Process Document for Joint Verification of the Sorbisense Ground Water Sampler and Sorbisense GSW40 Passive Sampler Joint Verification Protocol for Volatile Organic Compounds in Groundwater and Sorbisense GWS40 Passive Sampler Joint Test Plan for Volatile Organic Compounds in Groundwater June 2009 Prepared by Amy Dindal Anne Gregg Zachary Willenberg Battelle Memorial Institute 505 King Avenue Columbus, OH 43201-2693 and Christian Gran Gerald Heinicke Louise Schliitter Mette Tjener Anders son NOWATECH/DHI Agern Alle 5, DK-2970 H0rsholm, Denmark and John McKernan Evelyn Hartzell Lora Johnson Lauren Drees U.S. Environmental Protection Agency 26 Martin Luther King Drive Cincinnati, OH 45268 ------- FOREWARD The U.S. Environmental Protection Agency (EPA), Advanced Monitoring Systems (AMS) Center of the Environmental Technology Verification Program (ETV) collaborated with the NOWATECH DHI Water Monitoring Center (DHIWMC), a pilot ETV program in the European Union, to conduct an international joint verification test of a passive ground water sampler. This document, which is actually a compilation of three separate documents, was used by NOWATECH and the AMS Center to jointly verify the performance of this technology. It is composed of a process document, a verification protocol, and a test plan for joint verification. Combined, these three documents satisfy the requirements of an EPA ETV approved verification test/QA plan and ensure that the requirements of both programs are met. The verification protocol and test plan were developed by NOWATECH with input from Battelle, EPA, and other stakeholders. Together these documents satisfy NOWATECH's programmatic requirements. The process document was developed by the AMS Center with input from NOWATECH and the EPA. It was developed as a supplement to the NOWATECH documents, to ensure that all of EPA ETV programmatic requirements are met. All three documents were reviewed and approved via the ETV process prior to the start of testing. ------- TABLE OF CONTENTS Process Document: Section Page 1 INTRODUCTION 6 2 QUALITY SYSTEMS 11 3 VERIFICATION PLANNING 11 4 VERIFICATION TEST IMPLEMENTATION 13 5 ASSESSMENT AND RESPONSE 15 6 DOCUMENTATION AND REPORTING 19 7 REFERENCES 23 Appendix A ROLES OF KEY PERSONNEL 24 Appendix B KICK OFF MEETING CHECKLIST 25 Appendix C REVIEW REPORT FORM 28 Appendix D JOINT VERIFICATION TESTING DOCUMENT AMENDMENT AND DEVIATIONS FORMS 29 Appendix E ASSESSMENT REPORTING FORM 32 Appendix F EXAMPLE VERIFICATION STATEMENT 34 Verification Protocol: 1 TABLE OF CONTENTS II 2 INTRODUCTION 1 2.1 Name of product 1 2.2 Name and contact of vendor 1 2.3 Name of center/verification responsible 1 2.4 Verification Test Organization 1 2.5 Expert group 2 2.6 Verification process 3 3 DESCRIPTION OF THE TECHNOLOGY 3 4 DESCRIPTION OF THE PRODUCT 4 5 APPLICATION AND PERFORMANCE PARAMETER DEFINITIONS 6 5.1 Matrix/matrices 6 5.2Target(s) 6 5.3 Effects 6 5.4 Performance parameters for verification 6 5.5 Additional parameters 8 6 EXISTING DATA 8 6.1 Summary of existing data 8 6.2 Quality of existing data 9 6.3 Accepted existing data 9 7 TEST PLAN REQUIREMENTS 9 7.1 Test design 10 ------- 7.2 Reference analysis 11 7.3 Data management 11 7.4 Quality assurance 11 7.5 Test report 11 8 EVALUATION 11 8.1 Calculation of performance parameters 12 8.2 Evaluation of test data quality 13 8.3 Compilation of additional parameters 13 8.3.1 User manual 13 8.3.2 Product costs 14 8.3.3 Occupational health and environment 15 9 VERIFICATION SCHEDULE 15 10 QUALITY ASSURANCE 15 APPENDIX 1 17 Terms and definitions used in the verification protocol 17 APPENDIX 2 22 References 22 APPENDIX 3 25 Application and performance parameter definitions 25 Test Plan: 1 TABLE OF CONTENTS II 2 INTRODUCTION 1 2.1 Verification protocol reference 1 2.2 Name and contact of vendor 1 2.3 Name of center/test responsible 1 2.4 Expert group 2 3 TEST DESIGN 2 3.1 Test sites 5 3.1.1 Types 5 3.1.2 Addresses 5 3.1.3 Descriptions 5 3.2 Tests 5 3.2.1 Test methods 6 3.2.2 Test staff 8 3.2.3 Test schedule 9 3.2.4 Test equipment 9 3.2.5 Type and number of samples 9 3.2.6 Operation conditions 11 3.2.7 Operation measurements 11 3.2.8 Product maintenance 11 3.2.9 Health, safety and wastes 11 4 REFERENCE ANALYSIS 12 4.1 Analytical laboratory 12 ------- 4.2 Analytical parameters 12 4.3 Analytical methods 12 4.4 Analytical performance requirements 13 4.5 Preservation and storage of reference samples 13 5 DATA MANAGEMENT 13 5.1 Data storage, transfer and control 13 6 QUALITY ASSURANCE 14 6.1 Test plan review 14 6.2 Performance control - reference analysis 14 6.3 Test system control 15 6.4 Data integrity check procedures 16 6.5 Test system audits 16 6.6 Test report review 17 7 TEST REPORT 17 7.1 Test site report 17 7.2 Test data report 17 7.3 Amendment report 17 7.4 Deviations report 17 APPENDIX 1 19 Terms and definitions used in the test plan 19 APPENDIX 2 24 Reference methods and references 24 APPENDIX 3 27 In-house test methods 27 APPENDIX 4 46 In-house analytical methods 46 APPENDIX 5 48 Data reporting forms 48 APPENDIX 6 89 Data management 89 APPENDIX 7 95 Deviations and amendments 95 ------- EXECUTIVE SUMMARY The Nordic Water Technology Verification Center's (NOWATECH) DHI Water Monitoring Center (DHI WMC), a pilot Environmental Technology Verification Program (ETV) in the European Union, and the United States Environmental Protection Agency ETV Program's (EPA ETV) Advanced Monitoring Systems (AMS) Center are jointly verifying the Sorbisense (vendor) GWS40 passive ground water sampler. Under this joint effort, NOWATECH was responsible for developing the verification protocol, preparing the test plan including quality assurance (test/QA), testing, and generating the verification report/verification statement in accordance with their requirements. The AMS Center provided technical and quality assurance oversight throughout the NOWATECH process to ensure EPA ETV requirements were also met, and facilitated reviews and audits by QA personnel, EPA Program management, and stakeholders of the verification protocol, test plan, testing, and verification report. The AMS center also developed a process document to supplement the protocol and test plan developed by NOWATECH and ensure that all of EPA ETV programmatic requirements are met. The process document, combined with the protocol and test plan, satisfy the requirements of an EPA approved verification test/QA plan. This document is a compilation of these three documents. The purpose of this verification is to evaluate a passive ground water sampling technology, which is capable of detecting 10 contaminants: mono-, di-, tri- and - tetrachloroethenes, chloroethene, benzene, toluene, ethylbenzene, xylenes (BTEX), and methyl-fert-butylether (MTBE). Passive sampling is based upon distribution of solutes between the sampled medium, and a collecting medium. Flow of solute from one medium to the other continues until equilibrium is established in the system. The amount of solute in the sampling medium is then determined analytically and can be used to calculate the concentration in the sampled medium. This result will then be compared to results from a standard analytical method for the contaminants of interest, providing information on the precision, accuracy, and range of the technology being verified. Other verification parameters will include determination of the limit of detection, and the robustness of the monitoring technology. ------- Battelle Qj NOWATECH The Business of Innovation WATER.ENVIRONMENT- HEALTH Environmental Technology Verification Program Advanced Monitoring Systems Center Process Document for US EPA ETV AMS CENTER and NOWATECH DHI WMC Joint Verification of the Sorbisense Ground Water Sampler ------- Process Document for US EPA ETV AMS CENTER and NOWATECH DHI WMC Joint Verification of the Sorbisense Ground Water Sampler February 10,2009 Prepared by Battelle 505 King Avenue Columbus, OH 43201-2693 ------- US ETV AMS Center and NOWATECH DHIWMC Joint Verification Process Document Page 3 of 3 5 Date: 2/10/2009 TABLE OF CONTENTS Section Page 1 INTRODUCTION 6 2 QUALITY SYSTEMS 11 3 VERIFICATION PLANNING 11 4 VERIFICATION TEST IMPLEMENTATION 13 5 ASSESSMENT AND RESPONSE 15 6 DOCUMENTATION AND REPORTING 19 7 REFERENCES 23 Appendix A ROLES OF KEY PERSONNEL 24 Appendix B KICK OFF MEETING CHECKLIST 25 Appendix C REVIEW REPORT FORM 28 Appendix D JOINT VERIFICATION TESTING DOCUMENT AMENDMENT AND DEVIATIONS FORMS 29 Appendix E ASSESSMENT REPORTING FORM 32 Appendix F EXAMPLE VERIFICATION STATEMENT 34 ------- US ETV AMS Center and NOWATECH DHIWMC Joint Verification Process Document Page 4 of 3 5 Date: 2/10/2009 List of Figures Page Figure 1. Organization Chart for the Joint Verification Test of Sorbisense GWS40 Passive Ground Water Sampler 7 List of Tables Table 1.0 Assessments for the Joint Verification 18 Table 2.0 Document and Reporting Responsibilities for the Joint Verification 22 ------- US ETV AMS Center and NOWATECH DHIWMC Joint Verification Process Document Page 5 of 3 5 Date: 2/10/2009 DISTRIBUTION LIST John McKernan Lauren Drees US EPA 26 West Marin Luther King Drive Mail Code: 208 Cincinnati, OH 45268 Christian Gran Gerald Heinicke Louise Schliitter DHI Agern Alle 5, DK-2970 H0rsholm, Denmark. Hubert de Jonge Vendor- Sorbi sense Niels Pedersens Alle 2 DK-8830 Tjele, Denmark Amy Dindal Anne Gregg Zachary Willenberg Battelle 505 King Ave. Columbus, OH 43201 ------- US ETV AMS Center and NOWATECH DHIWMC Joint Verification Process Document Page 7 of 35 Date: 2/10/2009 section. The names of the key personnel and their roles during this verification are presented in Appendix A. United States Environmental Protection Agency, Environmental Technology Verification Program (US EPA ETV) Battelle, US EPA ETV Advanced Monitoring Systems Center Stakeholder Committee Sorbisense (Vendor of GWS40) Expert Group/External Peer Reviewers Nordic Water Technology Verification Centers Project (NOWATECH) DHI, NOWATECH Water Monitoring Center DHI Testing Staff Figure 1. Organization Chart for the Joint Verification Test of Sorbisense GWS40 Passive Ground Water Sampler ------- US ETV AMS Center and NOWATECH DHIWMC Joint Verification Process Document Page 8 of 35 Date: 2/10/2009 1.1 Sorbisense Involvement Sorbisense, the technology vendor, has entered into agreements with both Battelle and DHI for this joint ETV verification. The vendor will provide the following support during joint verification of the vendor's technology: »»» A person from the vendor's organization to be Battelle's and DHI's point of contact and to lead vendor's participation in joint verification of the vendor's technology; *»* Review and comment on the joint verification testing documents, including Verification Protocol, Test Plan, Verification Report, Verification Statement, and other documents pertaining to joint verification of the vendor's technology as requested by Battelle and/or DHI; »»» Permission to post/cite information about the vendor's technology, including the Verification Protocol, Test Plan, Verification Report, and Joint Verification Statement, on the US ETV website (http://www.epa.gov/etv/) and in other program publications; *»* Equipment/materials for testing, appropriate training in its operation, and on- site support on an as needed basis; »»» At no cost to DHI or Battelle or US EPA, the vendor's technology and associated equipment/materials for testing, appropriate training in its operation, and on-site support on an as needed basis; and »»» Written descriptions, diagrams, and/or photographs of the vendor's technology, as input for the Verification Protocol, Test Plan and Verification Report. 1.2 DHI Involvement During the verification of vendor's technology, DHI will: »»» Provide a person from DHI's organization to be Battelle's and the vendor's point of contact and to lead DHI's participation in verification of the vendor's technology; *»* Prepare and revise the Verification Protocol, Test Plan, Verification Report, Verification Statement, and other documents pertaining to the verification of ------- US ETV AMS Center and NOWATECH DHIWMC Joint Verification Process Document Page 9 of 35 Date: 2/10/2009 the vendor's technology and allow Battelle, US EPA, and the Expert Group the opportunity to review and comment on these documents; »»» Assemble a team of qualified technical staff to conduct the verification test in accordance with the Verification Protocol, Test Plan, and this document; »»» Ensure that all quality procedures specified in the Verification Protocol, Test Plan, NOWATECH Center Quality Manual Template1, and this document are followed; *»* Conduct a (virtual) j oint kick-off meeting with Battelle prior to test initiation; »»» Provide a summary of the QA activities performed by the DHI WMC Internal Auditor during the verification testing; and »»» Provide permission to post/cite information about DHI's involvement in the joint verification, including the Joint Verification Protocol, Test Plan, Verification Report, and Verification Statement, on the US ETV website on the US ETV website and in other program publications. 1.3 Battelle Involvement During the ETV verification of the vendor's technology, Battelle will: »»» Provide a person from Battelle's organization to be DHI's and the vendor's point of contact; »»» Prepare a procedural document outlining the process of the vendor's technology verification for acceptance by the US EPA (this document); »»» Provide input, review, and comment on the Verification Protocol, Test Plan, Verification Report, Verification Statement, and other documents pertaining to verification of the vendor's technology; *»* Conduct a (virtual) j oint kick-off meeting with DHI (using checklist in Appendix B) prior to test initiation; »»» Strive to obtain US EPA approval for the final Verification Protocol, Test Plan, Verification Report, including a Verification Statement; and »»» Comply with all quality procedures and program requirements specified in the Test/QA Plan, Quality Management Plan for the ETV AMS Center (ETV AMS Center QMP)2, and in the U.S "Environmental Technology Verification Program Quality Management Plan" (US ETV QMP)3, as follows: ------- US ETV AMS Center and NOWATECH DHIWMC Joint Verification Process Document Page 10 of 35 Date: 2/10/2009 o Prepare and get US EPA ETV approval of an audit checklist and provide the checklist to DHI prior to the audit; o Conduct a technical systems audit once during the verification test; o Audit at least 10% of the verification data; o Prepare and distribute an assessment report for each audit; o Verify implementation of any necessary corrective action; and o Provide a summary of the quality assurance/quality control (QA/QC) activities and results for the verification reports. 1.4 NOWATECH Involvement NOWATECH responsibilities are based on the requirements stated in the NOWATECH Center Quality Manual Template.1 1.5 US EPA Involvement A complete list of US EPA's responsibilities in the AMS Center are based on the requirements stated in the AMS Center ETV QMP.2 The US EPA will provide technical and quality oversight of all ETV AMS Center activities to ensure compliance with the US ETV program requirements. 1.6 Stakeholder Committee and Expert Group Involvement The AMS Center's Water Stakeholder Committee is made up of buyers and users of such technologies. This committee assists in prioritizing the types of technologies to be verified and in specific cases, provides testing support. It also has representatives that assist in review of the Test/QA plans, Verification Reports, and Verification Statements. The AMS Center Water Stakeholder Committee provided concurrence for the Center to proceed with testing in this area. The stakeholders have been kept apprised of progress throughout the planning process for this test and have provided input during progress meetings on the test design. In addition, the US ETV AMS Center obtains the peer review of two external peer reviewers and one EPA peer reviewer who are not directly involved with the verification test. The NOWATECH ETV program uses an Expert Group to perform the external peer review ------- US ETV AMS Center and NOWATECH DHIWMC Joint Verification Process Document Page 11 of 35 Date: 2/10/2009 of the documents and give input on the verification. For this test, the Expert Group is made up of three individuals to fulfill the requirements of both programs. These individuals are named with their affiliations in the Verification Protocol6 and Test Plan7. 2 QUALITY SYSTEMS The Battelle and DHI quality systems to be implemented for this joint verification will conform with the specifications listed in: • ANSI/ASQ E4-2004, " Specifications and Guidelines for Quality Systems for Environmental Data Collection and Environmental Technology Programs"4 or the comparable International Standards Organization (ISO) 90015. Per the US EPA ETV QMP3' verification organization quality systems, such as DHFs quality systems, are to be reviewed and approved by verification organization management, the AMS Center Manager, and the AMS Center Quality Manager. Since not all of the NOWATECH/DHI quality documents have been finalized, this process document will serve to define the specific quality activities that will be performed by Battelle and DHI for this joint verification. 3 VERIFICATION PLANNING In performing the verification test, DHI and Battelle will follow the technical and QA procedures specified in the NOWATECH Verification Protocol6, NOWATECH Test Plan7, and this process document. Because DHI is preparing the Verification Protocol, Test Plan, conducting the testing activities, and preparing the Verification Report and Verification Statement, the procedure and expectations of the US EPA ETV program need to be clarified in a document that explains the process and requirements (this document). 3.1 Planning the Test Design Initially, the verification test design process produced a Verification Protocol6 and Test Plan7 based upon the NOWATECH and US EPA ETV processes. These two documents together represent the equivalent of a US ETV AMS Center Test/QA plan. ------- US ETV AMS Center and NOWATECH DHIWMC Joint Verification Process Document Page 12 of 35 Date: 2/10/2009 The protocol includes an Application and Performance Parameter Definition Document (Appendix 3 in the Verification Protocol6) that developed relevant parameters and ranges hereof for verification considering the vendor stated performance, government standards, and other technologies and methods in the market. It also evaluated existing data that has been collected to decide whether it could be used as part of the verification or whether it could be used as the vendor stated claims to help decide on relevant performance parameters to test during the verification. The Application and Performance Parameter Definition Appendix was not jointly produced and is a specific process within the NOWATECH program; therefore, it was not reviewed by the US EPA ETV program. In designing this verification test, DHI staff used consensus-accepted test design and a previously peer reviewed US EPA ETV Test/QA Plan8. The design also takes into account constraints of time, scheduling, and resources. All relevant activities pertaining to environmental data operations have been identified, as well as performance specifications and the appropriate controls. Finally, a process document (this document) was produced by Battelle to address the process and differences between the programs to ensure a successful joint verification. Collectively, these three documents (the NOWATECH Verification Protocol6, NOWATECH Test Plan7, and Process Document for the US EPA ETV AMS Center and NOWATECH DHI WMC Joint Verification of the Sorbisense Ground Water Sampler) are referred to as the "testing documents". The US EPA ETV process utilized its Water Stakeholder Committee to guide the test design process. It provided concurrence for the Center to proceed with testing in this area. The stakeholders have been kept apprise of progress throughout the planning process for this test and have provided input during progress meetings on the test design. The committee also identified potential peer reviewers to perform a formal technical review of the testing documents. The NOWATECH ETV program uses an Expert Group to perform the external peer review of the documents and give input on the verification. For this test, the Expert Group is made up of individuals to fulfill the requirements of both programs. It includes three individuals that have extensive experience in the field of ground water monitoring, one EPA reviewer and two non-EPA reviewers. These reviewers have no direct involvement in the verification test beyond providing their reviews. The comments from the reviews ------- US ETV AMS Center and NOWATECH DHIWMC Joint Verification Process Document Page 13 of 35 Date: 2/10/2009 performed by the Expert Group of the testing documents and the Verification Report and Verification Statement will be reconciled by DHI. The review process will utilize the Review Report Form produced by the NOWATECH and is included in Appendix C. 4 VERIFICATION TEST IMPLEMENTATION This technology performance verification will be implemented according to the Verification Protocol6 and the Test Plan7 (including technical procedural documents) prepared during planning. Generation of verification test data will not be initiated until the approved Verification Protocol and Test Plan are in place. Any data generated before the required documents are approved will have to be repeated. In performing the verification test, DHI will perform an internal audit of the data collection and handling that follows the technical and QA procedures specified in these documents, as well as, the NOWATECH Center Quality Manual Template1. The Battelle AMS Center will perform a technical systems audit (TSA) to be sure that these requirements are being met. A virtual joint kick-off meeting will be held prior to the start of the verification test to review procedures for the test with all verification testing staff. The joint kick-off meeting checklist is provided in Appendix B. Test personnel will have access to the approved testing documents, approved changes to testing documents, and all referenced documents. When a prescribed sequence for the work is defined in the testing documents, work performed shall follow that sequence. Changes to that sequence need to be documented by either amendment (planned changes) or deviation (unplanned changes). All verification test activities will be documented. Suitable documents are bound notebooks (e.g. laboratory record books, or LRBs), field and laboratory data sheets, spreadsheets, computer records, and output from instruments (both electronic and hardcopy). All documentation is implemented as described in the testing documents. All implementation activities are traceable to the testing documents and to the test personnel. The responsibilities of specific test personnel listed in these testing documents that leave the project before it is completed will be reassigned. When work cannot be implemented according to the approved testing documents, DHI shall be responsible for providing a written amendment or a deviation report for the test records. Amendments are produced for changes that are made to the testing document before ------- US ETV AMS Center and NOWATECH DHIWMC Joint Verification Process Document Page 14 of 35 Date: 2/10/2009 the proposed change will be made. Amendments must be approved by the DHI WMC Verification Responsible, the DHI WMC Internal Auditor, Battelle AMS Center Manager, and the Battelle AMS Center Quality Manager. Following approval, the amendment will be distributed to all internal personnel holding a copy of the testing documents. A deviation report is produced for any changes to the testing document that occurred during the test. Deviation reports must be retained in the verification test records and summarized in the Verification Report. Frequent deviations from established procedures should result in a retrospective review of the written document and possible revision. Amendments and deviations will include all the information displayed on the forms shown in Appendix D. All persons responsible for performing verification testing and Sorbisense will receive copies of the final versions of the Verification Protocol6 and the Test Plan7 and associated documentation provided by DHI. Current versions of the Verification Protocol6 and the Test Plan7 and any applicable methods and SOPs are required to be physically in place at the technology verification testing sites. Battelle oversight and inspection of the verification test will be provided by the Battelle AMS Center Quality Manager and will be over the course of one week. An audit checklist will be prepared and approved by the EPA AMS Center Project Officer and EPA AMS Center Quality Manager. The audit checklist will be provided to DHI prior to the audit. The audit will begin with an "In Briefing" conducted by the Battelle AMS Center Quality Manager to specify and clarify the necessary points of the audit. Testing during laboratory, standpipe, and field activities will be observed along with viewing the external laboratory performing the reference analyses. To verify full implementation of the testing documents, the inspection will include the testing process and any documentation associated with the process, such as sample chain of custody transfers, instrument maintenance and calibration, sample preparation and analysis, and data records. At the conclusion of the audit there will be an "Exit Briefing" held to discuss the findings and corrective actions necessary. The Battelle AMS Center Quality Manager will also provide a written report, verify the completion of any corrective actions needed, and retain a copy of the report with permanent Battelle AMS Center Quality Manager records. The report will be commented on by DHI WMC and comments addressed before it is distributed. The Assessment Reporting Form is presented in Appendix E. The EPA AMS Center Project Officer will be included in the routing of the inspection results and a written copy provided to both the EPA AMS Center Project Officer and EPA AMS Center Quality Manager. ------- US ETV AMS Center and NOWATECH DHIWMC Joint Verification Process Document Page 15 of 35 Date: 2/10/2009 5 ASSESSMENT AND RESPONSE Assessments will be planned, scheduled, conducted, and reported in order to measure the efficacy of the Battelle and DHI WMC quality procedures and verification execution. The testing will be audited internally by the WMC Internal Auditor in accordance with the Verification Protocol6 and Test Plan7. The WMC Document Reviewer and Internal Auditor equate to the Battelle AMS Center Quality Manager. The WMC Document reviewer will perform the technical review of the Test Plan and Verification Report documents. The WMC Internal Auditor will perform an audit based upon identified critical points. The procedure includes two main steps: • Check that the protocol/plan is prepared and followed in accordance with the DHI QMS and the WMC QM (horizontal audit) • Check of verification/test parameters and data at the identified critical points, ie a vertical audit in lab, office and/or field. Data from the testing will be controlled by the Verification Responsible and the Test Responsible when received. Data integrity will be controlled by the Test Responsible (transfer of raw data to spreadsheets) and Verification Responsible (calculations as part of evaluations) as spot checks (5% of the data). Monitoring of the work process to be conducted by the Battelle AMS Center Quality Manager will be done to: • Ensure satisfactory performance based on requirements, • Ensure required actions (as specified in implementation documents) are performed so that routine measurements meet specifications, • Ensure preventive maintenance is performed and documented as specified in facility and study records, • Ensure calibrations are performed as planned and prescribed, • Ensure corrective actions are implemented and documented as planned in response to items of nonconformance. Assessment types, responsibility, and schedule for this joint verification will be as shown in Table 1.0, and are defined as follows: Quality Systems Audit (QSA), an on-site review of the implementation of the WMC quality procedures. This review is used to verify the existence of, and ------- US ETV AMS Center and NOWATECH DHIWMC Joint Verification Process Document Page 16 of 35 Date: 2/10/2009 evaluate the adequacy of, the internal quality system. This review will be done in conjunction with the Technical Systems Audit. Technical Systems Audit (TSA), a qualitative on-site evaluation of sampling and/or measurement systems associated with a particular verification test. The objective of the TSA is to assess and document the acceptability of all facilities, maintenance, calibration procedures, reporting requirements, sampling, and analytical activities, and quality control procedures in the test. Conformance with the testing documents and associated methods and/or Standard Operating Procedures is the basis for this assessment. The Battelle AMS Center Quality Manager will prepare and use an audit checklist that is approved by the EPA AMS Center Quality Manager. The checklist will be available to DHI before the audit takes place. This review will be done in conjunction with the QSA. Performance Evaluation Audits (PE), a quantitative evaluation of the measurement systems used. The type and frequency of performance evaluation self-audits are specified in the Test plan for the joint verification test. The value or composition of reference materials must be certified or verified prior to use, and the certification or verification must be adequately documented. The Battelle AMS Center Quality Manager will review results of PE audits during the TSA; however, it is most preferable for the PE results to be shared with Battelle as soon as they are available, so that any issues can be resolved. Audits of Data Quality, an examination of the verification data after they have been collected and verified by project personnel. The Battelle AMS Center Quality Manager will audit at least 10% of all verification data, including equations and calculations. ------- US ETV AMS Center and NOWATECH DHIWMC Joint Verification Process Document Page 17 of 35 Date: 2/10/2009 Table 1.0 Assessments for the Joint Verification Assessment Subject of Minimum Reason for Tool Assessors Responders Assessment Frequency Assessment Report Reviewed by Quality Systems Audit Technical Systems Audits Performance Evaluation Audits Audits of Data Quality Battelle AMS Center Quality Manager Battelle AMS Center Quality Manager and DHI Internal Auditor Battelle AMS Center Quality Manager and DHI Internal Auditor Battelle AMS Center Quality Manager and DHI Internal Auditor DHI DHI DHI DHI NOWATECH Quality Manual Template Verification Protocol, Test Plan, and Process Document Verification Protocol, Test Plan, and Process Document raw data and summary data once once once At least 10% of the verification data assess quality management practices of verification collaborators assess technical quality of verification tests assess measurements performance assess data calculations and reporting EPA directors of quality assurance EPA AMS Center Project Officer Battelle AMS Center Manager and Test Coordinator NOWATECH WMC Verification Responsible EPA AMS Center Project Officer EPA AMS Center Quality Manager Battelle AMS Center Manager and Test Coordinator NOWATECH WMC Verification Responsible EPA AMS Center Project Officer EPA AMS Center Quality Manager Battelle AMS Center Manager and Test Coordinator NOWATECH WMC Verification Responsible EPA AMS Center Project Officer EPA AMS Center Quality Manager Battelle AMS Center Manager and Test Coordinator NOWATECH WMC Verification Responsible 5.1 Assessment Reports Each assessment must be fully documented. The Battelle AMS Center Quality Manager and the DHI WMC Verification Responsible will archive all assessment reports generated for this verification test. Each assessment must be responded to by the appropriate level of management. The Battelle quality assessment reports shall require a written response by the person performing the inspected activity, and acknowledgment of the assessment by the Battelle AMS Center Test ------- US ETV AMS Center and NOWATECH DHIWMC Joint Verification Process Document Page 18 of 35 Date: 2/10/2009 Coordinator. The Assessment Reporting Form is provided in Appendix E. An assessment report will also be prepared by the WMC Internal Auditor and provided to the Battelle AMS Center test coordinator for archive. Corrective action must be documented and approved on the original assessment report, with detailed narrative in response to the assessor's finding. Initials and date are required for each corrective action response. Acknowledgment of the response will be provided by the Battelle Test Coordinator. Implementation of corrective actions must be verified by the Battelle AMS Center Quality Manager or the DHI Internal Auditor to ensure that corrective actions are adequate and have been completed. This will be done in real-time if corrective actions can be immediately performed and signed off on the assessment report. Alternatively, should the corrective action require additional approvals not immediately available on-site, the DHI Internal Auditor may need to repeat the inspection, as the designee of the Battelle AMS Center Quality Manager, in order to corroborate the implementation and effectiveness of the corrective action. 5.2 Stop Work Assessor responsibility and authority to stop work during a verification test for quality considerations is delegated to DHI and Battelle. DHI must ensure compliance with all applicable Danish federal, state, and local safety policies during the performance of verification testing. Should it be determined during an assessment that test objectives of acceptable quality cannot be achieved during performance of verification testing, the Battelle AMS Center is responsible for immediately notifying the DHI WMC Verification Responsible of the need to consider a stop work order. The DHI WMC Verification Responsible will then direct the staff accordingly. The EPA AMS Center Quality Manager will notify the EPA AMS Center Project Officer if work of inadequate quality is discovered. Documentation is required of any stop work order and the corrective action implemented and shall be maintained as part of the Battelle quality ------- US ETV AMS Center and NOWATECH DHIWMC Joint Verification Process Document Page 19 of 35 Date: 2/10/2009 records, with a copy provided to the EPA AMS Center Project Officer and EPA AMS Center Quality Manager. 5.3 Response Responses to TSA adverse findings should be addressed within 10 working days after the TSA report is completed. However, it is expected that findings that have a direct impact on the conduct of a verification test will be corrected immediately following notification of the finding. Responses to each adverse finding will be documented in the assessment report. Ideally, assessment reports will provide space after each adverse finding for a response to be recorded. The response will indicate the corrective action taken or planned to address the adverse finding. The response should be signed and dated by the staff responsible for implementing the corrective action. Any corrective action that cannot be immediately implemented will be verified following completion by the Battelle AMS Center Quality Manager or designee. Once all corrective action associated with an assessment report has been taken, the Battelle AMS Center Quality Manager or designee will initial the corrective action in the assessment report thus documenting verification of the corrective action. Any impact that an adverse finding had on the quality of verification test data should be addressed in the verification report. The TSA report, with responses to adverse findings recorded within, will be sent to EPA within 10 working days after the Battelle AMS Center Quality Manager has verified all corrective actions. 6 DOCUMENTATION AND REPORTING 6.1 Responsibilities for these activities concerning documentation and reporting are summarized in Table 2.0 and are detailed below. 6.1.1 Preparation Individual case requirements and this document shall guide document ------- US ETV AMS Center and NOWATECH DHIWMC Joint Verification Process Document Page 20 of 3 5 Date: 2/10/2009 and record content and/or format. Guidance for content and/or format are derived by the EPA ETV and NOWATECH directives and the following documents: • ANSI/ASQ E4-20044. • ETV AMS Center QMP2. • US EPA document "EPA QA/R-2, EPA Requirements for Quality Management Plans, March 2001. • NOWATECH Center Quality Manual Template1. 6.1.2 Review/Approval. Record review/approval for joint verification testing documents shall be performed by qualified technical and/or management personnel as described in Table 2.0. The individual reviewer shall have access to all needed references. ------- US ETV AMS Center and NOWATECH DHIWMC Joint Verification Process Document Page 21 of 35 Date: 2/10/2009 Table 2.0 Document and Reporting Responsibilities for the Joint Verification* Preparation/ Record Type Updating Review Approval Finals Distributed to: Verification Protocol and Test Plan (including SOPs, amendments and deviations) Raw data Verification Report ETV Verification Statement Audit Reports Audit Reports DHI DHI DHI DHI DHI Internal Auditor Battelle AMS Center Quality Manager Battelle AMS Center Manager Battelle AMS Center Qualify Manager EPA AMS Center Quality Manager EPA AMS Center Project Officer NOWATECH WMC Verification Responsible DHI Document Reviewer Stakeholders/Expert Group Vendor WMC Internal Auditor Battelle AMS Center Manager Battelle AMS Center Qualify Manager EPA AMS Center Quality Manager NOWATECH WMC Verification Responsible Vendor Stakeholders/Expert Group Battelle AMS Center Manager Battelle AMS Center Qualify Manager EPA AMS Center Project Officer EPA AMS Center Quality Manager NOWATECH WMC Verification Responsible WMC Document Reviewer Vendor ETV Program Director Stakeholders/Expert Group DHI Test Responsible NOWATECH WMC Verification Responsible Battelle AMS Center Manager Battelle Verification Test Coordinator NOWATECH WMC Verification Responsible WMC Test Responsible EPA AMS Center Project Officer EPA AMS Center Quality Manager NOWATECH WMC Verification Responsible N/A EPA AMS Center Project Officer EPA AMS Center Quality Manager NOWATECH WMC Verification Responsible EPA Laboratory Director Battelle Management EPA AMS Center Project Officer EPA AMS Center Quality Manager DHI Director RDI and Quality Management NOWATECH Steering Committee Head N/A N/A Testing Staff Vendor EPA AMS Center Project Officer EPA AMS Center Quality Manager NOWATECH WMC Verification Responsible EPA can request copies ETV Program Director EPA AMS Center Project Officer ETV Webmaster Vendor NOWATECH WMC Verification Responsible ETV Program Director EPA AMS Center Project Officer Battelle AMS Center Manager NOWATECH WMC Verification Responsible ETV Webmaster Vendor NOWATECH WMC Verification Responsible Battelle AMS Center Quality Manager Battelle AMS Center Manager Battelle Verification Test Coordinator EPA AMS Center Project Officer EPA AMS Center Quality Manager EPA AMS Center Project Officer EPA AMS Center Quality Manager Battelle AMS Center Manager Battelle Verification Test Coordinator NOWATECH WMC Verification Responsible *See Appendix A for the roles and names of the individuals filling these roles. A6.2 Reporting The end result of the joint verification process will be a Verification Report and Verification Statement for the Sorbisense GWS40. The review and approval procedures for the verification report and statement for US EPA ETV program purposes are given in Table 2.0. The Verification Report will be peer-reviewed by external reviewers in the Expert Group and the Verification Statement will be signed by an EPA laboratory director, Battelle management, the DHI Director of Research and Quality Management and the NOWATECH Steering Committee Head. Appendix F presents a preliminary template for a ------- US ETV AMS Center and NOWATECH DHIWMC Joint Verification Process Document Page 22 of 3 5 Date: 2/10/2009 Verification Statement. This document will be expanded and organized to meet US EPA ETV and NOWATECH program requirements. All logos will appear on the Verification Statement. These will include: US ETV, Battelle, NOWATECH, DHI, and US EPA logos. All logos except the US EPA logo will appear on the cover page of all other joint testing documents (Test Plan, Verification Protocol, Verification Report). All of these testing documents will be made publicly available on the US EPA ETV Web site (www.epa.gov/etv) regardless of the technology's performance. The vendor will comply with both the NOWATECH and US EPA ETV policies on referencing the verification documents of their technology. ------- US ETV AMS Center and NOWATECH DHIWMC Joint Verification Process Document Page 23 of 3 5 Date: 2/10/2009 REFERENCES 1. NOWATECH. ETV Test Center and Test Organization: Center Quality Manual Template. December 2008. 2. Battelle. Quality Management Plan for the ETV Advanced Monitoring Systems Center. Version 7.0. 11-17-2008. 3. United States Environmental Protection Agency. Environmental Technology Verification Program Quality Management Plan. Version 3.0. January 2008. 4. American Society for Quality. ANSI/ASQ E4-2004. Quality systems for environmental data and technology programs - Requirements with guidance for use. 1-4-2004. 5. International Standardization Organization. ISO 9001. Quality management systems -Requirements. 11-15-2008. 6. DHI. Sorbisense GWS40 Passive Sampler, Joint Verification Protocol. January 2009. 7. DHI. Sorbisense GWS40 Passive Sampler, Joint Test Plan. January 2009. 8. Sandia National Laboratories. Groundwater Sampling Technologies Verification Test Plan. Environmental Technology Verification Program. Version 2.0. July 1999. ------- US ETV AMS Center and NOWATECH DHIWMC Joint Verification Process Document Page 24 of 3 5 Date: 2/10/2009 APPENDIX A ROLES OF KEY PERSONNEL NOWATECH Role: NOWATECH person who signs the Verification Statement: NOWATECH Steering Committee Head - Christian Gran DHI Water Monitoring Center (DHI WMC) Roles: DHI person who signs the Verification Statement: Director of Research and Quality - J0rn Rasmussen WMC Verification Responsible: Christian Gran WMC Test Responsible: Gerald Heinicke WMC Document Reviewer: Anders Lynggaard Jensen WMC Internal Auditor: Louise Schliitter WMC Verification and Test staff: several - see protocol and plan US EPA ETV Roles: EPA person who signs the Verification Statement: National Risk Management Research Laboratory (NRMRL) Director - Sally Gutierrez EPA AMS Center Project Officer: John McKernan EPA AMS Center Quality Manager: Lauren Drees, EPA NRMRL Director for Quality Assurance Battelle Advanced Monitoring Systems (AMS) Center Roles: Battelle person who signs the Verification Statement: Chemical, Environmental and Materials Operations Manager - Lisa McCauley AMS Center Manager: Amy Dindal AMS Center Quality Manager: Zach Willenberg AMS Center Test Coordinator: Anne Gregg Parallel Roles between the NOWATECH and US EPA ETV programs: Verification Responsible = Center Manager Test Responsible = Center Test Coordinator Internal Auditor + Document Reviewer = Center Quality Manager ------- US ETV AMS Center and NOWATECH DHIWMC Joint Verification Process Document Page 25 of 3 5 Date: 2/10/2009 APPENDIX B KICK OFF MEETING CHECKLIST ETV JOINT VERIFICATION TEST KICK-OFF MEETING PURPOSE To prepare verification testing staff for the NOWATECH and US EPA ETV AMS Center joint verification test and review critical logistical, technical, and administrative aspects of the test. The kick-off meeting will be scheduled prior to the start of testing. It should be near the start of the test but allow time for the test coordinator to address any lingering issues. FORM The kick off meeting will be virtual, i.e. based upon phone and WebEx sharing of documents. STAFF TO ATTEND • Verification test coordinator/responsible (DHI and Battelle) • ETV program manager (Battelle) • QA manager (Battelle) • US EPA ETV program staff and NOWATECH (invited but optional) All testing staff involved in all. phases of test will subsequently have a kick-off meeting on- site with the DHI WMC verification Responsible. The external laboratory is informed through requisitions of analyses only. PROJECT MANAGEMENT • Review roles/responsibilities of all staff attending meeting • Stakeholders, EPA/ETV program manager, and EPA/QA staff pre-notified of testing schedule and start date? • Review test schedule • Formal distribution of final, signed hard-copy Test/QA plan made to all staff involved. • Documentation of all pertinent forms. o Peer review forms on Protocol document and Test plan. Must include one EPA reviewer/two non-EPA peer reviewers. o Final Test/QA plan approved by vendor. o Vendor-Collaborator agreement signed and stored in project files? o Documentation that the vendor is satisfied that the staff operating the technology are proficient in its use. QUALITY ASSURANCE ------- US ETV AMS Center and NOWATECH DHIWMC Joint Verification Process Document Page 26 of 3 5 Date: 2/10/2009 • Copies of all standard methods cited or included in the Test plan available to testing staff and in laboratory where test will be performed? • EPA QA staff pre-notified of test start date? • Remind testing staff to sign and date everything. • If samples are to be transported between labs, field sites, and DHI bring chain-of- custody form to meeting, review how to complete, and where to obtain form. • Review deviation/amendment procedures at meeting - what to do in the middle of a test if testing document cannot be followed - who to notify/what forms to file. • Review testing document at meeting - identify key testing procedures and critical steps to ensure no ambiguity or questions. • Are or will there be copies of the certificates of analysis in the verification test records? • When will PE audit be performed? Who will perform? Has materials/equipment been purchased or obtained for the PE audit? What are QC limits? What to do if QC limits are not met? Who to contact? • Will regular communication between DHI and Battelle be maintained? If so, how? Daily/weekly email updates? TECHNICAL • Emphasize to testing staff to document anything and everything that is observed about the technologies, particularly if there are unusual sample results (e.g., sample color). • Are provisions made to handle daily preparation of solutions/standards, if necessary? • Take digital photos of all test activities. DATA/REPORTING • Review data recording forms or sheets at meeting or discuss how/where will data be recorded for each testing activity • How are data going to be converted electronically? Are data saved in technology undergoing verification and then exported to Excel? Or will data be recorded manually by the operators? If so, how will transcription errors be avoided? • Data review - who will be doing two week review for each data set collected? If Battelle staff not on-site, how will data be transmitted to Battelle? • Distribute and review report schedule. Reporting should begin at the same time as testing. ------- US ETV AMS Center and NOWATECH DHIWMC Joint Verification Process Document Page 27 of 3 5 Date: 2/10/2009 APPENDIX C REVIEW REPORT FORM Review report Document title: Reviewer name: Name: Organization: Address: Telephone: E-mail Document date: November 2008 Review date: Review results Rate items Contents Scope Organization Data quality Method validity Conclusions Other (specify) Satisfactory Unsatisfactory Overall recommendation Acceptable as is Minor revisions Major revisions Not acceptable Reason ------- US ETV AMS Center and NOWATECH DHIWMC Joint Verification Process Document Page 28 of 3 5 Date: 2/10/2009 Revision details Topic Report chapter, section, page Revision required Reason Revision action(to be filled in by document owner during revision after review) Add additional rows, if pertinent. ------- US ETV AMS Center and NOWATECH DHIWMC Joint Verification Process Document Page 29 of 3 5 Date: 2/10/2009 APPENDIX D JOINT VERIFICATION TESTING DOCUMENT AMENDMENT AND DEVIATIONS FORMS AMENDMENT TESTING DOCUMENT TITLE AND DATE: AMENDMENT NUMBER: EFFECTIVE DATE: PART TO BE CHANGED/REVISED: CHANGE/REVISION: REASON FOR CHANGE: ORIGINATED BY: Battelle AMS Center Test Coordinator or DHI WMC Test Responsible DATE APPROVED BY: DHI WMC Internal Auditor DHI WMC Verification Responsible DATE DATE Battelle AMS Center Quality Manager Battelle AMS Center Manager DATE DATE Required Distribution with documentation - All individuals/organizations listed on distribution for the applicable Test/QA Plan, including but not limited to: ------- US ETV AMS Center and NOWATECH DHIWMC Joint Verification Process Document Page 30 of 35 Date: 2/10/2009 Battelle AMS Center Manager NOWATECH WMC Verification Responsible Testing Staff Battelle Quality Manager WMC Internal Auditor Subcontractors (if any) EPA/ETV AMS Center Project Officer EPA/ETV AMS Center Quality Manager Vendor ------- US ETV AMS Center and NOWATECH DHIWMC Joint Verification Process Document Page 31 of 35 Date: 2/10/2009 DEVIATION REPORT TESTING DOCUMENT TITLE AND DATE: DEVIATION NUMBER: DATE OF DEVIATION: DESCRIPTION OF DEVIATION: CAUSE OF DEVIATION: IMPACT OF DEVIATION ON THE TEST: CORRECTIVE ACTION: ORIGINATED BY: Battelle AMS Center Test Coordinator or DHI WMC Test Responsible DATE ACKNOWLEDGED BY: DHI WMC Quality Manager Battelle AMS Center Quality Manager DATE DATE Required Distribution with documentation - All individuals/organizations listed below: Battelle AMS Center Manager NOWATECH WMC Verification Responsible Battelle AMS Center Quality Manager WMC Internal Auditor ------- US ETV AMS Center and NOWATECH DHIWMC Joint Verification Process Document Page 32 of 35 Date: 2/10/2009 APPENDIX E ASSESSMENT REPORTING FORM Quality Assurance Routing Sheet Verification Test: Audit Type: Test Coordinator: Vendor: Auditor: Date: Test Coordinator, please complete the attached form indicating CORRECTIVE ACTION TAKEN (IF NEEDED), sign and date this Routing Sheet in the space provided beside your name, and return the entire set when completed to the Battelle AMS Center Quality Manager no later than . Route To Signature Date WMC Test Responsible AMS Center Test Coordinator Approval Battelle AMS Center Manager Battelle AMS Center Quality Manager NOWATECH WMC Verification Responsible ------- US ETV AMS Center and NOWATECH DHIWMC Joint Verification Process Document Page 33 of 35 Date: 2/10/2009 Audit Comment Sheet Instructions: The Battelle AMS Center Quality Manager will fill out the first column for the audit indicated above. The Verification Test Coordinator (or assigned responder) will respond to the comments and initial and date the response in column three. The Battelle AMS Center Quality Manager will verify and document that the response/corrective action has been completed by initialing and dating the final column. QA Comment Testing Coordinator Response/Corrective Actions Responder Initials/ Date QA Initials/ Date ------- US ETV AMS Center and NOWATECH DHIWMC Joint Verification Process Document Page 34 of 35 Date: 2/10/2009 APPENDIX F EXAMPLE JOINT VERIFICATION STATEMENT THE ENVIRONMENTAL TECHNOLOGY VERIFICATION PROGRAM This is a preliminary template of a Verification Statement that may be expanded and organized to meet NOWATECH and US EPA ETV program requirements. NOWATECH and DHI logos will be added. U.S. Environmental Protection .Agency Batreiie UK Business of Innovation TECHNOLOGY TYPE: APPLICATION: TECHNOLOGY NAME: COMPANY: ADDRESS: WEB SITE: E-MAIL: PHONE: FAX: ETV Joint Verification Statement • Description of EV and the organizations involved in this joint verification. • Name technology category and technology (product) that was jointly verified. VERIFICATION TEST DESCRIPTION • Describe the verification test- when, how • Describe the performance parameters • Describe the QA performed TECHNOLOGY DESCRIPTION Describe the technology (product) ------- US ETV AMS Center and NOWATECH DHIWMC Joint Verification Process Document Page 35 of 35 Date: 2/10/2009 VERIFICATION RESULTS • Summary of results by performance parameters Signature blocks for: NOWATECH Steering Committee Head - Christian Gran DHI Director of Research and Quality - J0rn Rasmussen Battelle Chemical, Environmental and Materials Operations Manager - Lisa McCauley US EPA National Risk Management Research Office of Research and Development - Sally Gutierrez NOTICE: ETV verifications are based on an evaluation of technology performance under specific, predetermined criteria and the appropriate quality assurance procedures. EPA and Battelle make no expressed or implied warranties as to the performance of the technology and do not certify that a technology will always operate as verified. The end user is solely responsible for complying with any and all applicable federal, state, and local requirements. Mention of commercial product names does not imply endorsement. ------- NOWATECH Hnrdir Innnvjtinn f cntf» Baireiie I'll.* I kii>Liiuif ^ Innovation Sorbisense GSW40 Passive Sampler Joint verification protocol Volatile organic compounds in groundwater January 2009 Version approved ------- Sorbisense GSW40 Passive Sampler Joint verification protocol Agern Alle 5 DK-2970 H0rsholm Denmark Tel: +4545169200 Fax: +4545169292 dhi@dhigroup.com www.dhigroup.com Vendor Sorbisense ApS Vendors representative Hubert deJonge Project Nordic Water Technology Verification Centers Authors Christian Gran Revision Joint verification protocol Description Key words Environmental technology verification, passive sampler, groundwater Project No 80144 Date January 2009 Approved by CHG ALJ ALJ By Checked Approved Date Classification £3 Open CD Internal CD Proprietary Distribution Sorbisense DHI UBA-A Battelle US EPA HdJ CHG, GHE, MTA DM AMG, ZJW LD No of copies File distribution only ------- TABLE OF CONTENTS TABLE OF CONTENTS 2 INTRODUCTION 1 2.1 Name of product 1 2.2 Name and contact of vendor 1 2.3 Name of center/verification responsible 1 2.4 Verification Test Organization 1 2.5 Expert group 2 2.6 Verification process 3 3 DESCRIPTION OF THE TECHNOLOGY 3 4 DESCRIPTION OF THE PRODUCT 4 5 APPLICATION AND PERFORMANCE PARAMETER DEFINITIONS 6 5.1 Matrix/matrices 6 5.2 Target(s) 6 5.3 Effects 6 5.4 Performance parameters for verification 6 5.5 Additional parameters 8 6 EXISTING DATA 8 6.1 Summary of existing data 8 6.2 Quality of existing data 9 6.3 Accepted existing data 9 7 TEST PLAN REQUIREMENTS 9 7.1 Test design 10 7.2 Reference analysis 11 7.3 Data management 11 7.4 Quality assurance 11 7.5 Test report 11 8 EVALUATION 11 8.1 Calculation of performance parameters 12 8.2 Evaluation of test data quality 13 8.3 Compilation of additional parameters 13 8.3.1 User manual 13 8.3.2 Product costs 14 8.3.3 Occupational health and environment 15 9 VERIFICATION SCHEDULE 15 10 QUALITY ASSURANCE 15 ------- APPENDIX 1 17 Terms and definitions used in the verification protocol 17 APPENDIX 2 22 References 22 APPENDIX 3 25 Application and performance parameter definitions 25 ------- 2 INTRODUCTION Environmental technology verification (ETV) is an independent (third party) assessment of the performance of a technology or a product for a specified application, under defined conditions and quality assurance. This verification is a joint verification with the US EPA ETV scheme and the Advanced Monitoring Systems Centre, Battelle, see the verification protocol III for details on organization and implications. The compliance of the test with both scheme's requirements is ensured through a process document 111. 2.1 Name of product The product is the Sorbisense GWS40 passive sampling system (106-012-11) with samplers (cartridges) for analysis of volatile organic compounds (VOCs) (no. 043-0091-12, 043-0101-12, 043-0102-12). The analysis of the samplers is performed by AlControl under ISO 17025 accreditation. The passive samplers and the subsequent analysis of the cartridges constitute the product. 2.2 Name and contact of vendor Sorbisense A/S, Niels Pedersens Alle 2, DK-8830 Tjele, Denmark, phone +45 8999 2505, +45 8999 2599. Contact: Hubert de Jonge, e-mail hubert@sorbisense.com. The laboratory responsible for the analysis of samples (subcontractor to the vendor) is: ALcontrol Laboratories, Steenhouwerstraat 15, 3194 AGHoogvliet, Netherlands, Contact: Jaap Willem Hutter, e-mail j.hutter@alcontrol.nl 2.3 Name of center/verification responsible NOWATECH Water Monitoring ETV Center, DHI, Agern Alle 5, DK-2970 H0rsholm, Denmark. Verification responsible: Christian Gran, e-mail chg@dhigroup.com, phone +45 95 16 95 70, mobile +45 29 65 34 47. US EPA Advanced Monitoring System Center, Battelle Memorial Institute, 505 King Avenue, Columbus, Ohio 43201-2693, US. Verification responsible: Anne M. Gregg (AMG), e-mail gregga@battelle.org, phone+1 614-424-7419 2.4 Verification Test Organization The verification will be conducted as a joint verification between the Nordic Water Technology Verification Centers (NOWATECH ETV) and the U.S. ------- Environmental Technology verification (US ETV) Program. The verification is planned and conducted to satisfy the requirements of the ETV scheme currently being established by the European Union (EU ETV) and the US ETV program. Verification and tests will be performed by DHI as NOWATECH Water Monitoring Center (DHI WMC) under contract with Nordic Innovation Centre, Nordic Council of Ministers. Battelle will be participating as the manager of the ETV Advanced Monitoring Systems (AMS) Center through a cooperative agreement with the U.S. Environmental Protection Agency (EPA). The day to day operations of the verification and tests will be coordinated and supervised by DHI personnel, with the participation of the vendor, Sorbisense. The testing will be conducted in the DHI laboratories, H0rsholm, Denmark and in the field in the Copenhagen area, Denmark. DHI will operate the samplers during the verification. Sorbisense will provide the sampling systems, the samplers and the analysis of samplers for the test. Furthermore, Sorbisense will provide user manuals and operation instructions, and will participate in development of protocol and plans with DHI. Battelle will ensure that the verification and tests is planned and conducted to satisfy the requirements of the US ETV program, including obtaining input and concurrence from its stakeholder group, as described in the process document 111. Battelle will also participate in the development of the plan document for the verification and tests and perform quality assurance of the verification and tests. EPA will participate in quality assurance of the verification and tests. An expert group is established to provide independent expert review of the planning, conducting and reporting of the verification and tests. The organization chart in Figure 1 identifies the relationships of the organization associated with this verification and tests. Figure 1 Organization of the verification and tests us EPA ETV NOWATECH ETV Battelle AMS Verifications DHI WMC Tests Sorbisense Battelle AMS stakeholders 2.5 Expert group The expert group assigned to this verification and responsible for review of the verification plan and report documents includes: ------- Dietmar Miiller (DM), e-mail dietmar.mueller@umweltbundesamt.at, Contaminated Sites, Umweltbundesamt, Spittelauer Lande 5, 1090 Wien, Austria, phone +43-(0)1 -313 04/5913 Mike Sherrier (MS), e-mail michael.p.sherrier@usa.dupont.com, DuPont, Barley Mill Plaza, Bldg 19-1132, 4417 Lancaster Pike, Wilmington, DE 19805, US, phone +1 302-892-1168 Cynthia Paul (CP), e-mail paul.cindy@epa.gov, U.S. Environmental Protection Agency, 919 Kerr Research Drive, P.O. Box 1198. Ada, OK 74820, US, phone: +1 580-436-8556. 2.6 Verification process Verification and tests will be conducted in two separate steps, as required by the EU ETV. The steps in the verification are shown in Figure 2. Figure 2 Verification steps References for the verification process are the Quality Management Plan for the Battelle AMS /3/ and the Quality Manual for the ETV operations at DHI following the NOWATECH Quality Manual Template /4/. A joint US EPA ETV and NOWATECH ETV verification statement will be issued after completion of the verification. Ensuring the compliance of the verification with the US ETV requirements is done following a process document developed by Battelle AMS. This verification protocol, the test plan and the process document shall be seen as one consolidated verification description. DESCRIPTION OF THE TECHNOLOGY The technology product to be verified is applying the technology of passive sampling. ------- Passive sampling is based upon distribution of solutes between the sampled medium, e.g. a water body, and a collecting medium, the sampler or sampling medium. Flow of solute from one medium to the other continues until equilibrium is established in the system, or until the sampling session is terminated by the user. The amount of solute in the sampling medium is then determined analytically and can be used to calculate the concentration in the sampled medium. With exposure until equilibrium, the sampled medium concentration can be calculated based on the solute distribution between the two media involved as obtained by e.g. experimental calibration of the device. With exposure until the sampling session is terminated by the user (before achieving equilibrium), the time-weighted average solute concentration in the sampled medium can be determined from the exposure time and the sampling rate for the solute in question. A wide range of products are available for passive sampling (equilibrium based and rate controlled) of solutes (inorganic and organic) from waters. 4 DESCRIPTION OF THE PRODUCT The Sorbisense passive sampler combines the principle of passive sampling with a patented tracer based calculation of the amount of water that the sampler has been exposed to. The sampler consists of a polypropylene cartridge containing, see Figure 3: • A sorbent that absorbs solutes from water passing the sampler. • Tracer salt that dissolves proportionally with the volume of water passing the cartridge. • Filters between sorbent and tracer salt compartments. Figure 3 Principle of the Sorbisense sampler . Sorbent Filter -——___ i __^ , Tracer salt Rlter Tracer salt i ^ \ I Rlter When the sampling period is over, the Sorbisense sampler is sent to a laboratory for extraction and analyses whereupon time-weighted average solute concentration is reported. For analysis, the cartridge is cut and the sorbent taken for batch extraction with acetone followed by quantification of sorbed compounds by headspace GC- ------- MS. The tracer salt (calcium citrate) is taken for extraction with 0.2 M HC1 and quantification of extracted calcium with ICP. The sampled water volume is calculated from: V = start ,tracersalt lab ,tracersalt ~K The solute water concentration is calculated from: C=MsoluJV = Msolute*K start,tracersalt start ,tracersalt V= water volume in L; Mstart: tracersalt = weighed amount of salt in production as mg Ca; Miab, tracersalt = extracted amount of salt in laboratory as mg Ca; C = VOC concentration in ug/L; Msoiute = mass of VOC detected in ug; K = solubility of the salt with the standard calibration value as 184 mg Ca/L. The product to be verified here is the Sorbisense GWS40 sampling system intended for sampling of shallow groundwater and equipped with samplers for volatile organic compounds. Figure 4 Mounting of the GWS40 sampling system The GWS40 is mounted with air hose, safety string and Sorbisense samplers (can be mounted in top and bottom of the GWS40) and is subsequently lowered to the desired measuring depth, see Figure 4. The water pressure will push water through the sampler slowly filling the GWS40. The air hose enables the air inside the GWS40 to escape to the atmosphere. When the measuring period is over, the samplers are removed and sent to the laboratory for analysis. ------- APPLICATION AND PERFORMANCE PARAMETER DEFINITIONS The application is defined as detailed in the application definition appendix, Appendix 3, in terms of matrix/matrices for use, targets of monitoring and effects. The passive sampler is supplied by the vendor as combined sampling and analysis, and the verification shall accordingly see these two steps as one. 5.1 Matrix/matrices The matrix of the application is groundwater and the field of application is investigations of (potentially) contaminated groundwater (groundwater investigations). 5.2 Target(s) The targets of the product are volatile organic contaminants (VOC), here mono-, di-, tri- and -tetrachloroethenes, benzene, toluene, ethylbenzene and xylenes (BTEX) and methyl-fert-butylether (MTBE), see Table 1. Table 1 Targets of the Sorbisense GSW40 VOC sampler Target compounds Chloroethene 1,1-Dichloroethene 1,2-Dichloroethenes Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene Xylenes MTBE 5.3 Effects The effects for the application are set in terms of limit of detection (LoD), precision, trueness, range of application and robustness. 5.4 Performance parameters for verification The ranges of performance relevant for the application, as derived in Appendix 3, are presented in Table 2. These ranges are used for planning the verification and testing only. For Sorbisense VOC sampling, concentrations above 2,000 |ig/L are not likely to be measurable (vendor information) and are not included in the verification. The calculation of the performance parameters explaining their principle is given in Table 5. ------- Table 2 Ranges of performance parameters relevant for groundwater investigations Compound Chloroethene 1,1-Dichloroethene 1,2-Dichloroethenes Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene Xylenes MTBE Limit of detection M9/L 0.02-0.05 0.1-1 0.1-1 0.1-1 0.1-1 0.1-1 0.5-5 0.5-5 0.5-5 0.2-2 Precision % <25 <25 <25 <25 <25 <25 <25 <25 <25 <25 Trueness % 75-125 75-125 75-125 75-125 75-125 75-125 75-125 75-125 75-125 75-125 Range of application M9/L LoD-1*10b LoD-1*10b LoD-1*10b LoD-1*10b LoD-0.1*10b LoD-1*10b LoD-0.1*10b LoD-0.1*10b LoD-0.1*10b LoD-1*10b Robustness % 100±15 100±25 100±25 100±25 100±25 100±25 100±25 100±25 100±25 100±25 Limit of detection shall be evaluated from the standard deviation of replicate measurements at less than 5 times the detection limit evaluated and will reflect a less than 5% risk of false blanks. Precision shall be evaluated under repeatability and reproducibility conditions. Repeatability is obtained as the standard deviation of measurements done with the same measurement procedure, same operators, same measuring system, same operating conditions and same location, and replicate measurements on the same or similar objects over a short period of time. Reproducibility is obtained as the standard deviation of measurements that includes different locations, operators, measuring systems, and replicate measurements on the same or similar objects. In laboratory terminology, repeatability is the within series precision and the reproducibility the between series precision. Trueness is the correspondence between (mean) concentrations found in measurements and corresponding true concentrations. In addition to conventional trueness, the trueness of time-weighted averages obtained with the sampler shall be verified. The range of application is the range from the LoD to the highest concentration with linear response. The parameters of robustness to be verified are sampling depth, sampling time, sampling concentration and groundwater ionic strength. Robustness is basically the trueness as found for different values of the robustness parameters. The version of the product to be verified is designed for sampling shallow aquifers, i.e. with sampling depths from 0.5 to 5 m below groundwater table (mbgw). The pressure on samplers will vary with depth to the sampling positions, and pressure variations in the range of 1.05-1.5 atmosphere shall accordingly be verified. Sampling time variations from 3 to 9 days shall be verified covering the different sampling times recommended by the vendor, as the exposure time may impact the performance. ------- In investigations of contaminated groundwater, both uncontaminated and strongly contaminated groundwater will be included. The concentrations verified shall therefore reflect the range from uncontaminated groundwater to highly contaminated groundwater, with at the least 3 concentrations distributed over a relevant range. In order to reflect the varying ionic strength of groundwaters, groundwater ionic strengths within the range 10-100 mS/m shall be verified, corresponding to the 5-95 percentile of Danish groundwaters 151. Information on the analytical performance for the sampler analysis will be obtained from the responsible laboratory for comparison. Impact of other factors such as groundwater flow, well construction or presence of other contaminants than the targets can not be ruled out and should be considered in planning the tests for the verification. 5.5 A dditional parameters Besides the performance parameters to be obtained by testing, compilation of parameters describing users manual, product costs and occupational health & safety issues of the product are required as part of the verification. 6 EXISTING DATA A test of Sorbisense samplers, similar but earlier product version, for volatile organic contaminants in groundwater wells has been conducted by the laboratory used by the vendor for sampler analysis. 6.1 Summary of existing data The summarized data as provided by the manufacturer is presented in Figure 5. The test was set up with polyvinylchloride (PVC) pipes simulating groundwater wells (standpipes), filled with spiked water and equipped with Sorbisense samplers inserted directly into the water using a pipe adaptor ("pipe"), Sorbisense samplers mounted in GWS samplers ("GWS") and water samples taken directly from the pipe ("water samples"). ------- Figure 5 Summarized data on sampler test for selected VOC as provided by the manufacturer Test parameter VOC Spike level: (average of results) VOC measuring range: VOC recovery: (average of results) VOC detection limit VOC concentration precision: Sotbtsense Water Samples 0, 6, 36, 120, 3000 ug/L GWS: 0 - 1980 ug/L Pipe: 0 - I860 uq/L GWS: 85 % of spiked level Pipe: 91% of spiked level 0.2ug/V (V= volume sampled'; GWS: 13 ,7% of mean Pipe: 8, 9% of mean Catulafted *wn 44 dujfcates each 0-2160 ug/L 75% of spiked levd 0.2 ug/L 30, 5% of mean caoi&ted Dram 44 trttfcates 3000,0 2500.0 -H 2000,0 GWS Rpe 1:1 relation 0 500 1000 1500 2000 2500 3000 Wilier samples (ug/L) 6.2 Quality of existing data It is not stated whether the testing and analysis were done under the laboratory's ISO 17025 accreditation 161, the test laboratory can not be considered independent, and the documentation made available for the verification is not sufficient to allow for an assessment of the data quality. 6.3 Accepted existing data It was decided that the existing data shall not be used as part of the verification due to the data quality issues, see Section 6.2. The data will be used as an indication of the performance range to be expected during planning. TEST PLAN REQUIREMENTS Based upon the application and performance parameter identification, Section 0, the requirements for test design have been set, see below. The detailed test ------- plan is prepared separately based upon the specification of test requirements presented below. 7.1 Test design The outline of the required tests is shown in Table 3. The principle behind the design is that three test scales are used: laboratory tests, standpipe tests and field tests. Each scale is further described below and provides information on specified performance parameters, with the smallest scale chosen for each parameter in order to maintain simplicity and controlled conditions in the test. Table 3 Test design scales and associated performance parameters Laboratory Limit of detection: best possible Precision and trueness: best possible Robustness, sampling time and groundwater ionic strength Trueness of time-weighted average concentration Stand pipe Limit of detection: realistic Precision (repeatability), true- ness and range of application Robustness, sampling depth None Field None Precision (reproducibility) General robustness None As an example of the application of the scale principle, consider the test for evaluation of trueness and robustness. Trueness as best possible estimate is evaluated from direct application at the laboratory scale (chloroethene only). Trueness as realistic estimate is evaluated from the stand pipe scale simulating a groundwater well (all but chloroethene), and the variation in trueness between groundwater wells (robustness) is evaluated at the field scale. Combining the scales thus provides the best possible estimates of real conditions performance. The laboratory tests shall apply direct application of standard solution to the samplers (best possible) or exposure of samplers to spiked water from a sample dispenser (robustness and trueness). The laboratory tests provides information on the response of the samplers to carefully controlled parameters and best possible information on the performance of the samplers with chloroethene, a compound that can not be included in standpipe tests due to practical and health and safety considerations. The standpipe test is intended to simulate ground water movement through a well established in the laboratory and to enable full control of solute concentrations. The standpipe test provides more realistic information on the performance of the samplers, while minimizing the variability of the test system as compared to field systems. The field tests shall provide information on the robustness of the sampling system under the real conditions of groundwater investigations. In planning the field tests, varying aquifer and well conditions should be aimed at in order to allow for consideration of any impact of factors such as groundwater flow, well 10 ------- construction or presence of other contaminants than the targets, as well as the impact of combined variation of robustness parameters. 7.2 Reference analysis Reference analysis must be done under ISO 17025 accreditation 161 using a GC-MS-SIM P&T method (EPA 624.2 or equivalent 111) and must be documented to satisfy the analytical requirements set for groundwater investigations in Denmark, see Table 4 and the application and performance parameter definitions, Appendix 3. Table 4 Required analytical quality for reference analysis Compound All Limit of detection ug/L 0.03 Precision 5 Trueness 90-110 Range of application ug/L 0.03-2000 7.3 Data management Data storage, transfer and control must be done in accordance with the requirements of ISO 9001 /8/ enabling full control and retrieval of documents and records. The filing and archiving requirements of the DHI Quality Manual must be followed (10 years archiving). 7.4 Quality assurance The quality assurance of the tests must include control of the reference system, control of the test system and control of the data quality and integrity. The test plan and the test report will be subject to review by the expert group as part of the review of this verification protocol and the verification report, see Figure 2. As this verification is a joint verification with the US EPA ETV, auditing from Battelle AMS Center is to be included in the test quality assurance. 7.5 Test report The test report must follow the principles of template of the DHI NOWATECH verification center quality manual template /4/ with data and records from the tests presented. For this joint verification, the principles (contents) of the US ETV format must be complied with as well. 8 EVALUATION The evaluation includes calculation of the performance parameters, see Section 5.4 for definition, evaluation of the data quality based upon the test quality assurance, see Section 7.4 for requirements, and compilation of the additional parameters as specified in Section 5.5. 11 ------- 8.1 Calculation of performance parameters Calculations are done according to generally accepted statistical principles such as those described in 191 and as described in Table 5, referring also to the test design shown in Table 3. Table 5 Calculations used for the test results Parameter Calculation Explanations Limit of detection, LoD is the Student's t factor for f = n, - 1 degrees of freedom, n being the number of measurements. 2r is the standard deviation of the measurements under repeatability conditions Precision (repeatability or reproducibility), as relative standard deviation, RSD imox imin d = • m 1.693 DJ is the range at level i Xjmin and Xjmax are the lowest and highest measurements at level i dj is the relative range at level i d is the mean relative range for all m levels Trueness, T Tt - T = y FJ^ m x. is the mean of Sorbisense measurements at level i, Xj y i is the mean of reference measurements at level i, y\ Ti is the trueness at level i y is the true value of the analyte T is the mean true value for all levels Range of application Visual identification of linear range, linear regression of results within linear range to yield slope, intercept and coefficient of regression (r2). Robustness See trueness, trueness reported for each specific parameter studied. Robustness, concentration integration '/T = yT is the true, mean concentration over the exposure period q and tj are the concentrations and exposure times for each concentrations steps Test of mean against true value IT- e| xtfT is Student's t-factor for two-sided test at 95% confidence level, n is number of measurements and c is the true concentration. 12 ------- Parameter Test of mean against mean value Calculation P7-yTI_ «. ^ 4 15?I n +• ffi _ HA' - £>s + SF - y)s nxm" n+m-2 Explanations The test requires that the variances are equal, v is n+m-2, and sd is the standard deviation of the difference between the two means. For field measurements, the reference measurements will be used as the true values. For laboratory and standpipe measurements, concentrations obtained from preparation of the matrices are checked against the reference measurements (reference samples). If preparation based concentrations match the reference measurements, mean trueness within 100% ± 2 x RSD (relative standard deviation), these are used as true values for the test measurements. If not, the reference measurements are used as the true values. Calculations will be performed in Excel 2007 set up for the purpose with the equations required. 8.2 Evaluation of test data quality The information of the test report on the reference system, the test system and data quality and integrity control will be evaluated against the requirements set in this protocol and the objectives set in the test plan. The spreadsheet used for the calculations will subject to control on a sample basis (spot validation). The external audit reports prepared by Battelle AMS Center, see Section 7.4, will be evaluated and major findings compiled and reported. 8.3 Compilation of additional parameters 8.3.1 User manual The verification criterion for the users manual is that it describes the use of the samplers adequately and understandable for the typical sampler and sampling planner. This criterion is evaluated through evaluation of a number of specific points of importance, see Table 6 for the parameters to include. A description is complete, if all essential steps are described, if they are illustrated with a figure or a photo, where relevant, and if the descriptions are understandable without reference to other guidance. 13 ------- Table 6 Criteria for user manual evaluation Parameter Product Principle of operation Intended use Performance expected Limitations Preparations Unpacking Transport Assembly Installation Function test Operation Steps of operation Points of caution Accessories Maintenance Trouble shooting Safety Chemicals Power Complete description Summary description No description Not relevant V V 8.3.2 Product costs The capital investment costs and the operation and maintenance cost will be itemized based upon a determined design basis /10/, see Table 7 for the items that will be included. Table 7 List of capital cost items and operation and maintenance cost items per product unit (sample) Item type Capital Site preparation Buildings and land Equipment Utility connections Installation Start up/training Permits Operation and maintenance Materials, including chemicals Utilities, including water and energy Labor Waste management Permit compliance Item Number None 14 ------- The design basis will be described and the cost items relevant for the Sorbisense sampler listed. Note that the actual costs for each item is not compiled and reported. 8.3.3 Occupational health and environment The risks for occupational health and safety and for the environment associated with the use of the product will be compiled. The compilation will list chemicals used during product operation and classified as toxic, T, or very toxic, Tx, for human health and/or very environmentally hazardous (N) according to /I I/. The information will be given as amount used per product unit (sample), see Table 8 for format. Table 8 Compilation of classified chemicals used during product operation Compound CAS number Classification Amount used per product unit Additional risks from installing, operating and maintaining the product will be evaluated, compiled and reported, if relevant. In particular, risks for human health associated with power supply and danger of infections will be considered. VERIFICATION SCHEDULE The verification is planned for 2008-9. The overall schedule is given in Table 9. Table 9 Verification schedule Task Application definition document Verification protocol with test plan Test Test reporting Verification Verification report Report document review Verification statement Timing May 2008 November 2008 to January 2009 January to March 2009 March 2009 March 2009 March 2009 April 2009 April 2009 10 QUALITY ASSURANCE The quality assurance of the verification is described in Table 10 and Figure 2, and the quality assurance of the tests in the test plan but summarized here, as well as in the process document 111. 15 ------- Table 10QA plan for the verification Initials Tasks Plan document with verification protocol and test plan Test system Report document with test report and verification report DHI ALJ Review - Review LSC Audit Battelle AMS Center ZW Audit US EPA ETV LD, JMK, EH Review - Review Expert Group CP, DM, MS Review - Review Internal review of plan and report documents is done by chief engineer Anders Lynggaard Jensen (ALJ), and test system audit (see test plan) is done following the GLP audit procedure by a trained auditor: head of laboratory products Louise Schluter (LSC). The Battelle quality manager, Zachary Willenberg (ZW), will perform a technical systems audit (TSA) during this verification and test. EPA QA staff, Lauren Drees (LD), John McKernan (JMK) and Evelyn Hartzell (EH) will do review of the plan and report documents. The expert group will do review of the plan and report documents. Reviews will be done using the NOWATECH review report template. 16 ------- APPENDIX 1 Terms and definitions used in the verification protocol 17 ------- The abbreviations and definitions used in the verification protocol and the test plan are summarized below. Where discrepancies exist between NOWATECH and US EPA ETV terminology, definitions from both schemes are given. Word ADQ AMS Center Analysis Analytical laboratory Application A-UBA BTEX CEN CWA DHI WMC Direct application DOC Drinking water control DS Effect EN ETV EU Evaluation NOWATECH Audit of data quality: An examination of a set of data after is has been collected and 1 00% verified by project personnel, consisting of tracing at least 1 0% of the test data from original recording through transferring, calculating, summarizing and reporting. Advanced Monitoring Systems Center at Battelle Analysis of Sorbisense samplers at the vendor identified laboratory Independent analytical laboratory used to analyze reference samples The use of a product specified with respect to matrix, target, effect and limitations Umweltbundesamt Austria Benzene, toluene, ethylbenzene and xylenes European Committee for Standardization CEN Workshop agreement (ETV) Water Monitoring Center at DHI A test design where a standard solution is applied directly to the Sorbisense samplers Dissolved organic carbon Control of drinking water quality against drinking water maximum concentrations. Danish Standard The way the target is affected, in this verification the way the target compounds are measured European standard Environmental technology verification (ETV) is an independent (third party) assessment of the performance of a technology or a product for a specified application, under defined conditions and adequate quality assurance. European Union Evaluation of test data for a US ETV EPA program that develops generic verification protocols and verifies the performance of innovative environmental technologies that have the potential to improve protection of human health and the environment An examination of the efficiency of a 18 ------- Word Experts GC Groundwater investigation Groundwater monitoring GWS ISO Laboratory sample dispenser Limit of detection LoD Limit of quantification LoQ Matrix mbgv mbs Method MS MTBE NOWATECH ETV P&T PE Performance claim Performance parameters Precision NOWATECH technology product for performance and data quality Independent persons qualified on a technology in verification or on verification as a process Gas chromatography Investigation of groundwater contamination with measurements controlled against groundwater maximum concentrations. Baseline monitoring of groundwater quality. Groundwater sampler International Standardization Organization Test device designed for controlled exposure of Sorbisense samplers to test solutions. Calculated from the standard deviation of replicate measurements at less than 5 times the detection limit evaluated. Corresponding to less than 5% risk of false blanks. Calculated from the detection limit, typically 3 times the LoD, the concentration, where the blank variation impacts the precision 20%. The type of material that the product is intended for m below groundwater table m below surface Generic document that provides rules, guidelines or characteristics for tests or analysis Mass spectrometry Methyl-fe/f-butylether Nordic Water Technology Verification Centers Purge and trap Performance evaluation: A quantitative evaluation of a measurement system, usually involving the measurement or analysis of a reference material of known value or composition The effects foreseen by the vendor on the target (s) in the matrix of intended use Parameters that can be documented quantitatively in tests and that provide the relevant information on the performance of an environmental technology product The standard deviation obtained from replicate measurements, here measured under repeatability or US ETV technology Peer reviewers appointed for a verification 19 ------- Word (Environmen- tal) product PVC QA Range of application Reference analyses Reference samples Repeatability Reproducibility Robustness RSD Sampler Samples Sampling system SIM SM Stakeholder Standard NOWATECH reproducibility conditions. Ready to market or prototype stage product, process, system or service based upon an environmental technology Polyvinylchloride Quality assurance The range from the LoD to the highest concentration with linear response, Analysis by a specified reference method in an accredited (ISO 17025) laboratory. Samples taken for and analyzed by a specified reference method in an accredited (ISO 17025) laboratory. The precision obtained under repeatability conditions, that is with the same measurement procedure, same operators, same measuring system, same operating conditions and same location, and replicate measurements on the same or similar objects over a short period of time The precision obtained under reproducibility conditions, that is with measurements that includes different locations, operators, measuring systems, and replicate measurements on the same or similar objects % variation in measurements resulting from defined changes in matrix properties. Relative standard deviation in %. Sorbisense sorbent cartridge Samples taken with and analyzed after the Sorbisense method. The sampling reservoir and venting system used to operate the Sorbisense samplers Selected ion monitoring Standard Methods for the Examination of Water and Wastewater, latest edition Generic document established by US ETV (Environmental) technology Buyers and users of technology, technology developers/vendors, the consulting engineers, the finance and export communities, government permitters, regulators, first responders, emergency response, disaster planners, public interest groups, and other groups interested in the performance of innovative environmental technologies. 20 ------- Word Stand pipe Target (Environmenta 1) technology Test/testing Trueness ISA US EPA Vendor Verification VOC VOX WS NOWATECH consensus and approved by a recognized standardization body that provides rules, guidelines or characteristics for tests or analysis Test device designed to simulate a groundwaterwell The property that is affected by the product, in this verification the target compounds measured. The practical application of knowledge in the environmental area Determination of the performance of a product by parameters defined for the application The % recovery of true value obtained either from knowledge on the preparation of test solutions or from measurements with reference methods. Technical system audit United States Environmental Protection Agency The party delivering the product or service to the customer Evaluation of product performance parameters for a specified application under defined conditions and adequate quality assurance Volatile organic compounds, here the compounds listed as target compounds/analytical parameters Volatile halogenated organic compounds, here the halogenated compounds listed as target compounds/analytical parameters Workshop (under CEN) US ETV An all-inclusive term used to describe pollution control devices and systems, waste treatment processes and storage facilities, and site remediation technologies and their components that may be utilized to remove pollutants or contaminants from, or to prevent them from entering, the environment. The technology developer, owner, or licensee seeking verification Establishing or proving the truth of the performance of a technology under specific, predetermined criteria, test plans and adequate data QA procedures 21 ------- A P P E N D IX 2 References 22 ------- 1. Gran, C. Sorbisense GWS40 Passive Sampler. Verification protocol. 2009. 2. Battelle. Process Document for US EPA ETV AMS Center and NOWATECH DHI WMC Joint Verification of the Sorbisense Ground Water Sampler. 2009. 3. Battelle. Quality management plan (QMP) for the ETV Advanced Monitoring Systems Center. Version 7.0. 17-11-2008. 4. NOWATECH. Verification test center quality manual. 2008. 5. Leerke Thorling. Data extract from the Danish Groundwater Monitoring Programme. 21-5-2008. 6. ISO. General requirements for the competence of testing and calibration laboratories. ISO 17025. 2005. 7. US EPA. Measurement of Purgeable Organic Compounds in Water by Capillary Column Gas Chromatography/Mass Spectrometry. Method 624.2. 1995. 8. International Standardization Organisation. EN ISO 9001. Quality management systems - Requirements. 15-11-2008. 9. ISO. Accuracy (trueness and precision) of measurement methods and results - Part 1. ISO 5725-1. 2004. 10. Gavaskar, A. and Gumming, L. Cost Evaluation Strategies for Technologies Tested under the Environmental Technology Verification Program. 2001. Battelle. 11. European Commission. Commission Directive on classification, packaging and labelling of dangerous substances. 2001/59/EC. 2001. 12. The Environment Agency's Monitoring Certification Scheme. Performance standards and test procedures for portable water monitoring equipment. 2008. 13. ISO. Water Quality - On-line sensors/analysing equipment for water - Specifications and prerformance tests. ISO 15839. 2006. 14. International Standardization Organisation. Water quality - Guide to analytical quality control for water analysis. ISO 13530. 1998. 15. Battelle Advanced Monitoring Systems Center. Test/QA Plan for Verification of Enzymatic Test Kits. Environmental Technology Verification Program . 21-9-2005. 16. Sandia National Laboratories. Ground Water Sampling Technologies Verification Test Plan. U.S.Environmental Protection Agency. Environmental Technology Verification Program . 1999. 17. EU Kommisionen. Commission directive laying down, pursuant to Directive 2000/60/EC of the European Parliament and of the Council, technical specifications for chemical analysis and monitoring of water status. Draft. 2008. 23 ------- 18. International Standardization Organisation. Water quality — Vocabulary — Part 2. ISO 6107-2. 1-5-2006. 19. European Parliament and Council. Directive 2006/118/EC of the European Parliament and of the Council of 12 December 2006 on the protection of groundwater against pollution and deterioration. 12-12-2006. 20. European Council of Ministers. Council Directive 98/83/EC of 3 November 1998 on the quality of water intended for human consumption. Council Directive 98/83/EC. 3-11-1998. 21. Miljeministeriet. Bekendtgorelse om kvalitetskrav til miljomalingerudfert af akkrediterede laboratorier, certificerede personer m.v. Bekendtgerelse 1353. 2006. 22. Jergensen, C., Boyd, H. B., Fawell, I, and Hydes, O. Establishment of a list of chemical parameters for the revision of the Drinking Water Directiv. 2008. 23. Miljestyrelsen. Liste over kvalitetskriterier i relation til forurenet jord. 1-12-2005. 24. Danmarks Miljeundersegelser. Liste over miljefremmede staffer i NOVANA. http://www.dmu.dk/NR/rdonlvres/A1758992-D52E-4C73-8701- BC1C8D25791D/0/MFS stofliste20070807.pdf. 7-8-2007. 25. Sandia National Laboratories. ETV joint verification statement - GORE-SORBER water quality monitoring. 2000. US EPA. 26. Parker, L. V. and Clark, C. H. Study of Five Discrete Interval-Type Groundwater Sampling Devices. 2002. US Army Corps of Engineers. 27. US Geological Survey, Naval Facilities Engineering Service Center, and Battelle. Demonstration and validation of a regenerated cellulose dialysis membrane diffusion sampler for monitoring groundwater quality and remediation progress at DoD sites. 18-4-2006. 24 ------- A P P E N D IX 3 Application and performance parameter definitions 25 ------- This appendix defines the application and the relevant performance parameters application as input for verification and test of an environmental technology following the NOWATECH ETV method. 1 Applications The intended application of the product for verification is defined in terms of the matrix, the targets and the effects of the product. The Sorbisense GWS40 passive sampling system with samplers (cartridges) and analysis of the samplers is provided by the vendor as one product, and the verification shall accordingly see these two investigation steps as one. 1.1 Matrix/matrices The matrix of the application is groundwater and the field of application is investigations on (potentially) contaminated groundwater (groundwater investigations). In groundwater investigations, the groundwater composition generally varies considerably, and the pressure on samplers will vary with depth to the sampling positions. The varying ionic strength, contaminant concentration and water pressure may impact the performance and this impact shall be evaluated as part of the verification. 1.2 Target(s) The targets of the application are volatile organic contaminants, here mono-, di-, tri- and -tetrachloroethenes, BTEX and MTBE. Investigations of contaminated groundwater generally include both uncontaminated and strongly contaminated groundwater. The concentrations verified shall accordingly reflect the range from uncontaminated groundwater to highly contaminated groundwater. With the claimed application at sampling depths from 0.5 mbs to 5 mbs (m below surface), pressure variation in the range 1-1.5 atmosphere shall be verified. Furthermore, with the claimed application, groundwater ionic strengths within the range 10-100 mS/m shall be verified, corresponding to the 5-95 percentile of Danish groundwaters 151. 1.3 Effects The effects for the application are generally reported in terms of limit of detection (LoD), precision, trueness, range of application and robustness. The effects claimed by the vendor are given in Appendix table 1 for all target compounds. The robustness is the change in trueness within the range of application for defined variations in water pressure, contaminant concentration, groundwater ionic strength and sampling time. 26 ------- Appendix table 1 Vendor claim of performance, general terms Compound Chloroethene 1,1-Dichloroethene 1,2-Dichloroethenes Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene Xylenes MTBE Limit of detection M9/L 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 1 Precision % <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 Trueness % >80 >80 >80 >80 >80 >80 >80 >80 >80 >80 Range of application ljg/L LoD-2000 LoD-2000 LoD-2000 LoD-2000 LoD-2000 LoD-2000 LoD-2000 LoD-2000 LoD-2000 LoD-2000 Robustness % 100±30 100±30 100±30 100±30 100±30 100±30 100±30 100±30 100±30 100±30 1.4 Exclusions Passive sampling at waste disposal sites is excluded from the defined application and is thus not covered by the verification, as the conditions with respect to ionic strength and DOC are outside the ranges covered by the verification conditions. Groundwater baseline monitoring and drinking water control are excluded as well, as the passive sampler will not satisfy the detection limit requirements for this purpose, see Chapter 0. 2 General performance Requirements No formal performance requirements for the application have been identified in the European Union or the US. The conventional performance parameters of analytical and monitoring methods and equipment are limit of detection (LoD), precision (repeatability and reproducibility), trueness, specificity, linearity and matrix sensitivity. The uncertainty of measurements may be used to summarize the performance. Parameters may be added to characterize e.g. on-line or on-site monitoring instruments. The listed parameters cover the requirements set or implemented in international standards and by testing and verification operators 112-161. 2.1 Regulatory requirements The general requirement for analytical quality in water monitoring in Europe will be established with the adoption of the Commission Directive on technical specifications for chemical analysis and monitoring of water status 111/ requiring not more than 25% relative standard deviation at the level of the relevant water quality standards. The limit of quantification, LoQ, must be at or below 30% of the relevant water quality standard (WQS), corresponding to a limit of detection at or below 10% of the WQS. The LoQ is as defined in ISO 6107-2: 2006 /18/. The Groundwater Directive 1191 only sets an absolute requirement for monitoring of tri- and tetrachloroethene during groundwater 27 ------- monitoring without stating the water quality standard and the quality requirement. The European Directive on drinking water /20/ defines performance requirements for methods used for control of drinking water quality for the VOCs benzene, tri- and tetrachloroethene, among others. These values cover the chemical analysis only, and quality requirements for drinking water control would mostly be seen as stricter than for groundwater investigations. The drinking water based performance requirements for analysis only should therefore be seen as strict compared to groundwater monitoring including also sampling, see Appendix table 2. Appendix table 2 Regulatory requirements from the European drinking water directive Compound Trichloroethene Tetrachloroethene Benzene Limit of detection M9/L 1 1 0.25 Precision % 25 25 25 Trueness % 75-125 75-125 75-125 Range of application ug/L 1 - - Robustness % - - - The Monitoring Certification Scheme of the British Environment Agency does not provide performance standards for groundwater or drinking water monitoring/127. Danish statute on quality requirements for environmental control 1211 specifies the requirements for control and monitoring of mono-, di-, tri- and - tetrachloroethenes and benzene in groundwater as shown in Appendix table 3. The detection limits stated are not justified by the maximum concentrations for groundwater, except for for chloroethene, see Section 2.2. Again, it should be noted that the requirements cover analysis only and must thus be seen as stricter than required for methods including sampling. Appendix table 3 Regulatory requirements for groundwater monitoring and control from the Danish analytical quality requirement statute Compound Chloroethene 1,1-Dichloroethene 1,2-Dichloroethenes Trichloroethene Tetrachloroethene Benzene Limit of detection M9/L 0.03 0.03 0.03 0.03 0.03 0.03 Precision % 5 5 5 5 5 5 Trueness % 100±10" 100±10 100±10 100±10 100±10 100±10 Range of application M9/L - - - - - - Robustness % - - - - - - 2.2 Application based requirements The application of the samplers in groundwater investigations further defines performance requirements in terms of the contaminant concentrations 1 -: no requirement 2 Assuming a 5% relative standard deviation 28 ------- monitored and controlled during investigations in general. The lower limit of concentrations to be monitored will in most cases be defined by the groundwater maximum concentrations (and as a lower limit the drinking water maximum concentrations) for the compounds in question, see Appendix table 4. Appendix table 4 Summary of groundwater and drinking water maximum concentrations, as summarized in /22/ and /23/ Compound Chloroethene 1,1-Dichloroethene 1,2-Dichloroethenes Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene Xylenes MTBE Groundwater Denmark ug/L 0.2 1 1 1 1 1 5 - 5 2-5 EU ug/L 0.5 - - 10 10 1 - - - - Drinking water US ug/L 2 7 70-100 5 5 5 1000 100 10*10J 20-40 WHO ug/L 0.3 30 50 70 40 10 700 300 500 - A general requirement for the limit of detection of 1/10 of the maximum concentration is applied widely, and the derived limits of detection are compiled in Appendix table 5. Required detection limits for both drinking water and groundwater control are in the same ranges in Austria. For the Danish groundwater monitoring program (GRUMO), requirements for detection limits are as given in Appendix table 5 7247. It should be noted, that the detection limits required here for groundwater monitoring do not comply with those required in Danish statute on quality requirements for environmental control 7217 covering also monitoring of the compounds in groundwater as shown in Appendix table 5. Appendix table 5 Summary of detection limit requirements derived from the groundwater and drinking water maximum concentrations and for the Danish groundwater monitoring programme, 2003 Compound Chloroethene 1,1-Dichloroethene 1,2-Dichloroethenes Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene Xylenes MTBE Groundwater maximum concentration based Denmark ug/L 0.02 0.1 0.1 0.1 0.1 0.1 0.5 - 0.5 0.2 Drink CO EU ug/L 0.05 - - 1 1 0.1 - - - - [ing water ma. ncentration be US ug/L 0.2 0.7 7 0.5 0.5 0.5 100 10 1000 2 Kimum ised WHO ug/L 0.03 3 5 7 4 1 70 30 50 - Groundwate r monitoring based Denmark ug/L 0.05 - - 0.02 0.02 0.04 0.04 - 0.02 - 29 ------- Application based requirements for trueness and precision have generally not been stated to the same degree as for the limits of detection, mainly because regulatory compliance rules in most cases do not consider the uncertainty of control results. No requirements for range of application and robustness have been identified. In practical performance of site investigations, the dissolved concentrations range from below detection limit to the limit of solubility. The upper limit of concentrations to be monitored will thus in most cases be defined by the solubilities of the target compounds are summarized in Appendix table 6. Appendix table 6 Summary of target compound solubilities Compound Chloroethene 1,1-Dichloroethene 1,2-Dichloroethenes Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene Xylenes MTBE Water solubility M9/L 2.8*10b 3.3*1 Ob 3.5-6.3*1 Ob 1.4*10b 0.24*1 Ob 1.8*10b 0.55*1 Ob 0.1 7*1 Ob 0.1 6-0.20*1 Ob 1.8*10b 3 State of the art performance Whereas a broad range of studies on the performance of analytical methods and sampling methods for VOC in groundwater have been published, independent and comparative studies of passive samplers used for VOC monitoring in groundwater are scarce. Examples of reported performances (sampling and analysis) are compiled in Appendix table 7. Appendix table 7 Summary of state of the art performance for passive samplers Sampler GORE- SORBER USGS PDB Dialysis membrane sampler USGS PDB Limit of detection ugTL - - 0.1-5 Precision % 14-21 0.9-4.3 17 21 Trueness % - 86-118 100% Range of applicatio n3 ug/L 5-2000 2-500 0.2-25*1 03 Robustne ss % - - - Reference /25/ 7267 1211 Reported performance (sampling and analysis) as obtained with reference sampling is given in Appendix table 8. Verified range of application, practical range may differ 30 ------- Appendix table 8 Summary of state of the art performance for reference samplers Sampler Grab sampling Grab sampling Low purge pump sampling Limit of detection ug/L - - - Precision % 12% 1.1-9.8 15 Trueness % - - - Range of applicatio n ug/L 5-2000 2-500 0.2-25*1 03 Robustne ss % - - - Reference 1251 I2&I 1211 The precision results obtained with the passive samplers do not greatly differ from the precision values obtained with reference sampling methods. As the precision data obtained with the reference methods will generally be accepted for groundwater monitoring and control, the precision data obtained with the passive samplers should also be considered acceptable. 4 Performance parameter definitions The statement of regulatory and application based requirements in terms of the analytical quality rather than the combined quality of analysis and sampling, as relevant for passive samplers, makes the identification of relevant criteria difficult for passive samplers. Only a limited number of studies on the contributions of sampling and analysis, respectively, to the limit of detection, precision and trueness of groundwater monitoring and control have been published. Therefore, the regulatory and application based requirements needs identified for analytical performance can not be directly translated into the combined sampling and analysis performance requirements relevant for passive samplers. The discrepancies between requirements based upon different approaches when comparing Appendix table 2, Appendix table 3 and Appendix table 5, further hampers the identification of relevant criteria. Therefore, relevant performance parameters for the application are set in Appendix table 9 based upon regulatory and application based requirements and state of the art performance. In order to address the general definition of performance parameters in terms of analytical quality only, information on this using the sampler should be obtained from the responsible laboratory for comparison, if possible. In addition to the straight forward performance parameters of limit of detection, precision, trueness and range of application, the robustness shall be 31 ------- tested for the critical parameters identified here: variations in water pressure, contaminant concentration, groundwater ionic strength and sampling time. Appendix table 9 Relevant ranges of performance parameters for groundwater investigations Compound Chloroethene 1,1-Dichloroethene 1,2-Dichloroethenes Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene Xylenes MTBE Limit of detection M9/L 0.02-0.05 0.1-1 0.1-1 0.1-1 0.1-1 0.1-1 0.5-5 0.5-5 0.5-5 0.2-2 Precision % <25 <25 <25 <25 <25 <25 <25 <25 <25 <25 Trueness % 75-125 75-125 75-125 75-125 75-125 75-125 75-125 75-125 75-125 75-125 Range of application M9/L LoD-1*10b LoD-1*10b LoD-1*10b LoD-1*10b LoD-0.1*10b LoD-1*10b LoD-0.1*10b LoD-0.1*10b LoD-0.1*10b LoD-1*10b Robustness % 85-115 100±25 100±25 100±25 100±25 100±25 100±25 100±25 100±25 100±25 32 ------- NOWATECH Nordk Innovation Ccntie Baflelie \\M il'.iiiinmr ^ Eanordtii Sorbisense GWS40 Passive Sampler Joint test plan Volatile organic compounds in groundwater -r January 2009 Version approved ------- Sorbisense GWS40 Passive Sampler Joint test plan Agern Alle 5 DK-2970 H0rsholm Denmark Tel: +4545169200 Fax: +4545169292 dhi@dhigroup.com www.dhigroup.com Vendor Sorbisense ApS Vendors representative Hubert de Jonge Project Nordic Water Technology Verification Centers Authors Gerald Heinicke Mette Tjener Andersson Revision Joint test plan Description Key words Environmental technology verification, passive sampler, groundwater Project No 80144 Date January 2009 Approved by GHE CHG CHG By Checked Approved Date Classification £3 Open n Internal n Proprietary Distribution Sorbisense DHI UBA-A Battelle US EPA HdJ CHG, GHE, MTA DM AMG, ZJW LD No of copies File distribution only ------- 1 TABLE OF CONTENTS 1 TABLE OF CONTENTS 2 INTRODUCTION 1 2.1 Verification protocol reference 1 2.2 Name and contact of vendor 1 2.3 Name of center/test responsible 1 2.4 Expert group 2 3 TEST DESIGN 2 3.1 Test sites 5 3.1.1 Types 5 3.1.2 Addresses 5 3.1.3 Descriptions 5 3.2 Tests 5 3.2.1 Test methods 6 3.2.2 Test staff 8 3.2.3 Test schedule 9 3.2.4 Test equipment 9 3.2.5 Type and number of samples 9 3.2.6 Operation conditions 11 3.2.7 Operation measurements 11 3.2.8 Product maintenance 11 3.2.9 Health, safety and wastes 11 4 REFERENCE ANALYSIS 12 4.1 Analytical laboratory 12 4.2 Analytical parameters 12 4.3 Analytical methods 12 4.4 Analytical performance requirements 13 4.5 Preservation and storage of reference samples 13 5 DATA MANAGEMENT 13 5.1 Data storage, transfer and control 13 6 QUALITY ASSURANCE 14 6.1 Test plan review 14 6.2 Performance control - reference analysis 14 6.3 Test system control 15 6.4 Data integrity check procedures 16 6.5 Test system audits 16 6.6 Test report review 17 7 TEST REPORT 17 7.1 Test site report 17 7.2 Test data report 17 7.3 Amendment report 17 7.4 Deviations report 17 ------- APPENDIX 1 19 Terms and definitions used in the test plan 19 APPENDIX 2 24 Reference methods and references 24 APPENDIX 3 27 In-house test methods 27 APPENDIX 4 46 In-house analytical methods 46 APPENDIX 5 48 Data reporting forms 48 APPENDIX 6 89 Data management 89 APPENDIX 7 95 Deviations and amendments 95 ------- 2 INTRODUCTION This joint test plan is the implementation of a test design de- veloped for verification of the performance of an environ- mental technology following the NOWATECH ETV method. The verification is a joint verification with the US EPA ETV scheme and the Advanced Monitoring Systems Centre, Bat- telle, see the verification protocol III for details on organiza- tion and implications. The compliance of the test with both scheme's requirements is ensured through a process docu- ment 111. 2.1 Verification protocol reference This test plan is prepared in response to the test design estab- lished in the Sorbisense GWS40 Passive Sampler, verifica- tion protocol, Volatile organic compounds in groundwater, Version final draft, December 2008 III. 2.2 Name and contact of vendor Sorbisense A/S, Niels Pedersens Alle 2, DK-8830 Tjele, Denmark, phone +45 8999 2505, +45 8999 2599. Contact: Hubert de Jonge, e-mail hubert@sorbisense.com. The laboratory responsible for the analysis of samples (sub- contractor to the vendor) is: ALcontrol Laboratories, Steen- houwerstraat 15, 3194 AGHoogvliet, Netherlands, Contact: Jaap Willem Hutter, e-mail j.hutter@alcontrol.nl 2.3 Name of center/test responsible NOWATECH Water Monitoring ETV Center , DHI, Agern Alle 5, DK-2970 H0rsholm, Denmark. Test responsible: Gerald Heinicke, e-mail ghe@dhigroup.com, phone +45 95 16 92 68, mobile +45 29 91 07 15. US EPA Advanced Monitoring System Center, Battelle Me- morial Institute, 505 King Avenue, Columbus, Ohio 43201- 2693, US. Test responsible: Anne M. Gregg (AMG), e-mail gregga@battelle.org, phone +1 614-424-7419 ------- 2.4 Expert group The expert group assigned to this test and responsible for re- view of test plan and test report includes: Dietmar Miiller (DM), e-mail dietmar.mueller@umweltbundesamt.at Contaminated Sites, Umweltbundesamt, Spittelauer Lande 5, 1090 Wien, Austria, phone+43-(0)1-313 04/5913 Mike Sherrier (MS), e-mail michael.p.sherrier@usa.dupont.com, DuPont, Barley Mill Plaza, Bldg 19-1132, 4417 Lancaster Pike, Wilmington, DE 19805, US, phone +1 302-892-1168 Cynthia Paul (CP), e-mail paul.cindy@epa.gov, U.S. Envi- ronmental Protection Agency, 919 Kerr Research Drive, P.O. Box 1198. Ada, OK 74820, US, phone: +1 580-436-8556. TEST DESIGN The test design outlined in the test protocol is summarized in Table 1. The term "samples" is used for samples taken with the Sorbisense sampler, whereas the term "reference sam- ples" is used for water samples taken for reference analysis. Acronyms are explained in Appendix 1. If nothing else is stated below, the standard conditions for the stand pipe include mid range ionic strength (30-70 mS/m conductivity), a sampling period of 6 days and a sampling depth of 0.5 m (0.05 atm overpressure). In Table 1, labels are given for each experiment and for ex- periments with different levels, a new label is given for each level. ------- Table 1 Test design Performance parameters Limit of detection (LoD) Precision (repeatability and reproducibility) Range of application Trueness Robustness, general Robustness, specific Reference for the robust- ness test levels Sampling depth Ionic strength Laboratory1 Direct application to samplers of VOX standard dilution in 7 replicates in the range LoD-5 x LoD. Triplicate analysis of VOX standard dilu- tion. Exp. H Direct application in 7 replicates to samplers of VOX standard at 1 0% of range. Exp. L Triplicate samples at 1 spiked 50% range VOC concentration4, 1 mid range ionic strength (35 mS/m) and 1 mid range sampling time (6 days) from the sample dispenser. Three reference samples distributed over the sampling period. Exp. BA n.a. Triplicate samples at 1 spiked mid range VOC concentration, 2 ionic strengths (10 and 100 mS/m), (6 days), Stand pipe2 7 replicate samples in the range LoD-5 x LoD, spiked cone. 7 reference samples distributed over the sampling period. Exp. J Triplicate samples and three ref- erence samples, the later distrib- uted over the sampling period, each at 5 spiked VOC cone. 10,25,50,75, 100% of range Exp. N, P, R, T, V Precision test above. Triplicate samples at 1 spiked VOC mid range concentration, 0.5 atm. overpressure. Three reference samples distrib- uted over the sampling period. Exp. CA n.a. Field n.a.3 Single samples and reference samples at three (Sorbisense) or four (reference) times from a total of 5 wells at 1-3 sites, inherent concentrations. Exp. AA, AB, AC, AD, AE n.a. n.a. n.a. 1 Direct application is done with chloroethene and the other chlorinated compounds, but without the BTEX and MTBE in the standard, other ex- periments are done with the full VOC set without chloroethene 2 Standpipe experiments are done with the full VOC set without chloroethene 3 n.a.: not applicable 4 from pure chemicals, without chloroethene ------- Performance parameters Laboratory1 Stand pipe Field from the sample dispenser. Three reference samples distributed over the sampling period for each ionic strength. Exp. DA, EA Sampling time Triplicate samples at 1 spiked VOC mid range concentration, mid range ionic strength and 2 sampling times (3 and 9 days), from the sample dispenser. Three reference samples distributed over the sampling period for each sam- pling time. Exp. FA, GA n.a. n.a. Concentration integration Triplicate samples at a step VOC con- centration, 3 concentrations (20, 50 and 80 % of range), each at 1/3 of 6 days sampling period, from the sample dis- penser. Three reference samples distributed over the sampling period. Exp. HA n.a. n.a. ------- 3.1 Test sites Both the laboratory tests and the standpipe tests will be conducted in the DHI labora- tory buildings, H0rsholm, Denmark. The field tests will be carried out on contaminated groundwater sites in the Copenha- gen area. 3.1.1 Types The test sites are summarized in Table 2. Table 2 Summary of test sites Scale Laboratory Standpipe Field Address/site DHI premises DHI premises S0borg hovedgade, S0borg S0borg hovedgade, S0borg S0borg hovedgade, S0borg Farum Bytorv, Farum R0de Vejrm0lle, Roskildevej, Al- bertslund Site de- tails None None AFV6 AFV4 B109 AFV1 K4 VOC profile for test All target compounds All target compounds All target compounds All target compounds, low cone. Chlorinated solvents BTEX + MTBE, high concentrations BTEX + MTBE, intermediary concen- trations Please, note that the field test sites are preliminary and may change after site data compilation and inspections. Changes will be documented by an amendment to this document. 3.1.2 Addresses See Table 2. 3.1.3 Descriptions See Table 2. 3.2 Tests The test program has been prepared to provide the information and to apply the ap- proaches presented for analytical quality control for water analysis (ISO 13530) /3/ and for performance test of on-line sensors/analysing equipment (ISO 15839) /4/. The field tests have been prepared to comply with the test requirements in the Cost Agree- ment (pre-standard) on verification of monitoring technologies for groundwater site characterization (CEN/WS 32:2008) 151. The test design, as described in Table 1, includes three test scales: laboratory, stand pipe and field. For chloroethene (vinyl chloride), the performance is only tested in a simplified labo- ratory design (direct application, best possible LoD, repeatability precision and true- ness) and in the field (worst realistic reproducibility precision and robustness) due to difficulties preparing, obtaining and handling chloroethene solutions. ------- 3.2.1 Test methods No standard methods exist for testing of passive samplers for groundwater monitoring. The test methods have accordingly been prepared for the purpose (see Appendix 3), with reference to the Ground Water Sampling Technologies Verification Test Plan prepared for the US EPA ETV program 161. Preparation of test solutions, reagents and chemicals are described in Appendix 3 as well. It should be noted that the methods in Appendix 3 are described at the detailed level of a work instruction for direct imple- mentation in the laboratory. For standpipe tests, groundwater, see Appendix 3.7, was used for preparing test solu- tions, and for laboratory tests, (clean) water, also see Appendix 3.7, was used. All dilu- tions were prepared in water. For the laboratory and standpipe tests, custom-made stainless steel test devices have been being prepared, see below. For direct application laboratory tests, a standard solution with chlorinated compounds only is applied to the samplers directly with a syringe, followed by equilibration and flushing with water using the sample dispenser, see Appendix 3.1 for method descrip- tion (no illustration). For the laboratory tests, a sample dispenser device, Figure 1, is designed as a closed system that enables direct exposure of samplers to test solutions with known and sta- ble VOC concentrations by conveying the test solution from a closed container by gravity, see Appendix 3.2. The container is equipped with spiking port, sampling port and magnetic stirrer to maintain homogeneous conditions in the sample container. Figure 1 Sample dispenser £ Samplinq oort '«*: 11 h _5 ~™ w o y valve and ver t' c GI r o 2 zi e Magnetic siirbar oo ------- The standpipe test device, Figure 2, is designed with a closed container filled with test solution where the sampling system with samplers can be suspended from the top, see Appendix 3.3. Air from the sample reservoir is vented through an air hose. The con- tainer is equipped with sampling ports and mixing is ensured through continuous pumping from top to bottom. For both the sample dispenser and the standpipe, the air entering the container to re- place dispensed liquid is saturated with VOCs at the same concentration as in the con- tainer, by using an air wash bottle. Figure 2 Standpipe Air exchange tube Steel pipe reci'rculation loop Sampling port with 3-way valve and nozzl end10Q811800378-3 The field sampling. Figure 3, is done by suspending the sampling systems with sam- plers in the screened intervals in depth with the pump of established wells with con- ------- tinuous pumping (monitoring wells or pump-and-treat wells), see Appendix 3.4. Ref- erence samples are taken from the pumped streams (pump depth sampling strategy). Figure 3 Field sampling Air hose Ground String . Groundwater table Sampler Reservoir- Reference sample | Pump, stationary, continuous pumping Screened interval and100811800378-2 3.2.2 In cases, where the pump is deeper than the maximum sampling depth or the installa- tions do not allow for positioning the sampler in pump depth, a position above is cho- sen (above pump sampling strategy). The sampler position is always within the screened interval and within the same aquifer unit as the pump. In such cases, a low volume reference sampling pump is positioned at the same depth as the sampler in- take. In all cases, a low purge sampling strategy is followed, allowing only for flushing of sampling equipment. Test staff The test staff is test responsible Ph.D. Gerald Heinicke (GHE), field responsible Mette T. Andersson (MTA) and test technician Susanne Klem (SEK). ------- 3.2.3 Test schedule The test schedule is given in Table 3, see Table 1 for identification of experiment la- bels. Table 3 Test schedule Task Test plan Pre-testing dispenser Test using dispenser Direct application Set up standpipe Test using standpipe Test field Test report draft Test report QA Test report Week number 2008 47 X X H, L 48 X 49 X X 50 X X 51 X X 52 X Week no. 2009 1 X 2 3 BA J Task Test plan Pre-testing dispenser Test using dispenser Direct application Set up standpipe Test using standpipe Test field Test report draft Test report QA Test report Week number 2009 4 DA N 5 EA P 6 7 FA, GA R T 8 HA V AA, AB, AC, AD, AE 9 CA X 10 X 11 X 12 X 13 X 3.2.4 Test equipment The test equipment includes (working procedures): Laboratory sample dispenser (Appendix 3.2) Stand pipe (Appendix 3.3) Field sampling (Appendix 3.4) The laboratory and stand pipe equipment has been designed and produced for the pur- pose. Equipment test procedures are described in Appendix 3.5. General laboratory equipment procedures including cleaning and calibration are those described and ISO 17025 accredited 111 for the DHI laboratories under the laboratory services manual of the DHI Quality Management System /8/. 3.2.5 Type and number of samples The types and number of samples are summarized in Table 4. ------- Table 4 Summary of type and number of samples Limit of detection Precision Range of application Trueness Robustness, general Robustness, specific Reference for the ro- bustness test levels Sampling depth Ionic strength Sampling time Concentration inte- gration Samples per test scale Samples totally5 Laboratory 7 analyses 3 reference analyses 7 analyses 3 samples 3 reference samples 1 reference analysis 6 samples 6 reference samples 2 reference analysis 6 samples 6 reference samples 2 reference analysis 3 samples 3 reference samples 3 reference analysis 32 samples 29 reference sam- ples/analyses Stand pipe 7 samples 7 reference samples 3 reference analysis 15 samples 15 reference samples 5 reference analysis 3 samples 3 reference samples 1 reference analysis 25 samples 34 reference sam- ples/analyses Field 15 samples 20 reference samples 15 samples 20 reference samples 72 samples 107 reference samples/analyses The term analysis covers analysis of Sorbisense samplers that have been exposed to standard solutions by direct application. The term "samples" is used for samples taken with the Sorbisense sampler and analyzed accordingly. The term reference analyses covers analysis of standards and standard dilutions after a reference method in an accredited (ISO 17025) laboratory. The term reference samples covers sampling of water and analysis after a reference method in an accredited (ISO 17025) laboratory. The analytical program shown above includes 26 reference analyses of standard and stock solutions, as well as of dilutions. If the stability of the solutions and the analyti- cal precision proves satisfactory in the initial part of the program, the number of repli- cate reference analysis may be reduced. The water and the groundwater used in laboratory tests will be controlled for blanks, and the groundwater further characterized for general groundwater parameters, see Appendices 2 and 3.7. Includes also pretesting samples and analyses not in the above rows 10 ------- In addition to the number of test samples, samples controlling the test systems will be required as described in Appendix 3.5. The total number of samples for this purpose is 18 reference samples. The samples will include test system blank samples. 3.2.6 Operation conditions The operation conditions applied during the verification of the product are: • Sampling temperature: ambient 5-25°C • Sampling depth: 0.5-5 m below the water surface • Sample volume: up to 600 mL • Sampling period: up to 9 days • Sampling replicates: one sampler per sampling event 3.2.7 Operation measurements During operation, the following operation conditions are recorded, as relevant, see Appendix 5 for data recording and reporting forms: • Sampling temperature • Depth of sample intake • Sample volume • Sampling period 3.2.8 Product maintenance Samplers are kept in sealed bags as delivered from the vendor at ambient temperature until used. Opened bags with unused samplers are resealed until used. No further maintenance is prescribed for the equipment. 3.2.9 Health, safety and wastes The use of the product does not imply special health, safety and waste issues. Laboratory work during testing will be done according to the DHI Safety Rules that are compliant with the extensive Danish rules for safe occupational health and the European regulations of work with chemicals. Work with VOC spiked solutions will be done using nitrile rubber gloves. Field work will be done according to the DHI rules for safe field work included in the DHI Safety Rules. Chemicals and test solutions are discarded according to Danish regulations for chemi- cal waste by collection and destruction, in casu by collection in drums followed by controlled destruction. 11 ------- 4 REFERENCE ANALYSIS The reference analysis applies to an aliquot of the test solutions that will be submitted to an analytical laboratory for analysis. These samples will verify the actual concen- trations of the test solutions and the results will be compared to the results of the prod- uct in this verification. 4.1 Analytical laboratory Reference analyses are done by Eurofms Danmark A/S, Smedeskovvej 38, DK-8464 Galten, Denmark. Contact Rita Splidt Pedersen, Eurofms Milj0 A/S, +45 70 22 42 66. 4.2 Analytical parameters The analytical parameters and the target VOC are given in Table 5. Table 5 Analytical parameters Analytical parameters Chloroethene 1,1-Dichloroethene 1,2-Dichloroethenes Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene Xylenes MTBE 4.3 Analytical methods The analysis are done using purge and trap gas chromatography with mass spectrome- try detection in the selected ion monitoring mode (P&T GC-MS-SIM) according to the packages given in Table 6. Table 6 Analytical packages, parameters and performance expectations from the contracted laboratory Analytical package DR124 chlorinated solvents and degradation projects DR102BTEX 231 45 MTBE Parameter Trichlorethene Tetrachlorethene 1,1-Dichlorethene trans-1 ,2-dichlorethene cis-1,2-dichlorethene Chloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Limit of detection ug/l 0,02 0,02 0,02 0,02 0,02 0,02 0,02 0,02 0,02 0,02 0,02 0,1 Uncertainty % 7,5 9,2 8,5 8,2 14 7,7 7,4 8,9 9,4 7,4 7,3 7,0 12 ------- The analytical method is based upon EPA Method 624 191 and ISO 15680 /10/ (see Appendix 2 for details). 4.4 Analytical performance requirements The analytical performance requirements are given in Table 7. It should be noted that the uncertainties stated by the laboratory, Table 6, includes both the random error under reproducibility conditions (requirements set here for the preci- sion under repeatability conditions) and the systematic errors (requirements set here for the trueness). For MTBE, concern may be raised whether the laboratory will be able to satisfy the required limit of detection. Table 7 Required analytical performances Compound Chloroethene 1,1-Dichloroethene 1,2-Dichloroethenes Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene Xylenes MTBE Limit of detection M9/L 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 Precision % 5 5 5 5 5 5 5 5 5 5 Trueness % 90-110 90-110 90-110 90-110 90-110 90-110 90-110 90-110 90-110 90-110 Range of application ug/L 0.03-2000 0.03-2000 0.03-2000 0.03-2000 0.03-2000 0.03-2000 0.03-2000 0.03-2000 0.03-2000 0.03-2000 4.5 Preservation and storage of reference samples All water samples for VOC reference analysis are taken in 3 x 40 mL autosampler vi- als with Teflon lined screw caps as delivered from the laboratory contracted for refer- ence sample analysis. The samples are not preserved but stored cold (1-5°C) and dark until delivered to the laboratory within a maximum of 3 days. 5 DATA MANAGEMENT In general, the data filing and archiving procedures of the DHI Quality Management System will be followed. 5.1 Data storage, transfer and control The data to be compiled and stored are summarized in Table 8. Analytical raw data will be filed and archived according to the specifications of the laboratories quality management systems under their ISO 17025 accreditation, Eu- rofins for reference analysis and AlControl for sample analysis (Sorbisense sampler analysis). 13 ------- Table 8 Data compilation and storage summary Data type Test plan and report Test details in laboratory and field Calculations Analytical re- ports Data media Protected PDF files Log book and pre-pre pared forms Excel files Paper Data recorder Test responsi- ble, DHI Technician, DHI Test responsi- ble, DHI Test responsi- ble, DHI Data re- cording tim- ing When ap- proved During collec- tion During calcula- tions When received Data storage Files and ar- chives at DHI Files and ar- chives at DHI Files and ar- chives DHI Files and ar- chives DHI Forms for data recording are given in Appendix 5. 6 QUALITY ASSURANCE The tests are performed under the quality management system of DHI which is ISO 9001 compliant /I I/, but not certified. The DHI laboratories have ISO 17025 accredi- tations 111 and OECD GLP approvals 1121 for a range of tests and ISO 17025 for sam- pling of drinking water. As part of the ISO 17025 and GLP inspections, the procedures for general laboratory processes, quality assurance and documentation/archiving are assessed. 6.1 Test plan review The test plan will be subject to internal review by the verification responsible from DHI WMC Verifications: senior chemist Christian Gran. Additionally, the test plan will be subject to review by the Battelle Advanced Monitoring Center quality manager (Zachary Willenberg, respectively), as well as by the US EPA ETV AMS project offi- cer, quality manager and ETV coordinator (John McKerna, Lauren Drees and Evelyn Hazell, respectively). External review of the test plan will be done by the expert group assigned to this veri- fication. 6.2 Performance control - reference analysis General chemistry, reference sample analyses and reference analyses are done under the ISO 17025 accreditation of Eurofins. The performance of Eurofins for the reference analysis will be evaluated (performance evaluation audit) from laboratory quality control data for the relevant period (precision under repeatability conditions, trueness). Data for the analytical quality control of the laboratory will include duplicate control samples at two concentrations (acceptance within 100%±10%) in each series and at the least one blank sample per 5 samples. The data from participation in a proficiency test arranged by Analytical Products Inc Sep- 14 ------- tember 2008 will be evaluated for the demonstrated precision and traceability for the compounds in question for relevant matrices. The detection limits and risks of false positives of the laboratory are controlled by submitting blank samples and low concentration samples as described in the test pro- gram. The precision and trueness of the laboratory is further evaluated by analysis of stock, standard and spike solutions used for the test (26 reference analyses). The reference analysis includes analysis of a standard with analytical certificate and of solutions pre- pared from pure chemicals at DHL The analytical reference performance control is summarized in Table 9, with reference to Appendix 3.6 and 3.7 for information on water, standard solution (purchased stan- dard with analytical certificate) and VOC solutions (prepared by DHI from pure chemicals). Table 9 Summary of analytical reference performance control Control type VOX standard solution VOC solutions Water Laboratory quality control Proficiency test Limit of detection - - X - - Precision - X - X X Trueness X X - X X 6.3 Test system control The laboratory test design includes test solutions of known concentrations, traceable back to added chemicals of p.a. quality or standards with analytical certificate, see Appendix 3.7 for specifications of purity etc. The known concentrations will be used to pre-test the test design, see Appendix 3.5. The water used for preparation of solutions will be controlled for contents of the target VOC as blanks by reference analysis. The stability of the test concentrations will be controlled continuously during the tests by taking and analyzing reference samples distributed over the sampling periods, con- sidering the "true concentrations" based upon added amounts and the reference analy- ses. The control of the field test system is done using analysis of reference samples and field blank samples. The analytical reference performance control is summarized in Table 10. Laboratory blanks/spiked samples are water, in some cases with ionic strength controlled by add- ing KC1, and the standpipe blanks/stand pipe samples are groundwater (matrix). 15 ------- Table 10 Summary of test system control Information/control type System contamination/blank sample reference analysis System contamination/field blank sample reference analysis System trueness/spiked sample reference analysis System variability/spiked sample reference analysis System trueness/natural sample reference analysis System variability/natural sample reference analysis Laboratory X - X X - - Standpipe X - X X - - Field - X - - X X 6.4 Data integrity check procedures All transfer of data from printed media to digital form and between digital media are checked by spot check of not less than 5% of the data (test or field responsible). If er- rors are found in a spot check, all data from the transfer are checked. 6.5 Test system audits Internal audit from DHI following the GLP audit procedure by a trained auditor is done, see the verification protocol for details. The Battelle quality manager, Zachary Willenberg, will perform a technical systems audit (ISA) at least once during this verification and test. The purpose of this audit is to ensure that the verification test is being performed in accordance with the AMS quality management plan /13/, this test plan, published reference methods and any methods used in the tests. In the ISA, the Battelle quality manager, or designee, may review the reference methods used, and compare actual test procedures to those speci- fied or referenced in this plan. In the TSA, the Battelle quality manager will observe testing in progress, observe the reference method sample preparation and analysis (when available), inspect documentation, and review technology-specific record books. He will also check standard certifications and may confer with other Battelle staff. A TSA report will be prepared, including a statement of findings and the actions taken to address any adverse findings. The AMS quality manager and the NOWATECH WMC verification responsible will receive a copy of Battelle's TSA re- port. The TSA findings will be communicated to technical staff at the time of the audit and documented in a TSA report. The Battelle Quality Manager will perform an audit of data quality (ADQ). This will be a review of data acquisition and handling procedures and an audit of at least 10% of the data acquired in the test and verification. The Battelle Quality Manager will trace the data from initial acquisition, through reduction and statistical comparisons, to final reporting. All calculations performed on the data undergoing the audit will be checked. 16 ------- 6.6 Test report review The test report will be subject to internal review by the verification responsible from DHIWMC Verifications: senior chemist Christian Gran. External review of the test report will be done by the expert group as part of the re- view of the verification report, that will include the full test report as an appendix. 7 TEST REPORT The test report will follow the template of the DHI NOWATECH verification center quality manual /14/ and will be included as an appendix in the verification report. The test report will contain the test plan, except for this Chapter 7 on test report format, with the data and records from the tests to be inserted as new Chapter 7. For this joint verification, the principles (contents) of the US ETV format will be complied with as well. 7.1 Test site report The test site report will include: well design drawing, well and pump data, operation data as outlined in Section 3.2.7 (forms in Appendix 5). 7.2 Test data report The test data will include all data recorded during the test and the data reported by the analytical laboratories, see Appendix 5 for data forms. 7.3 Amendment report The report section on deviations will compile all changes of this test plan occurring before testing with justification of deviations and evaluation of any consequences for the test data quality. 7.4 Deviations report The report section on deviations will compile all deviations from this test plan occur- ring during testing with justification of deviations and evaluation of any consequences for the test data quality. 17 ------- 18 ------- A P P E N D I X 1 Terms and definitions used in the test plan 19 ------- The abbreviations and definitions used in the verification protocol and the test plan are summarized below. Where discrepancies exist between NOWATECH and US EPA ETV terminology, definitions from both schemes are given. Word ADQ AMS Center Analysis Analytical laboratory Application A-UBA BTEX CEN CWA DHI WMC Direct applica- tion DOC Drinking water control DS Effect EN ETV EU Evaluation NOWATECH Audit of data quality: An examination of a set of data after is has been col- lected and 1 00% verified by project personnel, consisting of tracing at least 10% of the test data from origi- nal recording through transferring, calculating, summarizing and report- ing. Advanced Monitoring Systems Cen- ter at Battelle Analysis of Sorbisense samplers at the vendor identified laboratory Independent analytical laboratory used to analyze reference samples The use of a product specified with respect to matrix, target, effect and limitations Umweltbundesamt Austria Benzene, toluene, ethylbenzene and xylenes European Committee for Standardi- zation CEN Workshop agreement (ETV) Water Monitoring Center at DHI A test design where a standard solu- tion is applied directly to the Sorbi- sense samplers Dissolved organic carbon Control of drinking water quality against drinking water maximum concentrations. Danish Standard The way the target is affected, in this verification the way the target com- pounds are measured European standard Environmental technology verification (ETV) is an independent (third party) assessment of the performance of a technology or a product for a speci- fied application, under defined condi- tions and adequate quality assur- ance. European Union Evaluation of test data for a technol- ogy product for performance and data quality US ETV EPA program that develops generic verification protocols and verifies the performance of innovative environ- mental technologies that have the potential to improve protection of human health and the environment An examination of the efficiency of a technology 20 ------- Word Experts GC Groundwater investigation Groundwater monitoring GWS ISO Laboratory sample dis- penser Limit of detec- tion LoD Limit of quanti- fication LoQ Matrix mbgv mbs Method MS MTBE NOWATECH ETV P&T PE Performance claim Performance parameters Precision (Environmen- NOWATECH Independent persons qualified on a technology in verification or on verifi- cation as a process Gas chromatography Investigation of groundwater con- tamination with measurements con- trolled against groundwater maxi- mum concentrations. Baseline monitoring of groundwater quality. Groundwater sampler International Standardization Organi- zation Test device designed for controlled exposure of Sorbisense samplers to test solutions. Calculated from the standard devia- tion of replicate measurements at less than 5 times the detection limit evaluated. Corresponding to less than 5% risk of false blanks. Calculated from the detection limit, typically 3 times the LoD, the concen- tration, where the blank variation im- pacts the precision 20%. The type of material that the product is intended for m below groundwater table m below surface Generic document that provides rules, guidelines or characteristics for tests or analysis Mass spectrometry Methyl-fe/f-butylether Nordic Water Technology Verification Centers Purge and trap Performance evaluation: A quantita- tive evaluation of a measurement system, usually involving the meas- urement or analysis of a reference material of known value or composi- tion The effects foreseen by the vendor on the target (s) in the matrix of in- tended use Parameters that can be documented quantitatively in tests and that pro- vide the relevant information on the performance of an environmental technology product The standard deviation obtained from replicate measurements, here meas- ured under repeatability or repro- ducibility conditions. Ready to market or prototype stage US ETV Peer reviewers appointed for a verifi- cation (Environmental) technology 21 ------- Word tal) product PVC QA Range of ap- plication Reference analyses Reference samples Repeatability Reproducibility Robustness RSD Sampler Samples Sampling sys- tem SIM SM Stakeholder Standard NOWATECH product, process, system or service based upon an environmental tech- nology Polyvinylchloride Quality assurance The range from the LoD to the high- est concentration with linear re- sponse, Analysis by a specified reference method in an accredited (ISO 17025) laboratory. Samples taken for and analyzed by a specified reference method in an ac- credited (ISO 17025) laboratory. The precision obtained under repeat- ability conditions, that is with the same measurement procedure, same operators, same measuring system, same operating conditions and same location, and replicate measurements on the same or similar objects over a short period of time The precision obtained under repro- ducibility conditions, that is with measurements that includes different locations, operators, measuring sys- tems, and replicate measurements on the same or similar objects % variation in measurements result- ing from defined changes in matrix properties. Relative standard deviation in %. Sorbisense sorbent cartridge Samples taken with and analyzed after the Sorbisense method. The sampling reservoir and venting system used to operate the Sorbi- sense samplers Selected ion monitoring Standard Methods for the Examina- tion of Water and Wastewater, latest edition Generic document established by consensus and approved by a rec- ognized standardization body that provides rules, guidelines or charac- USETV Buyers and users of technology, technology developers/vendors, the consulting engineers, the finance and export communities, government permitters, regulators, first respond- ers, emergency response, disaster planners, public interest groups, and other groups interested in the per- formance of innovative environmental technologies. 22 ------- Word Standpipe Target (Environ- mental) tech- nology Test/testing Trueness ISA US EPA Vendor Verification VOC VOX WS NOWATECH teristics for tests or analysis Test device designed to simulate a groundwaterwell The property that is affected by the product, in this verification the target compounds measured. The practical application of knowl- edge in the environmental area Determination of the performance of a product by parameters defined for the application The % recovery of true value ob- tained either from knowledge on the preparation of test solutions or from measurements with reference meth- ods. Technical system audit United States Environmental Protec- tion Agency The party delivering the product or service to the customer Evaluation of product performance parameters for a specified application under defined conditions and ade- quate quality assurance Volatile organic compounds, here the compounds listed as target com- pounds/analytical parameters Volatile halogenated organic com- pounds, here the halogenated com- pounds listed as target com- pounds/analytical parameters Workshop (under CEN) USETV An all-inclusive term used to describe pollution control devices and sys- tems, waste treatment processes and storage facilities, and site remedia- tion technologies and their compo- nents that may be utilized to remove pollutants or contaminants from, or to prevent them from entering, the envi- ronment. The technology developer, owner, or licensee seeking verification Establishing or proving the truth of the performance of a technology un- der specific, predetermined criteria, test plans and adequate data QA procedures 23 ------- A P P E N D IX 2 Reference methods and references 24 ------- Reference analysis, VOC Water samples are taken as 40 mL samples in autosampler vials filled completely from the bottom and allow to overflow. A precise volume of subsample is transferred from the sampler vial to the airsparger via a sample loop and using helium as the pressure gas. The subsample is purged with helium and the purged compounds trapped on a VOCARB 3000 adsorbent, followed by thermal desorption at 240°C and transfer of desorbed compounds to the gas chro- matograph (GC). GC separation is followed by selected ion monitoring and quantifica- tion against external standard. Selectivity is ensured by applying a maximum limit of 20% deviation of mass ratios for the selected masses from reference run. The equipment used is Tekmar Aquatek 70/Velocity XPT and Agilent 6890 GC/5973 or 5975 MS Standard method references are EPA Method 624.2 191 and ISO 15680 /10/. 2 General chemistry Groundwater from wells in the field test will be characterized for general chemistry parameters using the below given methods. Analysis for pH and conductivity is done on-line in the field. Parameter PH Conductivity Nitrate Fluoride Chloride Bicarbonate Sulphate Method DS287 DS288 EN 10304 EN 10304 EN 10304 DS256 EN 10304 Parameter DOC Iron Ammonium Sodium Potassium Calcium Magnesium Method EN 1484 SM3500C DS224 SM3500C SM3500C SM3500C SM3500C General chemistry data for groundwater for the laboratory tests, see Appendix 3.7, will be obtained from the water work delivering the water. 25 ------- 2 References 1. Gran, C. Sorbisense GWS40 Passive Sampler. Joint verification protocol. 2008. 2. Battelle. Process Document for US EPA ETV AMS Center and NOWATECH DHI WMC Joint Verifica- tion of the Sorbisense Ground Water Sampler. 2009. 3. ISO. Guidance on Quality assurance of environmental water sampling and handling. 5667-14. 1998. 4. ISO. Water Quality - On-line sensors/analysing equipment for water - Specifications and prerformance tests. ISO 15839. 2006. 5. CEN. Environmental technology verification - Soil and groundwater site characterization, monitoring and remediation Technologies. CEN/WS CWA 32. 2008. 6. Sandia National Laboratories. Ground Water Sampling Technologies Verification Test Plan. U.S. Environ- mental Protection Agency. Environmental Technology Verification Program . 1999. 7. ISO. General requirements for the competence of testing and calibration laboratories. ISO 17025. 2005. 8. DHI. DHI Quality Manual. 2008. 9. US EPA. Measurement of Purgeable Organic Compounds in Water by Capillary Column Gas Chromatog- raphy/Mass Spectrometry. Method 624.2. 1995. 10. ISO. Water quality ~ Gas-chromatographic determination of a number of monocyclic aromatic hydrocar- bons, naphthalene and several chlorinated compounds using purge-and-trap and thermal desorption. ISO 15680. 2003. 11. International Standardization Organisation. EN ISO 9001. Quality management systems - Requirements. 15-11-2008. 12. OECD. OECD Principles of Good Laboratory Practice. OECD GLP Document No. 1. 21-1-1998. 13. Battelle. Quality Management Plan (QMP) for the ETV Advanced Monitoring Systems Center. Version 7.0. 17-11-2005. 14. NOWATECH. Verification test center quality manual. 2008. 26 ------- A P P E N D IX 3 In-house test methods 27 ------- The in-house test methods are the detailed specifications (work instructions) of the tests to be performed including specific information on the practical work planned, Appendices 3.1 to 3.4. The pre-testing is described in Appendix 3.5 and the check of solutions used in Appendix 3.6. Reagents are described in Appendix 3.7 and apparatus in Appendix 3.8. The volumes of solutions used for different experiments are summarized in Appendix 3.9. The storage and shipping of samples is described in Appendix 3.10. 28 ------- Appendix 3.1 Direct application of halogenated hydrocarbons standard to samplers. For personal safety and to avoid contamination, wear nitrile gloves for all handling of equip- ment. a) Place 7 samplers in the fume cupboard in a vial stand. b) Add the spike (50 jiL of 24.7 |ig/mL VOX standard dilution for SxLoD, 50 jiL standard solution for 10 % of range) directly into the adsorber resin of the sampler using a 50 jiL gas tight syringe. c) Place each sampler into a separate 100 mL glass bottle with PTFE-lined screw cap. d) Place 3-4 of the 100 mL bottles into a 2 L wide-neck glass bottle with Teflon-lined screw cap. e) Let the samplers equilibrate at 4°C for 24 hours at least. f) Remove the samplers from the glass bottles. g) Connect 3 of the samplers to the sample dispenser using new 1/16" capillaries. h) Convey 300 ml (collect in 500 mL graduated cylinders) of water through each sampler during ca. 4 hours. This is done in batches of 2-3 samplers, before the sample dispenser has been used with VOCs, but after the blank test of the sample dispenser. i) Prepare the samplers for shipping. 29 ------- Appendix 3.2 Laboratory sample dispenser. For personal safety and to avoid contamination, wear nitrile gloves for all handling of equip- ment. 1 Preparations a) Start with the clean, empty dispenser, lid attached, air exchange pipe detached from the wash bottle. Make sure the stir bar in the dispenser is positioned in the middle of the dispenser bottom and rotating when stirrer is switched on. b) Connect the sampler capillaries to the 1/16 inch fittings. Place the ends of the capillaries above the lid of the lab dispenser to avoid leakage. c) Add 35 mL potassium chloride stock solution to the dispenser through the spiking port, using a 100 mL syringe with Luer lock. For the tests with different ionic strength add 10 mL for 10 mS/m or 100 mL for 100 mS/m). Rinse with 100 mL of water d) Fill the dispenser with water (see separate instruction below) e) Add the VOC spike to the dispenser (see separate instruction below). f) Fill the wash bottle with water up to the 5.5 L-mark, using the PTFE tubing. g) Add the adequate spike directly to the wash bottle (under the water surface) and close the wash bottle. h) Connect the exchange pipe and tighten the fittings. i) Start the magnetic stirrers in the wash bottle. j) Take down the end of the capillaries from the dispenser. Let at least 1 mL go to drain. k) Make sure that 30 minutes have passed since the magnetic stirrers have been started; then, connect a sampler to each capillary. 1) Start the magnetic valve timer. m) Note the time and possible deviations 2 Filling the dispenser with water a) Attach one end of the PTFE tube to the vertical nozzle of the sampling port. Attach the other end to the water tap (MilliQ). b) Open the two-way valve in the lid of the dispenser. c) Open the sampling port valve. Open the water tap to fill the dispenser until water over- flows from the open two-way valve. d) Close the water tap. Close the spiking port valve. e) Remove the PTFE tube and close the open ends with tinfoil. f) Drain 200 mL of water from the dispenser through the sampling port. Measure conduc- tivity and temperature in the drained water. g) Continue with step le 3 Addition of spike to the lab dispenser a) Start the dispenser's magnetic stirrer b) Open a stock solution vial with appropriate volume. c) Fill the appropriate amount into the suitable gaslight syringe with Luer lock, with nee- dle attached. 30 ------- d) Remove the needle from the syringe and connect the syringe to the dispenser's spiking port. e) Open the spiking port valve and add the contents to dispenser. f) Close the spiking port valve and remove the syringe. g) Attach the needle and fill syringe with methanol. Detach the needle and add also the methanol to the dispenser. h) Close the spiking valve, and remove the syringe. i) Fill a 100 mL syringe with Luer lock with water. Add the water to the dispenser. Close the spiking port valve and remove the syringe. j) Close the two-way valve in the lid of the dispenser. k) Continue with step If 4 During exposure a) Control the amount of liquid that has passed through each sampler after /^ the sampling time and full sampling time by collecting in pre-weighed 1000 mL bottles. b) Take water phase sample from the dispenser after 2 hours, 1A the sampling time and full sampling time, following the sampling instruction. 5 Reference sampling instructions a) Wipe the vertical nozzle of the sample tap with acetone-soaked paper tissue. Rinse the nozzle with water from a bottle, dry with paper tissue. b) Set the magnetic valves to open. c) Open the sample tap and drain 25 mL to waste. d) Place the nozzle in a 40 mL P&T vial, open the sample valve by ca. 45 degrees and fill the vial slowly from below. Let the sample overflow for at least 3 seconds. Close the sample tap, and close the vial. e) Repeat c) for the 2 following P&T vials. f) Start the magnetic valve timer. g) Repeat a) to clean the nozzle after sampling. h) Store cold 1-5°C and dark for no more than 3 days and transfer to laboratory. 5 End of exposure a) Stop both magnetic stirrers. b) Open the two-way valve in the lid of the dispenser. c) Drain the dispenser through the sample tap, into containers for disposal. d) Remove the samplers and send them for analysis. e) Detach the air exchange pipe from the wash bottle6 and tilt the container towards the sample tap to empty completely. f) Detach the magnetic valve from the other side of the wash bottle. g) Empty the wash bottle. Attach the air exchange pipe lightly until next use. 6 Whenever detaching the connections of the wash bottle, detach the nut on the steel side of the fitting, not on the glass side. 31 ------- Appendix 3.3 Standpipe 1 Preparations Wear nitrile gloves for all handling of equipment. a) Mount the needed number of samplers with samplers into the empty Standpipe. Tighten with the provided strings b) Connect the air exchange pipes to the lid. c) Close the Standpipe. d) Open the two-way valve in the lid of the Standpipe. e) Fill the Standpipe from the bottom with ground water, using PTFE tubing, until water overflows from the open two-way valve. f) Stop the water flow, close the sampling port valve and remove the PTFE tubing. g) Drain 200 mL from the Standpipe. Measure conductivity and temperature in the drained water. h) Start the circulation pump. i) Add the spike to the Standpipe (see separate instruction). j) Fill the wash bottle with water up to the 5.5 L-mark, using the PTFE tubing. k) Add an adequate spike directly to the wash bottle (under the water surface) and close the wash bottle. 1) Connect the air exchange pipe. m) Start the magnetic stirrer in the wash bottle. Start the magnetic valve timer. n) Note the time and possible deviations 2 Addition of spike to the Standpipe a) Make sure the magnetic valves are closed. b) Open a stock solution vial with appropriate volume. c) Fill the appropriate amount into the suitable gaslight syringe with Luer lock, with nee- dle attached. d) Remove the needle from the syringe and connect the syringe to the Standpipe's spiking port. e) Open the spiking port valve and add the contents to Standpipe. f) Close the spiking port valve and remove the syringe. g) Fill a 100 mL syringe with Luer lock with water. Add the water to the dispenser. Close the spiking port valve and remove the syringe. h) Close the two-way valve in the lid of the Standpipe. i) Continue with step Ih 3 During the exposure Take water phase sample from the dispenser after 2 hours, /^ the sampling time and full sampling time, following the sampling instruction. 32 ------- 4 Reference sampling instructions a) Wipe the vertical nozzle of the sample tap with acetone-soaked paper tissue. Rinse the nozzle with water from a bottle, dry with paper tissue. b) Set the magnetic valves to open. c) Open the sample tap and drain 25 mL to waste. d) Place the nozzle in a 40 mL P&T vial, open the sample valve by ca. 45 degrees and fill the vial slowly from below. Let the sample overflows for at least 3 seconds. Close the sample tap, and close the vial. e) Repeat c) for the 2 following P&T vials. f) Start the magnetic valve timer. g) Repeat a) to clean the nozzle after sampling. h) Store cold 1-5°C and dark for no more than 3 days and transfer to laboratory. 4 End of exposure a) Stop the magnetic stirrer in the air wash bottle. b) Stop the recirculation pump. c) Open the two-way valve in the lid of the standpipe. d) Remove the air exchange pipe. e) Drain the standpipe into containers for disposal, using the sample tap. f) Open the standpipe and take up the sampler g) Remove the samplers and send them for analysis h) Measure the sampled water volume by collecting in 1000 mL pre-weighed glass bottles and weighing i) Tilt the container towards the sample tap to empty completely. j) Empty the wash bottle. Attach the air exchange pipe lightly. 33 ------- Appendix 3.4 Field sampling 1 Data compilation First planning step includes data compilation in order to allow for the detailed plan- ning: Full Address S0borg hovedgade 23, S0borg S0borg hovedgade 17-19, S0borg S0borg hovedgade 189, S0borg Fa rum Bytorv 36, Farum Roskildevej 2-4, Al- bertslund Well iden- tification AFV6 AFV4 B109 AFV1 K4 Well regis- tration number 201.5751 201.5749 201.5743 193.2283 200.5185 Contact, name, phone, e-mail Region Hovedstaden, Jens Lerche Mortensen, +45 48 20 53 33, jens.lerche.mortensen@ regionh.dk Region Hovedstaden, Jens Lerche Mortensen, +45 48 20 53 33, jens.lerche.mortensen@ regionh.dk Region Hovedstaden, Jens Lerche Mortensen, +45 48 20 53 33, jens.lerche.mortensen@ regionh.dk Jord»Milj0, Charlotte Juhl S0egaard, +45 35 82 04 02, cjs@jordmil.dk Jord»Milj0, Charlotte Juhl S0egaard, +45 35 82 04 02, cjs@jordmil.dk Well iden- tification AFV6 AFV4 B109 AFV1 K4 Filter (mbs) 7 5-13.3 9.5-14.5 13.5-46.5 8-15 7.5-9.5 Diameter (mm) 125 160 165 160 160 Groundwa- ter table (mbs) 7.7 11.5 22 7.3 5.3 Geology Sand Sand Sand Sand Limestone Well iden- tification AFV6 Pump (mbs) 13 Yield (m3/hour) 0.2 Pumping pattern Start at water level < 12 mbs, stop at 13 mbs Access for samplers Should be possible to place next to pump mbs: meter below surface 34 ------- Well iden- tification AFV4 B109 AFV1 K4 Pump (mbs) 14 37 12 8.5 Yield (m3/hour) 1.5-2.5 2-2.5 1.5-2 2.5 Pumping pattern Start at water level < 8.5 mbs, stop at 9.5 mbs Continuously, stop for cleaning 15 min/day Continuously 3 min pumping, 5 min stop, etc. Access for samplers Should be possible to place next to pump Good access Should be possible to place next to pump Should be possible to place next to pump 2 Reference sampling strategy The second planning step is to select the reference sampling strategy (pump depth or above pump) and to select the sampling (0.5-5 mbgvt8) and reference sampling posi- tions. The pump depth sampling strategy applies sampling of the pumped stream. In cases where the pump is positioned deeper than the maximum sampler depth, a posi- tion above the pump is chosen, the above pump strategy. Well iden- tification AFV6 AFV4 B109 AFV1 K4 Sampler position (mbs) 13 14 27 12 8.5 Sampler posi- tion to in well groundwater table distance (m) 1-2 3.5-4.5 4 1 0.5-3.5 Reference sampling position (mbs) 13 14 27 12 8.5 Sampling strategy Pump depth Pump depth Above pump Pump depth Pump depth 3 Sampling The sampling is done as follows: a) Mount a sampling system with a sampler in the well at the selected depth b) Secure the position with the provided string c) Leave the sampler in position for 6 days d) Take up the sampler e) Remove the sampler and send it for analysis f) Repeat twice mbgv: m below groundwater table 35 ------- The reference sampling is done as follows, for the pump depth strategy: a) Mount sampling tube upon pump exit sampling tap b) Flush tap and tube 5-10 minutes with lowest flow filling the tube c) Fill sample containers from the bottom and allow to overflow 2-3 times d) Store and preserve samples as prescribed and send to the laboratory The reference sampling is done as follows, for the above pump strategy: a) Ensure that well pump is running at routine yield b) Lower the pump into the well to the selected depth c) Purge with the lowest flow filling the tube for 5-10 minutes, max 5% of stationary pump yield d) Ensure stability (within 10%) of indicator parameters (pH, dissolved oxygen, con- ductivity) e) Fill sample containers from the bottom and allow to overflow 2-3 times ensuring no head space in the containers e) Store and preserve samples as prescribed and send to the laboratory Reference sampling is done before, between and after each sampling, totally 4 times. Field blanks are prepared during the first reference sampling at each site. Water is transferred to sample bottles on site and the samples at stored, transported and ana- lyzed as reference samples. Sampling is done using a Grundfos MP1 pump equipped with 10 mm Teflon tubes, leaving the tubes in each well. Indicator parameters (pH, dissolved oxygen, conductiv- ity, temperature) are measured in a flow through on-line cell. 36 ------- Appendix 3.5 Pre-testing Laboratory sample dispenser Objective Test design Samples Blank test Dispenser filled with water. Triplicate reference sam- ples 1) of water, 2) from dispenser directly 30 min after addition, and 3) from dispenser after 6 days. VOC stability in dispenser Dispenser filled with water, spiked to SxLoD. Triplicate samples 1) of 0.1 g/L VOC solution, 2) from dispenser 30 minutes after addition, and 3) from dis- penser after 6 days. 37 ------- Appendix 3.6 Preparation of solutions for reference analysis 1 10 g/L VOC stock solution Check of concentrations is done initially and each time a subsample is taken out for use. Initial testing is done by filling a 1,5 mL capped vial with stock solution at -20 °C, us- ing a low-flow pipette. Close vial. Produce triplicate vials in this way. Place each of the 1 mL capped vials in a larger capped vial. Store cold 1-5°C and dark for no more than 3 days and transfer to laboratory with information of concentration range. Check during use: after using part the stock solution in the vial for spiking, fill one 1,5 mL capped vials with the solution using a gas-tight syringe. Close the vial and place it in a larger capped vial. Store cold 1-5°C and dark for no more than 3 days and transfer to laboratory with information on concentration range. Produce 2 more vials and keep at -20 °C for possible future reference 2 0.1 g/L VOC solution Check during use is done after using part the solution in the vial for spiking by trans- ferring 1 mL to a cap vial using a low-flow pipette. Close vial, shake well. Produce triplicate vials in this way. Close the vials and place each in a larger capped vial. Store cold 1-5°C and dark for no more than 3 days and transfer to laboratory with informa- tion of concentration range. 3 VOX Standard dilution Check during use is done after using part the stock solution in the 6 mL vial with VOX standard dilution for spiking. Fill three 1.5 mL capped vials with the solution using a gas-tight syringe. Close the vials and place them in a P&T vial. Store cold 1-5°C and dark for no more than 3 days and transfer to laboratory with information of concentra- tion range 38 ------- Appendix 3.7 Reagents 1 Water Laboratory grade water from Millipore system with electrical conductivity below 10 MQ/cm. Dissolved organic carbon below 0.1 mg/L and target VOC below the limit of detection 0.02 |ig/L is expected and verified in first blank test series. 2 Groundwater Potable water as obtained from the supply network at DHL Groundwater characteris- tics are as follows: Parameter PH Conductivity Nitrate Fluoride Chloride Bicarbonate Sulphate Value 7.6 71 mS/m 2.4 mg/L 0.62 mg/L 44 mg/L 340 mg/L 21 mg/L Parameter DOC Iron Ammonium Sodium Potassium Calcium Magnesium Value 1 .5 mg C/L 0.02 mg/L 0.058 mg/L 30 mg/L 3.8 mg/L 85 mg/L 22 mg/L Target VOC is below the limit of detection 0.02 |ig/L. 3 VOX standard Standard solution "QTM Volatile Halocarbons Mix" produced by Supelco, purchased from Sigma-Aldrich, product number 48001, lot number LB59726, with analytical certificate, MFG date July 2008, nominal concentrations as follows (among other VOCs): Compound Chloroethene 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Nominal concentration ug/L 1998 2000 2000 1951 2000 2000 Chemicals Compound 1,1-Dichloroethene trans-1 ,2- Dichloroethene Pro- ducer Supelco Supelco Quality Analytical standard Analytical standard Purity 99.9% 99.9% Batch LB56468 LB57511 39 ------- Compound cis- 1 ,2- Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene m-Xylene o-Xylene MTBE Methanol Potassium chloride Pro- ducer Fluka Fluka Supelco Fluka Fluka Fluka Fluka Fluka Fluka Fluka Fluka Quality Analytical standard Puriss. p. a. Analytical standard Puriss. p. a. Puriss. p. a. Puriss. p. a. Puriss. p. a. Puriss. p. a. Puriss. p. a. Puriss. p. a. For trace analysis of chlorinated hydrocar- bons Puriss. p. a. Purity 99.7% >99.5% 99.9% 99.9% >99.7% >99.0% >99.0% >99.0% >99.5% >99.8% >99.5% Batch 7333X 1368013 LB56979 1369911 1392028 1388758 1399073 1406896 1399802 1379978 80150 5 10 g/L VOC stock solution Prepare a 10 g/L solution of each target VOC as follows: a) Fill a 250 mL volumetric flask (with glass stopper) with methanol, refrigerate to -20°C and mark the level. b) Keep 210 mL methanol in the volumetric flask, place on ice in fume cup- board. c) Add the volume indicated below of each chemical using low flow pipettes, starting with the highest boiling compound and keeping the pipette below the methanol surface while emptying. Close the flask after each addition. d) Refrigerate flask to -20°C e) Fill the volumetric flask to the new mark with methanol refrigerated to -20°C. f) Shake by hand until no phase difference is visible. g) Distribute the stock solution into 1.5, 3.5 and 10 ml capped vials using a low flow pipette. Check cap tightness (tight when cannot be twisted), wrap with aluminum foil and place in freezer, -20°C. Compound Chloroethene 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m-Xylene uL pipetted - 2000 2000 1 500 1 750 1 500 2750 2750 2750 2750 3000 Density 9/L - 1.218 1 .2565 1.2837 1 .4642 1 .6227 0.87865 0.8669 0.867 0.8802 0.8642 ug pipetted - 2 436 000 2513000 1 925 550 2 562 350 2 434 050 2416288 2 383 975 2 384 250 2 420 550 2 592 600 Concentration g/L - 9.74 10.05 7.70 10.25 9.74 9.67 9.54 9.54 9.68 10.37 40 ------- Compound MTBE uL pipetted 3250 Density 9/L 0.74 ug pipetted 2 405 000 Concentration g/L 9.62 6 0.1 g/L VOC solution Prepare a 0.1 g/L solution from the lOg/L solution as follows, directly before use. a) Open a 1.5 mL vial of 10 g/L stock solution b) Fill a 10 mL capped vial with 10 mL of methanol using a low flow pipette at 20°C±2°C c) Add 100 jiL of 10 g/L stock solution using a gas tight syringe with cemented needle, keep needle under methanol surface while emptying. d) Close the vial, check for tightness. e) Shake by hand. f) Use after letting the solution equilibrate at room temperature for 1 hour. 7 24.7 ug/L VOX standard dilution for direct application Prepare a 24.7 |ig/mL stock solution of halogenated hydrocarbons as follows: a) Add 6 mL of methanol to a 6 mL cap vial using a low flow pipette. b) Transfer 75 jil of the 2000 |ig/mL volatile hydrocarbon standard to the cap vial using a 50 jiL gas tight syringe, keeping the needle below the methanol surface while emptying. c) Close the vial, check for tightness. d) Shake by hand. e) Use after letting the solution equilibrate at room temperature for 1 hour. 8 205 g/L KC1 stock solution Prepare a 205 g/1 stock solution of potassium chloride: a) Place a 1000 mL volumetric flask with 200 mL of water b) Weigh the flask with water c) Add portions of KC1 dried at 105°C overnight and shake well d) When all 205 g of KC1 is dissolved, allow the solution to equilibrate to room temperature. e) Fill the flask to the mark. f) Transfer to a 1000 mL glass bottle and close with a blue cap screw lid. 41 ------- Appendix 3.8 Apparatus 1 Glass syringes and adapters a) 1 gas tight glass syringe with stainless steel Luer-lock, 2.5 mL b) 1 gas tight glass syringe with stainless steel Luer-lock, 5 mL c) 1 gas tight glass syringe with stainless steel Luer-lock, 10 mL d) 1 stainless steel Luer/Luer adapter with valve, each for lab dispenser and standpipe. e) 6 needles with Luer adapter, 22 ga (0.394 mm ID) f) 1 gas tight syringes with fixed needle, 25 jiL g) 2 gas tight syringes with fixed needle, 50 jiL h) 1 gas tight syringe with fixed needle, 100 jiL i) 1 gas tight syringe with fixed needle, 500 jiL j) 1 gas tight syringe with fixed needle, 1000 jiL k) Glass syringe with Luer lock, 100 mL 2 Glassware a) Volumetric flasks 250 mL and 1000 mL with glass stopper b) Low flow glass pipettes at 250, 500, 7500, 1000, 1250, 1500, 2000 and 2500 ,iL c) 3 stir bars, glass coated d) Capped vials for 1.5, 3.5, and 10 mL, caps with PTFE seals. e) 25 mL Erlenmeyer flask with mark f) 200 mL Erlenmeyer flask with mark g) 1000 mL bottle with blue screw cap h) 1000 mL bottles with red screw cap i) 500 mL graduated cylinders 3 Miscellaneous a) Micropipettes with tips at 100 jiL, 1 mL and 5 mL b) Dedicated, water flushed PTFE tubes, 8x6 mm diameter c) Nitrile gloves 3 Field a) GrundfosMPl pump b) Transformer box c) 220 V generator d) Dedicated, water flushed 10 mm PTFE tubes e) On-line flow through devices (WTW) for monitoring of indicator parameters (pH, dissolved oxygen, conductivity) 42 ------- Appendix 3.9 Spike volumes and solutions Experiment H L BA DA EA FA GA HA HA HA J N P R T V CA Lab dispenser or standpipe (mL) 0.050 0.050 4.00 4.00 4.00 4.00 4.00 1.50 4.00 6.00 2.50 2.00 5.00 10.00 15.00 20.00 10.00 Wash bottle (mL) — — 0.55 0.55 0.55 0.55 0.55 0.2 0.55 0.85 0.125 0.10 0.25 0.50 0.80 1.00 0.50 Solution VOX standard dilution VOX standard 1 0 g/L VOC stock solution 1 0 g/L VOC stock solution 1 0 g/L VOC stock solution 1 0 g/L VOC stock solution 1 0 g/L VOC stock solution 1 0 g/L VOC stock solution 1 0 g/L VOC stock solution 1 0 g/L VOC stock solution 0.1 g/L VOC solution 1 0 g/L VOC stock solution 1 0 g/L VOC stock solution 1 0 g/L VOC stock solution 1 0 g/L VOC stock solution 1 0 g/L VOC stock solution 1 0 g/L VOC stock solution 43 ------- Appendix 3.10 Managing, storing and shipping of samples/samplers 1 Managing samples a) Prior to each individual test, the sampling responsible (test technician or field responsible) labels the correct type and number of sample vials, according to information in the test plan and the data forms. For cap vials, only the labels are prepared, to avoid contamination. b) The test responsible checks the array of labeled sample bottles and labels against the test plan and the data forms. c) After sampling, the sampling responsible takes a photo of the sample vials and sends the photo to the test responsible immediately. d) The sampling responsible stores the sample vials. e) The test responsible prepares a requisition for analysis, and sends it to the sam- pling responsible. f) The sampling responsible ships the samples, and making sure that they are sent within the maximum stated storage time. g) The sampling responsible informs the test responsible immediately when the samples have been sent. h) The sampling responsible keeps a copy of the requisition with a note of the date of shipping. 2 Sample storing, reference samples Water samples are taken in 40 mL P&T vials. Samples are stored cold 1-5°C and dark for no more than 3 days prior to transfer to the laboratory. 3 Sample storing, samplers Samplers are equipped with protective caps in both ends, placed in transportation tubes and stored cold 1-5°C and dark for no more than 7 days prior to transfer to the laboratory. 4 Sample shipping, reference samples Water samples (P&T vials) are sent in cooling boxes with cooling elements. Cap vials with stock solution or stock dilution are placed individually into a P&T vial and may be sent in a non-isolated package, with one cooling element. 44 ------- 5 Sample shipping, samplers Samplers are packed in the transport tubes in a cardboard box at ambient temperature. 45 ------- A P P E N D IX 4 In-house analytical methods 46 ------- None 47 ------- A P P E N D I X 5 Data reporting forms 48 ------- A Check of 10 g/L VOC stock solution, reference analyses, unopened vial Compound Date 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Dec.1,2008 A1 Not taken A2 Cone Not taken A3 entration mg/L Jan. 8, 2009 A4 Jan. 8, 2009 A5 Jan. 8, 2009 A6 aA Check of 10 g/L VOC stock solution, reference analyses, used in test BA. Spare vials are not sent for analysis, but kept in the freezer. Compound Date 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Usage Date aA1 Concen Spare Vial aA2 tration g/L Spare Vial aA3 49 ------- bA Check of 10 g/L VOC stock solution, reference analyses, used in test DA. Spare vials are not sent for analysis, but kept in the freezer. Compound Date 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Usage Date bA1 Concen Spare Vial bA2 tration g/L Spare Vial bA3 50 ------- cA Check of 10 g/L VOC stock solution, reference analyses, used in test EA. Spare vials are not sent for analysis, but kept in the freezer. Compound Date 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Usage Date cA1 Concen Spare Vial cA2 tration g/L Spare Vial cA3 o!A Check of 10 g/L VOC stock solution, reference analyses, used in test FA. Spare vials are not sent for analysis, but kept in the freezer. Compound Date 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Usage Date dA1 Concen Spare Vial dA2 tration g/L Spare Vial dA3 51 ------- eA Check of 10 g/L VOC stock solution, reference analyses, used in test GA. Spare vials are not sent for analysis, but kept in the freezer. Compound Date 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Usage Date eA1 Concen Spare Vial eA2 tration g/L Spare Vial eA3 fA Check of 10 g/L VOC stock solution, reference analyses, used in test HA for 20 % of range. Spare vials are not sent for analysis, but kept in the freezer. Compound Date 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Usage Date fA1 Concen Spare Vial fA2 tration g/L Spare Vial fA3 52 ------- gA Check of 10 g/L VOC stock solution, reference analyses, used in test HA for 50 % of range. Spare vials are not sent for analysis, but kept in the freezer. Compound Date 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Usage Date QA1 Concen Spare Vial QA2 tration g/L Spare Vial gA3 hA Check of 10 g/L VOC stock solution, reference analyses, used in test HA for 80 % of range. Spare vials are not sent for analysis, but kept in the freezer. Compound Date 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Usage Date hA1 Concen Spare Vial hA2 tration g/L Spare Vial hA3 53 ------- IA Check of 10 g/L VOC stock solution, reference analyses, used in test N. Spare vials are not sent for analysis, but kept in the freezer. Compound Date 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Usage Date iA1 Concen Spare Vial iA2 tration g/L Spare Vial iA3 jA Check of 10 g/L VOC stock solution, reference analyses, used in test P. Spare vials are not sent for analysis, but kept in the freezer. Compound Date 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Usage Date JA1 Concen Spare Vial JA2 tration g/L Spare Vial JA3 54 ------- kA Check of 10 g/L VOC stock solution, reference analyses, used in test R. Spare vials are not sent for analysis, but kept in the freezer. Compound Date 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Usage Date kA1 Concen Spare Vial kA2 tration g/L Spare Vial kA3 IA Check of 10 g/L VOC stock solution, reference analyses, used in test T. Spare vials are not sent for analysis, but kept in the freezer. Compound Date 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Usage Date IA1 Concen Spare Vial IA2 tration g/L Spare Vial IA3 55 ------- mA Check of 10 g/L VOC stock solution, reference analyses, used in test V. Spare vials are not sent for analysis, but kept in the freezer. Compound Date 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Usage Date mA1 Concen Spare Vial mA2 tration g/L Spare Vial mA3 nA Check of 10 g/L VOC stock solution, reference analyses, used in test CA. Spare vials are not sent for analysis, but kept in the freezer. Compound Date 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Usage Date nA1 Concen Spare Vial nA2 tration g/L Spare Vial nA3 56 ------- B Check of 0.1 g/L VOC solution, reference analyses, used in lab dispenser pre-testing Compound Date 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Preparation Date B1 Concen Preparation Date B2 tration g/L Preparation Date B3 aB Check of 0.1 g/L VOC solution, reference analyses, used in test J Compound Date 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Preparation Date aB1 Concent Preparation Date aB2 ration mg/L Preparation Date aB3 57 ------- C Check of VOX standard dilution, reference analyses Compound Date Chloroethene 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Preparation Date C1 Concent Preparation Date C2 ration mg/L Preparation Date C3 aD Check of MiliQ water from tap Compound Date Chloroethene 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Sample 1 aD1 Concent Sample 2 aD2 ration ug/L Sample 3 aD3 58 ------- bD Check of water from lab dispenser sample tap after 30 minutes. Compound Date Chloroethene 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Sample 1 bD1 Concent Sample 2 bD2 ration ug/L Sample 3 bD3 D Check of water from lab dispenser sample tap after 6 days Compound Date Chloroethene 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Sample 1 D1 Concent Sample 2 D2 ration ug/L Sample 3 D3 59 ------- cD Check of ground water (blank) Compound Date: Chloroethene 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Sample 1 cD1 Concenl Sample 2 cD2 ration ug/L Sample 3 cD3 E VOC stability check of sample dispenser, reference samples after 30 minutes Compound Date 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Sample 1 E1 Concenl Sample 2 E2 ration ug/L Sample 3 E3 60 ------- aE VOC stability check of sample dispenser, reference samples after 6 day Compound Date 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Sample 1 aE1 Concent Sample 2 aE2 ration ug/L Sample 3 aE3 F and G are omitted, covered by experiment J. 61 ------- H LoD direct application, samples Compound Date of spiking Temperature Chloroethene 1,1-Dichloroethene 1,2-Dichloroethenes Trichloroethene Tetrachloroethene Date of rinsing mL passed (measured) mL passed (by tracer salt) ID H1 ID H2 M ID H3 ass on sampler |j ID H4 g ID H5 ID H6 ID H7 is omitted, covered by experiment C. 62 ------- J LoD standpipe, samples Compound 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE mL sampled (measured) mL sampled (by tracer salt) ID J1 ID J2 Co ID J3 ncentration |j ID J4 3/L ID J5 ID J6 ID J7 Dates Setup Sampled Pressure head at sep-up cm - - - - - - Temperatures Setup Sampled External pressure bar - - - - - - K LoD standpipe, reference samples Compound 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Sample 1 Date K1 Sample 2 Date K2 Co Sample 3 Date K3 ncentration ug/L Sample 4 Date K4 Sample 5 Date K5 Sample 6 Date K6 Sample 7 Date K7 63 ------- L Precision direct application, samples Compound Date of spiking Temperature Chloroethene 1,1-Dichloroethene 1,2-Dichloroethenes Trichloroethene Tetrachloroethene Date of rinsing mL passed (measured) mL passed (by tracer salt) ID L1 ID L2 M ID L3 ass on sampler |j ID L4 g ID L5 ID L6 ID L7 M omitted, dilution volume will be insufficient 64 ------- N Precision standpipe 10%, samples Compound 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE mL sampled (measured) mL sampled (by tracer salt) C ID N1 oncentration |j ID N2 g/L ID N3 Dates Setup Sampled Pressure head at sep-up cm - - - - - - Temperatures Setup Sampled External pressure bar - - - - - - O Precision standpipe 10%, reference samples Compound 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene Sample 1 Date O1 Concentration ug/L Sample 2 Date O2 Sample 3 Date O3 65 ------- Compound MTBE Concentration ug/L P Precision standpipe 25%, samples Compound 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE mL sampled (measured) mL sampled (by tracer salt) C ID P1 oncentration |j ID P2 g/L ID P3 Dates Set up Sampled Pressure head at sep-up cm - - - - - - Temperatures Set up Sampled External pressure bar - - - - - - Q Precision standpipe 25%, reference samples Compound 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene Sample 1 Date Q1 Concentration ug/L Sample 2 Date Q2 Sample 3 Date Q3 66 ------- Compound o-Xylene m+p-Xylene MTBE Concentration ug/L R Precision standpipe 50%, samples Compound 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE mL sampled (measured) mL sampled (by tracer salt) C ID R1 oncentration |j ID R2 g/L ID R3 Dates Set up Sampled Pressure head at sep-up cm - - - - - - Temperatures Set up Sampled External pressure bar - - - - - - S Precision standpipe 50%, reference samples Compound 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Concentration ug/L Sample 1 Date S1 Sample 2 Date S2 Sample 3 Date S3 67 ------- Compound Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Concentration ug/L 68 ------- T Precision standpipe 75%, samples ompound 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE mL sampled (measured) mL sampled (by tracer salt) ID T1 Concentrat ID T2 ion (jg/L ID T3 Dates Set up Sampled Pressure head at sep-up cm - - - - - - Tem- pera- tures Set up Sam- pled Exter- nal pres- sure bar - - - - - - 69 ------- U Precision standpipe 75%, reference samples Compound 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Sample 1 Date U1 Concentration ug/L Sample 2 Date U2 Sample 3 Date U3 V Precision standpipe 100%, samples Compound 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE mL sampled (measured) mL sampled (by tracer salt) C ID V1 oncentration |j ID V2 g/L ID V3 Dates Set up Sampled Pressure head at sep-up cm - - - - - - Temperatures Set up Sampled External pressure bar - - - - - - 70 ------- X Precision standpipe 100%, reference samples Compound 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Sample 1 Date X1 Concentration ug/L Sample 2 Date X2 Sample 3 Date X3 Z omitted, redundant initially. 71 ------- AA Precision field, samples, and groundwater chemistry Well number Samples Compound Chloroethene 1,1-Dichloroethene trans-1,2-Dichloroethene cis-1,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE L sampled (by tracer salt) Date set up Date sampled Temperature, °C Depth water table set up, mbs Depth water table sampling, mbs Depth top sampler, mbs Depth bottom well, mbs Pump yield m3/L AA General chemistry Parameter Conductivity Nitrate Fluoride Chloride Bicarbonate Sulphate Value mS/m mg/L mg/L mg/L mg/L mg/L Parameter Value DOC mg C/L Iron mg/L Ammonium mg/L Sodium mg/L Potassium mg/L Calcium mg/L Magnesium mg/L 72 ------- AA Precision field, reference samples Well number Compound Chloroethene 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Sample 1 Date AA4 Concentr; Sample 2 Date AA5 jtion ug/L Sample 3 Date AA6 Sample 4 Date AA7 73 ------- AB Precision field, samples, and groundwater chemistry Well number Samples Compound Chloroethene 1,1-Dichloroethene trans-1,2-Dichloroethene cis-1,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE L sampled (by tracer salt) Date set up Date sampled Temperature, °C Depth water table set up, mbs Depth water table sampling, mbs Depth top sampler, mbs Depth bottom well, mbs Pump yield m3/L AB General chemistry Parameter Conductivity Nitrate Fluoride Chloride Bicarbonate Sulphate Value mS/m mg/L mg/L mg/L mg/L mg/L Parameter Value DOC mg C/L Iron mg/L Ammonium mg/L Sodium mg/L Potassium mg/L Calcium mg/L Magnesium mg/L 74 ------- AB Precision field, reference samples Well number Compound Chloroethene 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Sample 1 Date AB4 Concentr; Sample 2 Date AB5 jtion ug/L Sample 3 Date AB6 Sample 4 Date AB7 75 ------- AC Precision field, samples, and groundwater chemistry Well number Samples Compound Chloroethene 1,1-Dichloroethene trans-1,2-Dichloroethene cis-1,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE L sampled (by tracer salt) Date set up Date sampled Temperature, °C Depth water table set up, mbs Depth water table sampling, mbs Depth top sampler, mbs Depth bottom well, mbs Pump yield m3/L AC General chemistry Parameter Conductivity Nitrate Fluoride Chloride Bicarbonate Sulphate Value mS/m mg/L mg/L mg/L mg/L mg/L Parameter Value DOC mg C/L Iron mg/L Ammonium mg/L Sodium mg/L Potassium mg/L Calcium mg/L Magnesium mg/L 76 ------- AC Precision field, reference samples Well number Compound Chloroethene 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Sample 1 Date AC4 Concentr; Sample 2 Date ACS jtion ug/L Sample 3 Date AC6 Sample 4 Date AC7 77 ------- AD Precision field, samples, and groundwater chemistry Well number Samples Compound Chloroethene 1,1-Dichloroethene trans-1,2-Dichloroethene cis-1,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE L sampled (by tracer salt) Date set up Date sampled Temperature, °C Depth water table set up, mbs Depth water table sampling, mbs Depth top sampler, mbs Depth bottom well, mbs Pump yield m3/L AD General chemistry Parameter Conductivity Nitrate Fluoride Chloride Bicarbonate Sulphate Value mS/m mg/L mg/L mg/L mg/L mg/L Parameter Value DOC mg C/L Iron mg/L Ammonium mg/L Sodium mg/L Potassium mg/L Calcium mg/L Magnesium mg/L 78 ------- AD Precision field, reference samples Well number Compound Chloroethene 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Sample 1 Date AD4 Concentr; Sample 2 Date ADS jtion ug/L Sample 3 Date AD6 Sample 4 Date AD7 79 ------- AE Precision field, samples, and groundwater chemistry Well number Samples Compound Chloroethene 1,1-Dichloroethene trans-1,2-Dichloroethene cis-1,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE L sampled (by tracer salt) Date set up Date sampled Temperature, °C Depth water table set up, mbs Depth water table sampling, mbs Depth top sampler, mbs Depth bottom well, mbs Pump yield m3/L AE General chemistry Parameter Conductivity Nitrate Fluoride Chloride Bicarbonate Sulphate Value mS/m mg/L mg/L mg/L mg/L mg/L Parameter Value DOC mg C/L Iron mg/L Ammonium mg/L Sodium mg/L Potassium mg/L Calcium mg/L Magnesium mg/L 80 ------- AE Precision field, reference samples Well number Compound Chloroethene 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Sample 1 Date AE4 Concentr; Sample 2 Date AE5 jtion ug/L Sample 3 Date AE6 Sample 4 Date AE7 81 ------- BA Reference robustness lab dispenser, samples Compound 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE mL sampled (measured) mL sampled (by tracer salt) C ID BA1 oncentration |j ID BA2 g/L ID BA3 Dates Set up Sampled Pressure head at sep-up cm - - - - - - Temperatures Set up Sampled External pressure bar - - - - - - BB Reference robustness lab dispenser, reference samples Compound 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Sample 1 Date BB1 Concentration ug/L Sample 2 Date BB2 Sample 3 Date BBS 82 ------- CA Sampling depth robustness standpipe, samples Compound 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE mL sampled (measured) mL sampled (by tracer salt) C ID CA1 oncentration |j ID CA2 g/L ID CAS Dates Setup Sampled Pressure head at sep-up cm - - - - - - Temperatures Setup Sampled External pressure bar - - - - - - CB Sampling depth robustness standpipe, reference samples Compound 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Sample 1 Date CB1 Concentration ug/L Sample 2 Date CB2 Sample 3 Date CBS 83 ------- DA Ionic strength robustness lab dispenser, 10 mS/cm, samples Compound 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE mL sampled (measured) mL sampled (by tracer salt) C ID DA1 oncentration |j ID DA2 g/L ID DAS Dates Set up Sampled Pressure head at sep-up cm - - - - - - Temperatures Set up Sampled External pressure bar - - - - - - DB Ionic strength robustness lab dispenser, 10 mS/cm, reference samples Compound 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Sample 1 Date DB1 Concentration ug/L Sample 2 Date DB2 Sample 3 Date DBS 84 ------- EA Ionic strength robustness lab dispenser, 100 mS/cm, samples Compound 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE mL sampled (measured) mL sampled (by tracer salt) C ID EA1 oncentration |j ID EA2 g/L ID EA3 Dates Setup Sampled Pressure head at sep-up cm - - - - - - Temperatures Setup Sampled External pressure bar - - - - - - EB Ionic strength robustness lab dispenser, 100 mS/cm, reference samples Compound 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Sample 1 Date EB1 Concentration ug/L Sample 2 Date EB2 Sample 3 Date EB3 85 ------- FA Sampling time robustness lab dispenser, 3 days, samples Compound 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE mL sampled (measured) mL sampled (by tracer salt) C ID FA1 oncentration |j ID FA2 g/L ID FAS Dates Setup Sampled Pressure head at sep-up cm - - - - - - Temperatures Setup Sampled External pressure bar - - - - - - FB Ionic strength robustness lab dispenser, 3 days, reference samples Compound 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Sample 1 Date FB1 Concentration ug/L Sample 2 Date FB2 Sample 3 Date FB3 86 ------- GA Sampling time robustness lab dispenser, 9 days, samples Compound 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE mL sampled (measured) mL sampled (by tracer salt) C ID GA1 oncentration |j ID GA2 g/L ID GAS Dates Setup Sampled Pressure head at sep-up cm - - - - - - Temperatures Setup Sampled External pressure bar - - - - - - GB Ionic strength robustness lab dispenser, 9 days, reference samples Compound 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Sample 1 Date GB1 Concentration ug/L Sample 2 Date GB2 Sample 3 Date GB3 87 ------- HA Concentration integration robustness, lab dispenser, samples Compound 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE mL sampled (measured) mL sampled (by tracer salt) C ID HA1 oncentration |j ID HA2 g/L ID HAS Date & time Start 20% End 20% Start 50% End 50% Start 80% End 80% - Temperatures Setup Sampled Pressure head at sep-up cm - - - - - - HB Concentration integration robustness, lab dispenser, reference samples Compound 1,1-Dichloroethene trans-1 ,2-Dichloroethene cis-1 ,2-Dichloroethene Trichloroethene Tetrachloroethene Benzene Toluene Ethylbenzene o-Xylene m+p-Xylene MTBE Sample 1 Date HB1 Concentration ug/L Sample 2 Date HB2 Sample 3 Date HB3 88 ------- APPENDIX 6 Data management 89 ------- In general, the data filing and archiving procedures of the DHI Quality Management System will be followed. All data recording and reporting is done in English, communication with Danish ex- ternal and internal can be in Danish. Data storage, transfer and control The data to be compiled and stored are summarized in Table 8. Analytical raw data will be filed and archived according to the specifications of the laboratories quality management systems under their ISO 17025 accreditation and are thus not the concern of DHI staff. Table 11 Data compilation and storage summary Data type Test plan and report Test details in laboratory and field Calculations Analytical re- ports Data media Protected PDF files Log book and pre-pre pared forms Excel files Paper Data recorder Test responsi- ble, DHI Technician, DHI Test responsi- ble, DHI Test responsi- ble, DHI Data re- cording tim- ing When ap- proved During collec- tion During calcula- tions When received Data storage Files and ar- chives at DHI Files and ar- chives at DHI Files and ar- chives DHI Files and ar- chives DHI Implementation All e-mail communication is filed in the Outlook Exchange folders, see below struc- ture. The DHI person receiving an e-mail (to field, not cc field) will file the e-mail. The DHI person sending an e-mail will use the "send and file" option and thereby ensure prompt filing of all e-mails sent. There is generally no need to widespread cc when sending e-mails, unless specific action or communication is required. All paper communication is immediately filed in the binder established by GHE and available in his office. The title page of the binder will resemble the folder structure at dkstor, see below. All recordings during testing in the laboratory or in the field are done in water proof writing in hardback log-books with all pages numbered page/total page number. The log books are filed with the staff member using them until the testing is completed, then with GHE and available at his office. All data needed for the tests are recorded in the data sheets available from Appendix 5 of the Test Plan. The format can be Word tables, Excel worksheets or paper sheets as decided by GHE as test responsible. The outline and format are mandatory and can only be deviated from by recording a deviation with justification, see the Test Plan. 90 ------- All calculations are done using Excel spreadsheets with names identifying the contents and with headings and notes explaining the calculations. All electronic files are stored at dkstor in the folder structure shown below. File names are constructed to identify the contents. Subfolders can be established as found con- venient, while again constructing folder names that identify the contents. When work- ing away from network connection (offline), copies of files can be used on own PC, but the server version is updated and the offline version deleted immediately after re- turning to network connection. 91 ------- Favorite Links ^, Documents £ Pictures ^ Music More » Name Folders I 80137 Sampler education pilot project 80142.MEMBAQ * 80144.NOWATECH Center documents ^ Sorbisense documents Calculation; External data reports A ,. Field info . Wells Glostrup Wells Statoil Wells Soborg Laboratory info * Jk> Plan & protocol Obsolete Review Reports jj Drafts Review > Jk X-Miscellaneous > Jl 11093220 (91252] VMG annoncering 11700096_Aftercare 11700116_Modellering_dikloramindannelse 11700363_o verfl a d eaf str.0 m n i n g 2 items ®]Review report Sorbisen,, te}] Review report Sorbisen.. Offline status: Online Offline availability: Not available O 3§ S S E B ^ 92 ------- fi| Reports In Public Folders - Microsoft i File Edit View CJQ Tools Acti New *• < • , ,'-.'- • : Folder List All Folders All Outlook Items ±1 ^4 80143 - OpenMI LIFE d _,J 80144 - NOWATECH Lj. 0 SECRETARIATS FILE VT^ L J. 1 Administration 8t Coi ^4 10 CEN Workshop i_4 ^ Client Comrnunicatio d _ 4 3 Other External Comrr •ff ^4 Aquateam ^4 Commission L^ DHI/AU _ DHl/MMK ^4 Joint verifications d _4 Sorbisense _4 External data re '_4 F'6^ info _4 Laboratory info ! •- 4 Plan and protocj _4 Reports J ^4 TESTNET info :i -4VTT L4 4 Internal Com muni cat I d L4 5 Contract & Invoices -,< LjiLJ.1"""^'""""^ 'i , Mall 93 ------- 94 ------- APPENDIX 7 Deviations and amendments 95 ------- 96 ------- Deviation reports The test plan version approved must be followed. If (or rather when) deviations are needed during testing, the deviations are noted and justified in the format: Deviation number Experiment label Test Plan Table 1 Test method step Test Plan Appendix 3 Deviation Cause Impact as- sessment Corrective action, if any Date Signature test or field responsible Date Signature verification responsible Date Signature Battelle AMS QM The verification protocol version approved must be followed. If deviations are needed during testing, the deviations are noted and justi- fied in the format: Deviation number Verification protocol Chapter Deviation Cause Impact as- sessment Corrective action, if any Date Signature verification responsible Date Signature internal audi- tor Date Signature Battelle AMS QM Deviation reports are continuously filed in and filed in the appropriate folder at dkstor, see Appendix 6. 97 ------- Amendment reports All changes in the protocol and test plan done in advance of verification and testing must be done by the document owner (protocol CHG, plan GHE) and approved by the verification responsible and the internal auditor. Amendments shall be made available for all involved. The amendments will mostly have the form of a revised section or chapter of the pro- tocol or plan, with the below given front page. Deviation reports are continuously filed in and filed in the appropriate folder at dkstor, see Appendix 6. 98 ------- AMENDMENT TESTING DOCUMENT TITLE AND DATE: AMENDMENT NUMBER: _ DATE OF REVISED PART: _ PART TO BE CHANGED/REVISED: CHANGE/REVISION: Reference to revised part REASON FOR CHANGE: ORIGINATED BY: DHIWMC Verification or Test Responsible DATE APPROVED BY: DHI WMC Internal Auditor DHI WMC Verification Responsible DATE DATE Battelle AMS Center Quality Manager Battelle AMS Center Manager DATE DATE 99 ------- 100 ------- |