Bromide Standard 0.1 mL Nitrate Standard 0.1 mL Sulfate Standard 1.25 mL

ICV/CCV 2 Solution

Fluoride Standard 0.15 mL DI Water

100 mL

1.5 mg F/L Chloride Standard 5.0 mL DI Water 50 mg Cl/L Nitrite Standard 0.4 mL DI Water 4.0 mg NO2-N/L

Bromide Standard 0.4 mL DI Water 4.0 mg Br/L Nitrate Standard 0.4 mL DI Water 4.0 mg NO3-N/L Sulfate Standard 5.0 mL DI Water 50 mg SO4/L

10.3. A Supp 5 Eluent 20x. Add 6.78 g Na2CO3 and 1.68 g NaHCO3 to ~500 mL DI water in a 1 L volumetric flask and dilute to mark. Use a stir bar and a magnetic stirring plate to fully dissolve the solids and degas the water for 20-30 minutes. Store in a glass container at room temperature. Expires in six months.

10.4. Suppressor Rinse Solution & Suppressor Regenerant Solution. Add respective reagents to ~500 mL DI water in a 1 L volumetric flask. Dilute to mark and mix thoroughly. Store in a glass container at room temperature. Expires in six months.

10.5. Supressor Cleaning Solution. Add 53 mL H2SO4 to ~500 mL DI water in a 1 L volumetric flask. Add 12.6 g oxalic acid and 50 mL acetone. Dilute to mark and mix thoroughly, making sure the oxalic acid is fully dissolved. Store in a glass container at room temperature. Expires in six months.

10.6. Calibration Solution (CAL6). Spike the respective amount of each anion standard into ~25 mL DI water in a class A 50 mL volumetric flask. Dilute to mark and mix thoroughly. Expires in 48 hours; alternatively, the solution expires in 28 days if nitrite and/or nitrate is not included or evaluated. Note: Be sure to use different lots for each standard than that which is used for the ICV/CCV Solution and the Spiking Solution.

10.7. ICV/CCV Solution. Spike the respective amount of each anion standard into ~100 mL DI water in a class A 200 mL volumetric flask. Dilute to mark and mix thoroughly. Expires in 48 hours; alternatively, the solution expires in 28 days if nitrite and/or nitrate is not included or evaluated. Note: Be sure to use different lots for each standard than that which is used for the Calibration Solution (CAL6).

10.8. Spiking Solution. Spike the respective amount of each anion standard into ~25 mL DI water in a class A 10 mL volumetric flask. Dilute to mark and mix thoroughly. Expires in 48 hours; alternatively, the solution expires in 28 days if nitrite and/or nitrate is not included or evaluated. Note: Be sure to use different lots for each standard than that which is used for the Calibration Solution (CAL6).



11.1. Table 11.1 – Calibration, Verification and Acceptance Criteria

Calibration Metric Parameter/Frequency Criteria Comments Calibration Curve Fit

Quadratic fit or linear regression.

Curve is valid for 90 days but must be confirmed every 30 days with a standard at the reporting limit.

r ≥ 0.990 for each analyte

If criteria are not met, remake the calibration standards and recalibrate the instrument.

A quadratic fit is allowed per the Federal Register (see 19.1 and 25.7); a minimum of six points must be included in the calibration.

If linear regression is used, a minimum of three calibration points and a blank is required.

Manufacturer recommends r > 0.9990 for each analyte with a relative standard deviation (RSD) of 5% or less. This is not required.

Initial & Continuing Calibration Verification (ICV/CCV)

ICV must be performed immediately after calibration. A CCV must be analyzed every 10 samples and at the end of the analytical sequence.

For WI-originating samples, if a quadratic curve is utilized two CCVs have to be analyzed at differing concentrations at the inflection points.


When measurements exceed the acceptance criteria, all analytical samples since the last compliant CCV must be reanalyzed. If the ICV or two consecutive CCVs exceed the control limits, the analysis must be terminated, the problem corrected and the system recalibrated.

Monthly Calibration Verification

Once 30 days after calibration and once 60 days after calibration.

The true value must be equal to or less than the reporting limit for each analyte.


If the initial calibration is utilized for greater than 30 days, the reporting limit must be verified every 30 days at the same criteria. If criteria are not met, the reporting limit must be raised to the next standard that meets the criteria until a new calibration has been performed per Minnesota Department of Health (MDH) rules. When necessary, make manual adjustments to the integration in order to obtain the most accurate peak areas. Include all documentation, including a before and after, of any manual integration.

Linear Calibration Range (LCR)

Must be determined initially and verified every 6 months or whenever a significant change in instrument response is observed or expected.


Verify the linear calibration range every six months by analyzing a blank and three standards quantitated against the calibration curve.

Initial & Continuing Calibration Blank (ICB/CCB)

Analyzed after every ICV/CCV The absolute value must be less than the reporting limit for each analyte. Per QAPP or client

If a CCB exceeds the RL, reanalyze all samples since the last compliant CCB. If the ICB or two consecutive CCBs exceed the control limits, the analysis must be terminated, the problem corrected and the system recalibrated.

Exception:


specifications, alternate criteria such as evaluating to ½ RL may apply.

If all the affected samples are non-detect or at least 10x the concentration of the failing result, the sample data may be accepted.

High Check Required by client-specific tech specs. Must be performed on the same day that client’s samples are analyzed. The high check must be above the mid-point of the calibration curve. Utilize CAL6 or ICV/CCV2 Solution.


If either/or check is outside the acceptance criteria, remake the respective check standard and re-analyze. If the reanalysis is outside the acceptance criteria, the instrument must be re-calibrated prior to the analysis of any samples that require this high check.

ICV/CCV 2 Required by WI DNR. If using a quadratic regression for any analytes, must be performed during analysis of any samples of Wisconsin origin for those analytes. Analyze immediately after each ICV/CCV. The analytes in the ICV/CCV 2 should be close to or at the inflection point. Utilize ICV/CCV 2 Solution.


If either/or check is outside the acceptance criteria, remake the respective check standard and re-analyze. If the reanalysis is outside the acceptance criteria, the instrument must be re-calibrated prior to the analysis of any samples of Wisconsin origin.

11.2. Generating a Calibration Curve

11.2.1. Turn the IC on and open the MagIC Net 2.3 software. Click Start HW in the Equilibration tab to allow the system to stabilize and the column heater to come up to temperature (35.0°C). This takes approximately 30 minutes.

11.2.2. Prepare the calibration solution (CAL6) using the volumes found in table 10.2. Alternatively, use the premade calibration stock solution purchased through Metrohm.

11.2.3. Pour an aliquot of calibration solution into a vial and load in the rack. Load five additional empty vials to accommodate dilutions made by the system.

11.2.4. Enter the calibration standards in the determination series of the MagIC software as CAL1, CAL2, CAL3, CAL4, CAL5 and CAL6. The sample type for each standard must be Standard 1, Standard 2, Standard 3, Standard 4, Standard 5 and Standard 6, respectively. CAL6 is the calibration standard made in table 10.1 and CAL1 through CAL5 are dilutions prepared from CAL6 by the system. The dilutions are as follows:

CAL1 = 100x dilution CAL4 = 4x dilution



Alternatively, CAL1 through CAL5 may be manually prepared by diluting the CAL6 in class A volumetric flasks. See table 10.1 for instructions for manual dilutions.

11.2.5. After the calibration standards have been analyzed, analyze a CCV and CCB (Note: This will be changed to ICV/ICB during evaluation of the calibration). Once complete, click on Database in the MagIC Net software.

11.2.6. Highlight the six calibration standards and the CCV and CCB, right click and select Reprocess…

11.2.7. In the reprocessing table, change the name of the CCV and CCB to ICV and ICB, respectively.

11.2.8. Click on CAL6 and update the retention time for each anion peak. Click Update once this is complete.


11.2.9. With CAL6 still highlighted, click on Reprocessing. This will open a small window prompting

you to reprocess the calibration. Select From standards of reprocessing table and Keep manual integration and click OK.

11.2.10. With CAL6 still highlighted, click on Reprocessing again. This time, select From standards of reprocessing table and Keep manual integration and click OK.

11.2.11. Next, click Method… and then Save as…

11.2.12. Select the method being used for analysis: EPA 300.0 Anions. Save, noting the day’s date and analyst initials.

Note: The method name in the instrument specifies EPA 300.0 Anions although the analysis is also applicable to SW-846 Method 9056A.

11.2.13. Now select OK in the lower right hand corner of the reprocessing table window. When prompted, select Calibration Changed and note the day’s date and analyst initials. It may take several minutes for the database to update the calibration information.

11.2.14. To report the calibration curve to a Q batch, follow the sample reporting steps in section 12.2.

12. Procedure


12.1.1. Batch up samples in Horizon and allow them to come to room temperature before analysis.

12.1.2. Turn the IC on and open the MagIC Net 2.3 software. Click Start HW in the Equilibration tab to allow the system to stabilize and the column heater to come up to temperature (35.0°C). This takes approximately 30 minutes.

12.1.3. Open LimsLink and click on Get Samples to create a prep run. Pull in the batch information and select Import Instrument and then Export to Metrohm.

12.1.4. In MagIC, go to the Determination series tab and click on Sample table. Select Import Data and then select IC.csv. The run sequence will be generated and fill out all blank cells other than those titled Info.

12.1.5. Begin the sequence by analyzing a CCV and CCB if they have not been performed within the last six hours. The sequence may be edited even after the analysis has begun. Therefore, samples may be added on to the end of a run, the order that samples are run may be altered or dilutions can be added and changed as the run progresses.

12.1.6. Critically evaluate all chromatograms in the Database and determine if any require manual integration or further dilution. Manual integration should be avoided if at all possible. If manual integration is used, both before and after chromatograms should be included in the data package along with a memo stating that the chromatogram was manually integrated.

12.1.7. If doubt exists over the identification of a peak in the chromatogram, confirmatory techniques such as sample dilution and fortification must be used.

12.2. Reporting Data

12.2.1. In the Database, highlight all analytical points pertinent to the batch being reported.

12.2.2. Open Determinations in the toolbar at the top of the window and select Export… Makes sure the selection specifies All selected data records and that the export template is set to LimsLink Export. Select OK.

12.2.3. Open the folder C:/Limslink Data/Test Data and find the file named TEST.csv. Rename this to the WETA batch number and close the folder.

12.2.4. Open LimsLink and create a new run under IC_QBATCH.

12.2.5. Open Import Instrument, select 10WT61 and scroll down to find the batch being reported. Select the batch to populate the spreadsheet.


12.2.6. Click on Options and Import / Export Data and click on Set Standard IDs. Once prompted, enter

the Q batch number of the most current calibration.

12.2.7. Select the appropriate standard IDs for the CCV and CCBs used in the run.

12.2.7.1. When posting initial calibration data to a Q batch, select the appropriate standard IDs for CAL1 through CAL6 as well as the ICV and ICB.

12.2.8. Click on Options and Import / Export Data again and select Get LIMS Info. Click Yes when prompted to use the entire run.

12.2.9. If any samples are reporting analytes at different dilutions, right click the appropriate sample cell and delete the X from the Use Element column in order to exclude the result from posted.

12.2.10. Highlight all the samples being reported, open Options and Import / Export Data and select Export Run to Epic Pro.

13. Quality Control

13.1. Table 13.1 – Quality Control


DI Water Analyzed once per batch of up to 20 samples.

The absolute value must be less than the reporting limit for each analyte. Per QAPP or client specifications, alternate criteria such as evaluating to ½ RL may apply.

If outside the acceptance criteria, reanalyze. If reanalysis still does not pass, terminate analysis and reject all batch data associated with the failing MB. Exception: If all batch samples are non-detect or at least 10x the concentration of the failing result, the sample data may be accepted.

Laboratory Control Sample (LCS) / Laboratory Control Sample Duplicate (LCSD)

1 mL of Spiking Solution : 9 mL DI Water

An LCS must be analyzed once per batch of up to 20 samples. An LCSD must be performed quarterly to generate data points to determine a precision limit for the laboratory.

90-110% of the true value Until sufficient data points (>20 points) have been generated, ≤ 20 % RPD will be utilized for criteria.

If LCS recovery is not within the criteria, reanalyze. If reanalysis does not pass, terminate analysis and reject all batch data associated with the failing LCS. The system may need to be recalibrated and/or require maintenance.


1 mL of Spiking Solution : 9 mL of client-provided sample

A pair of MS/MSD must be analyzed once every ten samples or once per batch, whichever is more frequent.

90-110% of the true value RPD ≤ 20%

If the MS recovery is not within the criteria, and the LCS is shown to be in control, the recovery problem is judged to be matrix related and the results may be accepted. If the concentration of matrix spike is less than 25% of the background concentration of the matrix, the matrix spike recovery should not be calculated. For Minnesota Admin Contract Clients – all MS/MSD failures require reanalysis of the MS/MSD and the original sample. If it is still out of control, investigate and document the cause in the associated narrative as well as qualifying appropriately.



14.1. All calculations are done internally within the MagIC NET 2.3 software.

14.2. Spike sample recovery is calculated as follows:

% Recovery =

SA

SRSSR

Where: SSR = Spike sample result, mg/L SR = Sample result, mg/L SA = Spike added, mg/L

14.3. The relative percent difference (RPD) is calculated as:

RPD = [|S-D| x 100] (S+D)/2

Where: S = Sample value, mg/L D = Duplicate sample value, mg/L



16. Corrective Actions for Out-of-Control Data


17. Contingencies for Handling Out-of-Control or Unacceptable Data

17.1. If not specifically listed in the tables in section 11 & 13, the contingencies are as follows. If there is no additional sample volume to perform re-analyses, all data will be reported as final with applicable qualifiers. If necessary, an official case narrative will be prepared by the Quality Manager or Project Manager.



18.2. Method Detection Limit (MDL) Study: An MDL study must be conducted every six months (per the method) per S-MN-Q-269 – Determination of Limit of Detection and Limit of Quantitation (or equivalent replacement) for each matrix per instrument.

18.3. Demonstration of Capability (DOC): Every analyst who performs this method must first document acceptable accuracy and precision by passing a demonstration of capability study (DOC) per S-ALL-Q-020 - Training Procedures (or equivalent replacement).

18.4. Periodic performance evaluation (PE) samples are analyzed to demonstrate continuing competence per SOP S-MN-Q-258 – Proficiency Testing Program (or equivalent replacement). Results are stored in the QA office.


19.1. The calibration curve may be fitted using a quadratic function in lieu of the linear regression model. In such a case, the minimum number of calibration points should be six, and in no case should concentrations be extrapolated for instrument responses that exceed that of the most concentrated calibration point. Ref. 25.7




20.2. Routine Maintenance – Refer to Metrohm USA IC User Guide (25.6.)

20.2.1. Weekly

20.2.2. The ultra-filtration membrane filter disk should be inspected for sediment build-up and algal growth. In this event, it should be changed and the acrylic apparatus holding it together be thoroughly rinsed and cleaned with E-pure DI water.

20.2.3. The water scrubber should be changed (beads changed and baked out) and the carbon dioxide scrubber should be checked and changed as needed.

20.2.4. On a bi-weekly schedule, flows should be checked through the autosampler pump tubes and through the suppressor acid and water pump tubes. If not to the manufacturer’s specification, replace any pump tubing as needed.

20.2.5. The remainder of the maintenance is to be performed on either a monthly, quarterly or annual basis. The annual maintenance is covered by a maintenance contract and performed as part of the annual preventative maintenance. All other maintenance is performed by the analyst. The frequency of maintenance is summarized below:

20.3. Table 20.1 Instrument Maintenance and Frequency

Maintenance Frequency Change suppressor rinse solution As needed Change suppressor regenerant solution As needed Triple rinse the dilution water reservoir and change water As needed Change A Supp 5 Eluent 20x As needed Replace the ultra-filtration disk, cleaned disk apparatus Weekly or as needed Replace the water scrubber and/or CO2 srubber As needed Change sampler and MSM pump tubing As needed Replace the RP guard disk and filter Monthly or as needed Triple rinse the eluent water reservoir and change water Weekly or as needed Replace the 3 inline filters Quarterly or as needed Change the trap on top of the eluent As needed Change the eluent aspirating filter As needed Replace check valves Annually Replace piston seals Annually Replace sapphire support rings Annually Replace sample waste lines Annually Clean pump rollers with deionized water Annually

21. Troubleshooting

21.1. Refer to the Metrohm operators’ manual for troubleshooting techniques.

22. Safety





23.1. Procedures for handling waste generated during this analysis are addressed in S-MN-S-003 - Waste Handling and Management (or equivalent replacement).




25. References




25.4. Methods for the Determination of Inorganic Substances in Environmental Samples, EPA/600/R-93/100, Method 300.0, Revision 2.1, August 1993.

25.5. Metrohm USA Operators Manual - stored on desktop of instrument computer

25.6. Federal Register/Vol. 77, No. 96/Friday, May 18, 2012/Rules and Regulations – Page 54, section (x.)

25.7. U.S. Environmental Protection Agency, Methods for the Determination of Inorganic Anions by Ion Chromatography, Revision 1, February 2007, SW-846 Method 9056A.



27. Revisions


S-MN-I-583-rev.04

Added SW-846 Method 9056A Table 10.1 – revised Calibration solution, ICV/CCV, and spiking solution Table 10.2 – added CAL5 – CAL1, ICV/CCV 2 solutions; removed solvent volume 10.6 – 10.8: added Expiration criteria 11.1 – Calibration Curve Fit revised; added High check and ICV/CCV2 11.1 – Calibration Fit Frequency changed to linear regression 11.1 – Added “If crieteria is not met…” 11.2.4 – Added “The sample type…respectively” and “Alternatively, CAL1…” 11.2.5 – Added procedure for CCB and CCB; removed “data from the calibration…” 11.2.6-11.2.13 – Added calibration procedure 11.2.12 – note for 9056 analysis added Table 13.1 – LCS/LCSD revised; Removed MS/MSD Stock Standard 14.3 – RPD equation revised 25.4 – Reference edited 25.7 – 9056A reference added

04Sep2014

APPENDIX B

CORRECTIVE ACTION REPORT

1 of 2

Corrective Action Report/

Corrective Action Plan

Project ID Project Name Document ID

Preparer’s Signature/Submit Date

Submitted to:

Description of the requirement or

specification

Reason for the Corrective Action

Location, affected sample, affected

equipment, etc. requiring corrective

action

Suggested Corrective Action


Preventative Action Plan

Preventative actions completed name/date:

Corrective actions completed name/date:

Approval signature/date:

EPA approval name/date:

Approval of corrective actions required by EPA? Yes No

(Continue on Back)

(Continue on Back)

(Continue on Back)

2 of 2

Suggested Corrective Action

(Continued)


(Continued)

Preventative Action Plan

(Continued)

Corrective Action Report/


APPENDIX C

DATA VALIDATION CHECKLISTS

Appendix A Quality Assurance and Quality Control Review of Inorganic Data

Quality Assurance and Quality Control Review of Inorganic Data Summaries of the samples collected for this investigation are included in the attached tables. The analytical protocols used to obtain metals and wet chemistry data during the [project] included [methods]. The quality of the inorganic data is summarized in the paragraphs below and in the report attachments. Executive Summary Enforcement quality data are supported by rigorous sampling and analysis procedures, quality assurance and quality control (QA/QC) protocols, and documentation requirements. Enforcement quality data include data that meet the Level A and B criteria (Attachment D) and are not qualified as estimated during the data validation process. In addition to the Level A/B assessment, the data are reviewed for qualifiers. Data that meet the Level A and B criteria and are free of qualifiers are of enforcement quality. Of the [X] total data points for inorganic data, (x) have been qualified due [XX]. None of the results have been rejected. The analytical data and the enforcement screening assessment are presented in Table 1 in the main text of the report. Sample number codes and sampling coordinates at each station are also identified in DSR tables. Of the [X] total data points, [X] percent of the data points are classified as screening quality due to QC exceedances, and [X] percent are classified as enforcement quality data and are unqualified. Quality Assurance and Quality Control Review of Inorganic Data Data validation checklists were completed using the data validation form for the EPA Addenda to the Clark Fork River Superfund Site Investigations Data Management/Data Validation Plan (EPA, 2000). The completed checklists are included in Attachments A through D. Laboratory data flags and qualifiers are listed in the DSR in Tables 1 and 2. Field Quality Control Samples The frequency and quality of field quality control as outlined in the quality assurance project plan (QAPP) and the [SAP title] are discussed in the following sections. Field Blank Results Field blank results are used to provide a measure of effectiveness of field decontamination procedures. [X] field blank samples were collected during this sampling effort, which meets the SAP-required field blank frequency of 1 per 20 natural samples. Positive field blank detections >2x the MDL were noted [X].

Field Duplicate Results Field duplicates are used to assess field and laboratory precision. [X] field duplicates were collected during this sampling effort, which meets the SAP-required field duplicate frequency of 1 per 20 natural samples. Results for [X] field duplicate samples were outside the EPA-required duplicate precision criteria for [X]. Reference Material Samples Collection of reference material samples was not required by the SAP.

Attachment A: Data Validation Checklist for Metals Analysis (2 pages)

Attachment A Data Validation Checklist

for Metals Analysis by ICP

Site: Sample Matrix: Laboratory: Project: Analysis Dates: Analyses: Sample Dates: Data Validators: Validation Dates: 1. Holding Times

Analyte Matrix Method Holding Time*

Collection Dates

Analysis Dates

Holding time met?

(Y/N)

Affected data

flagged? (Y/N)

Clark Fork LAP Clark Fork LAP Clark Fork LAP

*Reference for holding time (Clark Fork River Superfund Site; LAP = Laboratory Analytical Protocol) Were any data flagged because of holding time problems? Y N Were any data flagged because of incorrect sample preservation? Y N Describe any actions taken: None required. 1. Blanks Was an initial calibration blank (ICB) analyzed? NA Was the ICB within the control window of < laboratory’s reporting limit (RL)? NA Were continuing calibration blanks (CCBs) performed at the frequency of 1/10 analyses? NA Were CCBs within the control window of < laboratory’s RL? NA Were preparation blanks (PBs) performed at the frequency of 1/20 or 1/prep batch? Y N Were PBs within the control window of < laboratory’s RL? Y N Were any data qualified because of blank problems? Y N Describe any actions taken because of blank results: None required. 2. Laboratory Control Sample Was the laboratory control sample (LCS) analyzed at the frequency of 1/20 or per prep batch? Y N What was the source of the LCS? SPEX, ISS, CPI Were LCS results within the control window of 80-120%? Y N Were any data qualified because of LCS problems? Y N Describe any actions taken because of LCS results: None required. 3. Duplicate Sample Results Was a laboratory duplicate sample (LDS) analyzed at the frequency of 1/20 or per prep batch? Y N Were the results of the LDS within the control window of +/- 20% RPD? Y N Were any data qualified because of LDS problems? Y N Describe any actions taken because of LDS results: None required. 4. Matrix Spike Sample Results Was a laboratory matrix spike sample (LMS) analyzed at the frequency of 1/20? Y N Were the results of the LMS within the control window of CLP’s 75-125%? Y N Were any data qualified because of LMS problems? Y N Describe any actions taken because of LMS results: None required. 5. Overall Assessment Are there analytical limitations of the data that users should be aware of? Y N If so, explain: There are no qualifications to this data based on laboratory QA/QC.

Attachment A Data Validation Checklist

for Metals Analysis by ICP

6. Authorization of Data Validation

Data Validator: Data Validation Reviewer:

Name: Name:

Signature: Signature:

Date: Date:

Attachment B: Data Validation Checklist for Wet Chemistry Analysis (2 pages)

Attachment B Data Validation Checklist

for General Chemistry

Site: Sample Matrix: Laboratory: Project: Analysis Dates: Analyses: Sample Dates: Data Validator: Validation Dates: 1. Holding Times

Analyte Matrix Method Holding Time* Collection Dates

Analysis Dates

Holding time met?

(Y/N)

Affected data flagged? (Y/N)

Clark Fork LAP Clark Fork LAP Clark Fork LAP Clark Fork LAP Clark Fork LAP Clark Fork LAP Clark Fork LAP

*Reference for holding time (Clark Fork Superfund Site; LAP = Laboratory Analysis Plan) Were any data flagged because of holding time problems? Y N Were any data flagged because of preservation problems? Y N Comments: None required. 2. Blanks Was an initial calibration blank (ICB) analyzed? (sulfate only) NA Was the ICB within the control window of <laboratory’s reporting limit? NA Were continuing calibration blanks (CCBs) performed? (sulfate only) NA Were CCBs within the control window of <laboratory’s reporting limit? NA Were preparation blanks (PBs) performed at the frequency of 1/20 or 1/prep batch? Y N Were PBs within the control window of <laboratory’s reporting limit? Y N Were any data qualified because of blank problems? Y N Describe any actions taken because of calibration results: None required. 3. Laboratory Control Sample Was a laboratory control sample (LCS) analyzed at a frequency of 1/20 or per prep batch? Y N What was the source of the LCS? ERA, Labchem, Ultra Were LCS results within the control window of 80-120% or +/- 0.2 for pH? Y N Were any data qualified because of LCS problems? Y N Describe any actions taken because of LCS results: None required. 4. Duplicate Sample Results Was a laboratory duplicate sample (LDS) analyzed at the frequency of 1/20? Y N Were the LDS results within the control window of +/- 20% RPD or +/- 0.2 for pH? Y N Were any data qualified because of LDS problems? Y N Describe any actions taken because of LDS results: None required. 5. Matrix Spike Sample Results Was a laboratory matrix spike sample (LMS) analyzed at the frequency of 1/20? (sulfate only) Y N Were the results of the LMS within the control window of 75-125%? Y N Were any data qualified because of LMS problems? Y N Describe any actions taken because of LMS results: None required. 6. Overall Assessment Are there any analytical limitations of the data that users should be aware of? Y N If so, explain: There are no limitations to this data based on laboratory QA/QC.

Attachment B Data Validation Checklist

for General Chemistry

7. Authorization of Data Validation

Data Validator: Data Validation Reviewer:

Name: Name:

Signature: Signature:

Date: Date:

Attachment C: Field Quality Assurance/Quality Control Checklist (1 page)

Attachment C Data Validation Checklist for Field Quality Control

Site: Sample Matrix: Laboratory: Project: Analysis Dates: Analyses: Sample Dates: Data Validator: Validation Dates: 1. Holding Times

Analyte Matrix Method Collection Date Affected data flagged? (Y/N)

2. Field QC Samples Field Blanks Were field blanks submitted as specified in the Sampling and Analysis Plan (SAP)? Y N Were any data qualified because of field blank problems? Y N Field Duplicates Were field duplicates submitted as specified in the SAP? Y N Were results for field duplicates within the target control limits in the CFRSSI QAPP? Y N Were any data qualified because of field duplicate results? Y N Field Reference Materials Were Field Reference Materials or Performance Evaluation Samples submitted as specified in the SAP? NA Were the results within the manufacturer’s specified control limits? NA

Comments:

Attachment D: Level A/B Assessment Checklist (2 pages)

Attachment D Level A/B Screening Checklist

I. General Information II. Screening Results Site: Data are: Project: Client: 1) Unusable Sample Matrix: 2) Level A 3) Level B I. Level A Screening

Criteria – The following must be fully documented: Yes/No Comments

1. Sampling date Yes

2. Sampling team or leader Yes

3. Physical description of sampling location Yes

4. Sample depth (soils) N/A

5. Sample collection technique Yes

6. Field preparation technique N/A

7. Sample preservation technique Yes

8. Sample shipping records and laboratory analysis dates Yes

9. Companion sampling efforts Yes

10. Visual classification of samples Yes

II. Level B Screening

Criteria – The following must be fully documented: Yes/No Comments

1. Field/laboratory instrumentation, standardization and methods/procedures Yes

2. Proper sample containers and container preparation Yes

3. Collection of field replicates (1/20 minimum) Yes

4. Proper and decontaminated sampling equipment N/A

5. Identity of sample taker Yes

6. Field custody documentation Yes

7. Shipping custody documentation Yes

8. Traceable sample designation number Yes

9. Field notebooks, custody records in secure repository Yes

Attachment D Level A/B Screening Checklist

10. Properly prepared and complete field forms Yes

11. Physical data/observations date and time Yes

12. Physical data/observations recorder, team leader Yes

13. Physical data/observation location Yes

Laboratory Report Forms and Chain of Custody Documentation

EPA Region 8 QA Document Review Crosswalk Page 1 of 10 Draft Final Long-Term Groundwater Monitoring Program QAPP

2-2015 QAPP Crosswalk

EPA REGION 8 QA DOCUMENT REVIEW CROSSWALK QAPP/FSP/SAP for: (check appropriate box)

Entity (grantee, contract, EPA AO, EPA Program, Other) Atlantic Richfield Company

Regulatory Authority and/or Funding Mechanism

___40 CFR 31 for Grants ___48 CFR Part 46 for Contracts ___ Interagency Agreement ___ EPA Administrative Order ___ EPA Program Funding ___ EPA Program Regulation ___ EPA CIO 2105

GRANTEE CONTRACTOR EPA

X Other

Document Title [Note: Title will be repeated in Header] Draft Final Long-Term Groundwater Monitoring Program QAPP

QAPP/FSP/SAP Preparer Pioneer Technical Services, Inc.

Period of Performance (of QAPP/FSP/SAP)

2015-2019 Date Submitted for Review

EPA Project Officer EPA Project Manager

Charlie Coleman PO Phone # PM Phone #

(406) 457-5038

QA Program Reviewer or Approving Official

Terry Moore Date of Review February 2015

Documents to Review: 1. QAPP written by Grantee or EPA must also include for review:

Work Plan(WP) / Statement of Work (SOW) / Program Plan (PP) / Research Proposal (RP) 2. QAPP written by Contractor must also include for review:

a) Copy of signed QARF for Task Order b) Copy of Task Order SOW c) Made available hard or electronic copy of approved QMP d) If QMP not approved, provide Contract SOW

3. For a Field Sampling Plan (FSP) or Sampling & Analyses Plan (SAP), the Project QAPP

must also be provided. OR

The FSP or SAP must be clearly identified as a stand-alone QA document and must contain all QAPP required elements (Project Management, Data Generation/Acquisition, Assessment and Oversight, and Data Validation and Usability).

Documents Submitted for QAPP Review: 1. QA Document(s) submitted for review:

QA Document

Document Date

Document Stand-alone

Document with QAPP

QAPP Yes / No FSP Yes / No Yes / No SAP Yes / No Yes / No SOP(s) Yes / No

2. WP/SOW/TO/PP/RP Date ___________ WP/SOW/TO/RP Performance Period _____________ 3. QA document consistent with the: WP/SOW/PP for grants? Yes / No SOW/TO for contracts? Yes / No 4. QARF signed by R8 QAM Yes / No / NA

Funding Mechanism IA / contract / grant / NA Amount _____________

Summary of Comments (highlight significant concerns/issues): 1. Comment #1 2. Comment #2 3. Comment #3 4. The Atlantic Richfield Company must address the comments in the Summary of Comments, as well as those identified in the Comment section(s) that

includes a “Response (date)” and Resolved (date)”.



Element

Acceptable Yes/No/NA

Page/ Section

Comments

A. Project Management A1. Title and Approval Sheet

a. Contains project title

Yes Title page, Approval Page, Footer

Revision # and date are included in the Revision Summary (page v), revision # also included in the footer of each page.

b. Date and revision number line (for when needed) c. Indicates organization=s name d. Date and signature line for organization=s project manager e. Date and signature line for organization=s QA manager f. Other date and signatures lines, as needed

A2. Table of Contents a. Lists QA Project Plan information sections Yes Pages ii

through iv

b. Document control information indicated A3. Distribution List

Includes all individuals who are to receive a copy of the QA Project Plan and identifies their organization

Yes Page ii

A4. Project/Task Organization a. Identifies key individuals involved in all major aspects of the project, including contractors

Yes Section 2.1

Project Organization Chart is Figure 1

b. Discusses their responsibilities c. Project QA Manager position indicates independence from unit generating data d. Identifies individual responsible for maintaining the official, approved QA Project Plan e. Organizational chart shows lines of authority and reporting responsibilities

A5. Problem Definition/Background a. States decision(s) to be made, actions to be taken, or outcomes expected from the information to be obtained

Yes Section 2.2

b. Clearly explains the reason (site background or historical context) for initiating this project c. Identifies regulatory information, applicable criteria, action limits, etc. necessary to the project



A6. Project/Task Description a. Summarizes work to be performed, for example, measurements to be made, data files to be obtained, etc., that support the project=s goals

Yes Section 2.3/Tables 1 & 2/Figure 2

b. Provides work schedule indicating critical project points, e.g., start and completion dates for activities such as sampling, analysis, data or file reviews, and assessments c. Details geographical locations to be studied, including maps where possible d. Discusses resource and time constraints, if applicable

A7. Quality Objectives and Criteria a. Identifies - performance/measurement criteria for all information to be collected and acceptance criteria for information obtained from previous studies, - including project action limits and laboratory detection limits and - range of anticipated concentrations of each parameter of interest Yes

Section 2.4.1/Tables 3 &12

DQO development is discussed in this section.

b. Discusses precision c. Addresses bias d. Discusses representativeness e. Identifies the need for completeness f. Describes the need for comparability g. Discusses desired method sensitivity

A8. Special Training/Certifications a. Identifies any project personnel specialized training or certifications

Yes Section 2.5

b. Discusses how this training will be provided c. Indicates personnel responsible for assuring training/certifications are satisfied d. identifies where this information is documented



A9. Documentation and Records a. Identifies report format and summarizes all data report package information

Yes Section 2.6/3.6

b. Lists all other project documents, records, and electronic files that will be produced c. Identifies where project information should be kept and for how long d. Discusses back up plans for records stored electronically e. States how individuals identified in A3 will receive the most current copy of the approved QA Project Plan, identifying the individual responsible for this

B. Data Generation/Acquisition B1. Sampling Process Design (Experimental Design)

a. Describes and justifies design strategy, indicating size of area, volume, or time period to be represented by a sample

Yes Sections 3.1.1-3.1.3

b. Details the type and total number of sample types/matrix or test runs/trials expected and needed c. Indicates where samples should be taken, how sites will be identified/located d. Discusses what to do if sampling sites become inaccessible e. Identifies project activity schedules such as each sampling event, times samples should be sent to the laboratory, etc. f. Specifies what information is critical and what is for informational purposes only g. Identifies sources of variability and how this variability should be reconciled with project information



B2. Sampling Methods a. Identifies all sampling SOPs by number, date, and regulatory citation, indicating sampling options or modifications to be taken

Yes Section 3.3/Table 13

b. Indicates how each sample/matrix type should be collected Yes Section 3.3.1

c. If in situ monitoring, indicates how instruments should be deployed and operated to avoid contamination and ensure maintenance of proper data

Yes Section 3.1.1

d. If continuous monitoring, indicates averaging time and how instruments should store and maintain raw data, or data averages

Yes Section 2.6.4 Reference SOP-GW-15

e. Indicates how samples are to be homogenized, composited, split, or filtered, if needed Yes Section 3.1.2/

3.1.3 Reference Field SOPs

f. Indicates what sample containers and sample volumes should be used Yes Section 3.2.2/

Table 11

g. Identifies whether samples should be preserved and indicates methods that should be followed Yes Section 3.2.2/

Table 11

h. Indicates whether sampling equipment and samplers should be cleaned and/or decontaminated, identifying how this should be done and by-products disposed of

Yes Section 3.1.4

i. Identifies any equipment and support facilities needed Yes Section 3.1.2 j. Addresses actions to be taken when problems occur, identifying individual(s) responsible for corrective action and how this should be documented

Yes Section 4.1 Reference Field SOPs



B3. Sample Handling and Custody a. States maximum holding times allowed from sample collection to extraction and/or analysis for each sample type and, for in-situ or continuous monitoring, the maximum time before retrieval of information

Yes

Sections 3.1.7 & 3.1.8/ Tables 10 & 11

b. Identifies how samples or information should be physically handled, transported, and then received and held in the laboratory or office (including temperature upon receipt) c. Indicates how sample or information handling and custody information should be documented, such as in field notebooks and forms, identifying individual responsible d. Discusses system for identifying samples, for example, numbering system, sample tags and labels, and attaches forms to the plan e. Identifies chain-of-custody procedures and includes form to track custody

B4. Analytical Methods a. Identifies all analytical SOPs (field, laboratory and/or office) that should be followed by number, date, and regulatory citation, indicating options or modifications to be taken, such as sub-sampling and extraction procedures

Yes Section 3.3/ Tables 13 & 14

b. Identifies equipment or instrumentation needed Yes Section 3.4 Reference Appendix A c. Specifies any specific method performance criteria Yes Section 3.2.2/

Table 12

d. Identifies procedures to follow when failures occur, identifying individual responsible for corrective action and appropriate documentation

Yes Section 4.1/ Table 5

e. Identifies sample disposal procedures Yes Section 3.1.4 f. Specifies laboratory turnaround times needed Yes Laboratory

Contract

g. Provides method validation information and SOPs for nonstandard methods

NA



B5. Quality Control a. For each type of sampling, analysis, or measurement technique, identifies QC activities to be used, for example, blanks, spikes, duplicates, etc., and at what frequency

Yes Section 3.3

b. Details what should be done when control limits are exceeded, and how effectiveness of control actions will be determined and documented

Yes Section 3.3

c. Identifies procedures and formulas for calculating applicable QC statistics, for example, for precision, bias, outliers and missing data

Yes Section 2.4.1/ Table 4

B6. Instrument/Equipment Testing, Inspection, and Maintenance a. Identifies field and laboratory equipment needing periodic maintenance, and the schedule for this

Yes Section 3.4/ 3.5

b. Identifies testing criteria c. Notes availability and location of spare parts d. Indicates procedures in place for inspecting equipment before usage e. Identifies individual(s) responsible for testing, inspection and maintenance f. Indicates how deficiencies found should be resolved, re-inspections performed, and effectiveness of corrective action determined and documented

B7. Instrument/Equipment Calibration and Frequency a. Identifies equipment, tools, and instruments that should be calibrated and the frequency for this calibration

Yes Section 3.4

b. Describes how calibrations should be performed and documented, indicating test criteria and standards or certified equipment c. Identifies how deficiencies should be resolved and documented

B8. Inspection/Acceptance for Supplies and Consumables a. Identifies critical supplies and consumables for field and laboratory, noting supply source, acceptance criteria, and procedures for tracking, storing and retrieving these materials Yes Section 3.5

b. Identifies the individual(s) responsible for this



B9. Use of Existing Data (Non-direct Measurements) a. Identifies data sources, for example, computer databases or literature files, or models that should be accessed and used

Yes Section 2.4.1/ 3.6

b. Describes the intended use of this information and the rationale for their selection, i.e., its relevance to project c. Indicates the acceptance criteria for these data sources and/or models d. Identifies key resources/support facilities needed e. Describes how limits to validity and operating conditions should be determined, for example, internal checks of the program and Beta testing

B10. Data Management a. Describes data management scheme from field to final use and storage

Yes Section 3.6

b. Discusses standard record-keeping and tracking practices, and the document control system or cites other written documentation such as SOPs c. Identifies data handling equipment/procedures that should be used to process, compile, analyze, and transmit data reliably and accurately d. Identifies individual(s) responsible for this e. Describes the process for data archival and retrieval f. Describes procedures to demonstrate acceptability of hardware and software configurations g. Attaches checklists and forms that should be used



C. Assessment and Oversight C1. Assessments and Response Actions

a. Lists the number, frequency, and type of assessment activities that should be conducted, with the approximate dates

Yes Section 4.0

b. Identifies individual(s) responsible for conducting assessments, indicating their authority to issue stop work orders, and any other possible participants in the assessment process c. Describes how and to whom assessment information should be reported d. Identifies how corrective actions should be addressed and by whom, and how they should be verified and documented

C2. Reports to Management a. Identifies what project QA status reports are needed and how frequently

Yes Section 4.3

b. Identifies who should write these reports and who should receive this information

D. Data Validation and Usability D1. Data Review, Verification, and Validation

Describes criteria that should be used for accepting, rejecting, or qualifying project data

Yes Section 5

D2. Verification and Validation Methods a. Describes process for data verification and validation, providing SOPs and indicating what data validation software should be used, if any

Yes Section 5

b. Identifies who is responsible for verifying and validating different components of the project data/information, for example, chain-of-custody forms, receipt logs, calibration information, etc. c. Identifies issue resolution process, and method and individual responsible for conveying these results to data users d. Attaches checklists, forms, and calculations



D3. Reconciliation with User Requirements a. Describes procedures to evaluate the uncertainty of the validated data

Yes Section 5

b. Describes how limitations on data use should be reported to the data users