#• \ "V ^ *1 PRO*^ Quality Assurance Project Plan for the Photochemical Assessment Monitoring Stations (PAMS) Required Site Network for Speciated Volatile Organic Compounds, Carbonyls, and Meteorological Parameters Including Mixing Layer Height - Revision 1 Model QAPP ------- ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 3 of 145 Quality Assurance Project Plan for the Photochemical Assessment Monitoring Stations (PAMS) Required Site Network for Speciated Volatile Organic Compounds, Carbonyls, and Meteorological Parameters Including Mixing Layer Height - Revision 1 By: Ningxin Wang, PhD Crystal McClure, PhD Jennifer DeWinter Sonoma Technology, Inc. 1450 N. McDowell Blvd. Petaluma, CA 94954 Prepared for: OAQPS/AQAD GSA Contract No. 47QRAA18D00D1 Work Order No. 3-10 Task Order No. 68HERH20F0357 U.S. Environmental Protection Agency Office of Air Quality Planning and Standards Air Quality Assessment Division Research Triangle Park, NC ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 4 of 145 Disclaimer Mention of commercial products or trade names will not be interpreted as endorsement. Some types of instruments currently in use may be described in text or in example figures or tables. Sometimes these products are given as a typical and perhaps well-known example of the general class of instruments. Other instruments in the class are available and may be fully acceptable. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 5 of 145 Revision History Revision Number Theme Description of Change(s) Section(s)/Table(s) 1 General Updated dates, links, and action items; addressed inconsistencies; added flexibility and clarifications where applicable; removed outdated background information about EPA's PAMS re-engineering plans Throughout 1 Annual Milestones Updated to June 1 except system review and revisions A6.3 1 TSA Frequency Updated to every 4 years CI.1.2 1 Ceilometers Removed hard target test and bias requirement A7.3, A7.3.4, B5.1.4 1 no2 Updated Gas Phase Titration (GPT) to be the only method for generating known concentrations of NO2 A6.3, B7.1.3, Cl.l 1 Auto-GC CAS-specific: noted that gases should not be humidified, MDLs cannot be calculated, how to calculate TNMOC/PAMSHC, guidance on ICAL. General: identified more poor integration compounds, added toluene as optional C6-C12 calibration parameter, changed ICAL intercept/slope criteria, added guidance on CCV, SYSB, and SSCVs B5.1, B7.1, D2.2, Table A6-2, Table B5-2 ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 6 of 145 Foreword This document is the Quality Assurance Project Plan (QAPP) for monitoring operations for the Photochemical Assessment Monitoring Stations (PAMS) Required Site Network for the parameters of speciated volatile organic compounds (VOCs), carbonyls, and meteorological measurements including mixing layer height (MLH). Any analysis performed by national contract laboratories will be covered in contract QAPPs approved by the Environmental Protection Agency (EPA) and will not need to be covered by the monitoring agency. EPA developed this national QAPP to ease the burden on state and local air monitoring agencies (see note below) in developing a QAPP for their PAMS Required Site Program as well as to improve data quality and consistency in the PAMS data. This QAPP was developed in accordance with the EPA quality assurance (QA) requirements described in EPA OA R-5, EPA Requirements for Quality Assurance Project Plans and the guidance in the accompanying document EPA OA/G-5, Guidance for Quality Assurance Project Plans. Monitoring agencies may use this model QAPP or develop their own QAPP. If using this model QAPP, monitoring agencies are expected to follow the QAPP as written, and only add pertinent details where indicated in yellow highlight. Regardless of whether the model QAPP is used, or a monitoring agency develops their own QAPP, the completed QAPP must be submitted to the appropriate EPA Regional Office for review and approval. Monitoring of the criteria pollutants O3 and NO2 for use in National Ambient Air Quality Standards (NAAQS) attainment decisions will already be occurring at the PAMS Required Site or at other sites operated by the responsible monitoring agency or primary quality assurance organization (PQAO); as such, approved QAPPs governing required monitoring activities will already be available. As the QA requirements for these criteria pollutants are described elsewhere, the scope of this QAPP does not include QA requirements for the measurement of ozone (O3) nor the nitrogen oxides NO, NOx, and NOy. NO and NOy are measured by monitoring agencies operating National Core (NCore) sites and will also be covered by an existing QAPP. As true NO2 is a new parameter specific to PAMS (though some monitoring agencies have replaced or opted for true NO2 analyzers over NOx analyzers), QA requirements for measurement of true NO2 are covered for monitoring agencies that do not have authority to modify the criteria gas pollutant QAPP to include true NO2 monitoring at the PAMS monitoring sites. These aspects are detailed in Monitoring agencies that cannot refer to an existing QAPP for true NO2 measurements will adopt the QA aspects of NO2 monitoring listed; however, monitoring agencies which have addressed QA requirements for true NO2 monitoring in another QAPP (e.g., a QAPP governing criteria pollutant monitoring) can satisfy the NO2 monitoring QA requirements by referring to their specific QAPP or QAPPs in those sections highlighted red. Mention or inclusion of O3 and oxides of nitrogen in this QAPP is in a manner that will not be in conflict with current EPA requirements or the monitoring organizations' approved QAPPs. EPA Regional staff will ensure the QA requirements for true NO2 measurements are sufficiently covered in the PAMS monitoring QAPP or in the criteria pollutant monitoring QAPP included by reference. VOCs data collection for this QAPP focuses on the use of field automated instruments and the companion technical assistance document provides details on this instrumentation. Although the monitoring agency may submit a waiver for VOC canister sampling and laboratory analysis, this ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 7 of 145 national QAPP will not cover those procedures and monitoring agencies will be required to submit a QAPP to cover VOC canister sampling and analysis. This QAPP covers the meteorological measurements made at the PAMS site. Although a waiver is available for using meteorological data from nearby meteorology sites, this QAPP does not attempt to address QA activities for such alternate meteorology measurement data. As explained in the table below, it is important to differentiate between the terms shall/must, should, and may in regulations and guidance documents. Distinct Terms in this QAPP Term Description Shall/Must Used when the element is required. Should Used when the element is recommended. • This term is used when extensive experience in monitoring provides a recommended procedure that would help establish or improve the quality of data or a procedure. The process that includes the term is not required, but if not followed, an alternate procedure should be developed that meets the intent of the guidance. May Used when the element is optional or discretionary. • The term also indicates that what is suggested may improve data quality, that it is important to consider, but it is not as important as those that have been suggested using the term "should." NOTE: The Ambient Air Monitoring program uses the term "Monitoring Agency" and "Primary Quality Assurance Organization" (PQAO) in many of its regulations and guidance documents. In many cases the monitoring agency and the PQAO are the same entity; in a few cases, a PQAO may represent a number of monitoring agencies. This document uses the term "monitoring agency" throughout but is meant to cover both situations. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 8 of 145 ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 9 of 145 A PROJECT MANAGEMENT Al Title and Approval EPA QAPP Category II By signing below, the Environmental Protection Agency (EPA) Office of Air Quality Planning and Standards (OAQPS) and EPA Regional technical and quality assurance (QA) leads for the Photochemical Assessment Monitoring Stations (PAMS) program have found this quality assurance project plan (QAPP) to be directly adoptable by any monitoring organization for the purpose of conducting monitoring for the PAMS Required Site Network Program once the monitoring organization specific details have been added. Signature by an EPA Regional representative, such as a Regional Administrator, QA manager, air monitoring program manager, or their delegated designee, signifies concurrence with all aspects of this QAPP. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 10 of 145 Title: Quality Assurance Project Plan for the Photochemical Assessment Monitoring Stations (PAMS) Required Site Network for Speciated Volatile Organic Compounds, Carbonyls, and Meteorological Parameters Including Mixing Layer Height - Revision 1 The attached QAPP for the EPA PAMS Required Site Network is hereby approved and commits the participants of the program to follow the elements described within. PQAO Program Manager PQAO QA Manager EPA Regional Office Other Signature: Name: Signature: Name: Signature: Name: Signature: Name: Date: Date: Date: Date: ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 11 of 145 Al.l EPA Regional Approval of Monitoring Agency QAPP The QA policies in EPA Order 5360.1 A2 require agencies that accept federal grant funding for their air monitoring programs to have a QA program with certain elements including quality management plans (QMPs), QAPPs, and the identification of a QA management function. To reduce the burden on state, local, or tribal (SLT) monitoring agencies, EPA has produced this National QAPP for PAMS Required Site Network monitoring agencies as a template and requires that SLT monitoring agencies review and either: (1) Revise this QAPP where indicated to reflect SLT policies and procedures; or (2) Develop their own QAPP to be consistent with the procedures outlined here. The appropriate EPA Region must approve the resulting monitoring agency QAPP for conformance to the requirements of this national QAPP. SLT monitoring agencies will submit a list detailing the deviations and departures from this QAPP to the Region and supply supporting documentation to demonstrate that the quality aspects of this QAPP remain satisfied. SLT monitoring agencies will complete the form in Appendix A which indicates whether the SLT monitoring agency adopts this national QAPP (and has included the requested additional detail, as required) or develops its own QAPP. The monitoring agency must submit the completed form to its EPA Region with its PAMS QAPP. The form in Appendix A can also be used for those monitoring agencies that have been delegated QAPP self-approval authority by the EPA Region. A1.2 Corrections to the National QAPP or Supporting SOPs The PAMS Required Site monitoring agency staff and their supervisors are responsible for implementing the applicable approved monitoring agency QAPPs and standard operating procedures (SOPs) and are responsible for the quality of the data. If changes or corrections are suggested for the approved national QAPP or supporting national SOPs, PAMS monitoring agency personnel will notify the Regional Representative who may notify the PAMS QA Lead at OAQPS. The PAMS QA Lead at OAQPS will review proposed changes with the EPA Regional PAMS Leads and determine if revisions to the national QAPP and/or national SOPs are appropriate. OAQPS will notify the PAMS monitoring agency site leads through a quality bulletin detailing amendment to the document(s). This quality bulletin (refer to example in Appendix B) will be distributed to the PAMS Required Site stakeholder e-mail list maintained by EPA OAQPS. When appropriate, new versions of the document(s) will be provided to the PAMS Required Site Network participants with instructions to discard the previous version. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 12 of 145 Acknowledgments This QAPP revision is the product of the combined efforts of EPA's OAQPS; EPA Regional offices; and SLT monitoring agencies. The following individuals are acknowledged for their contributions: EPA Regional PAMS Leads Region: 1 Alysha Murphy and Tyler Way 2 Gavin Lau 3 Meighan Long 4 Darren Palmer 5 Jacqueline Nwia 6 David Anderson 7 Stephen Krabbe 8 Ethan Brown 9 Randall Chang 10 Will Wallace Office of Air Quality Planning and Standards Corey Mocka Trisha Curran Kevin Cavender Sonoma Technology, Inc., under EPA Task Order 68HERH20F0357, Work Order 3-10 Ningxin Wang, PhD Crystal McClure, PhD Jennifer DeWinter ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 13 of 145 Table of Contents Disclaimer 4 Revision History 5 Foreword 6 A PROJECT MANAGEMENT 9 A1 Title and Approval 9 Al.l EPA Regional Approval of Monitoring Agency QAPP 11 A1.2 Corrections to the National QAPP or Supporting SOPs 11 A2 Acronyms and Abbreviations 18 A3 Distribution List 21 A4 Project/Task Organization 21 A4.1 EPA OAQPS 22 A4.2 EPA Regional Offices 23 A4.3 SLT PAMS Required Site Monitoring Agencies 24 A4.4 Analytical Support Laboratory 25 A4.5 PAMS Support Contractor 26 A4.6 PAMS Required Site Workgroup 26 A5 Problem Definition/Background 27 A5.1 Monitoring Agency PAMS Required Site(s) 29 A6 Project Task/Description 30 A6.1 Required Measurements 30 A6.2 Personnel to Accomplish Tasks 31 A6.3 Schedule for PAMS Required Site Activity Milestones 36 A6.4 Summary of Assessment Techniques 38 A7 Quality Objectives and Criteria 38 A7.1 Data Quality Objectives 38 A7.2 Data Quality Indicators 39 A7.3 Measurement Quality Objectives 39 A7.3.1 Representativeness 41 A7.3.1.1 Temporal Representativeness 41 A7.3.1.2 Spatial Representativeness - Chemical Measurement Probe Siting Criteria ...42 A7.3.1.3 Spatial Representativeness - Meteorology 43 A7.3.2 Completeness 45 ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 14 of 145 A7.3.3 Precision 45 A7.3.4 Bias 47 A7.3.5 Sensitivity 50 A8 Special Training/Certifications 51 A8.1 Site Operator Training 51 A8.2 Auditor Training 53 A8.3 Analytical Support Laboratory Analyst Training 53 A9 Documentation and Records 54 A9.1 Recording of Data 56 A9.1.1 Paper Records 56 A9.1.2 Electronic Records 56 A9.2 Chain-of-Custody Records 56 A9.3 QA/QC Records 57 A9.4 Records Archival and Retention 57 A9.5 Sample Retention 57 B DATA GENERATION AND ACQUISITION 59 B1 Sampling Process Design (Experimental Design) 59 Bl.l Sample Collection Schedule 60 B 1.1.1 Carbonyls by TO-11A 60 Bl.l.2 Speciated VOCs by Auto-GC 61 B1.1.3 Continuous Measurement Methods 62 Bl.1.3.1 True NO 62 B1.1.3.2 Meteorological Instruments 62 B1.2 Quality Control Measurements 62 B2 Sampling and Measurement Methods 63 B2.1 Chemical Parameters 63 B2.1.1 Carbonyls by TO-11A 64 B2.1.2 Speciated VOCs by Auto-GC 64 B2.1.3 True NO2 by CAPS or Photolytic Conversion to NO with Chemiluminescent Detection 66 B2.2 Meteorology 66 B3 Sample Handling and Custody 67 B3.1 Carbonyls by TO-11A 67 B3.1.1 Chain of Custody 68 B4 Analytical Methods 69 B4.1 Carbonyls by TO-11A 69 ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 15 of 145 B4.2 Speciated VOCs by Auto-GC 69 B4.3 True NOi by FEM 69 B5 Quality Control 70 B5.1 Quality Control for Field Activities 70 B5.1.1 Quality Control for Carbonyls Sample Collection 70 B5.1.2 Quality Control for Speciated VOCs Collection and Analysis 72 B5.1.3 Quality Control for True NO2 Analysis 75 B5.1.4 Quality Control for Meteorology 77 B5.2 Quality Control for Laboratory Activities 78 B6 Instrument/Equipment Acceptance, Testing, Inspection, and Maintenance 81 B6.1 Instrument Acquisition for New Required PAMS Sites 82 B6.2 Instrument Acceptance Testing and Shakedown 82 B6.2.1 Initial Instrument Acceptance and Shakedown 82 B6.2.2 Annual Instrument Shakedown 83 B6.3 Equipment Inspections 83 B6.4 Instrument Maintenance 83 B7 Instrument/Equipment Calibration and Frequency 85 B7.1 Instrument Calibration 86 B7.1.1 Carbonyls Instrument Calibration 86 B7.1.1.1 Carbonyls Field Sampling Instrument Calibration and Calibration Verification 86 B7.1.1.2 Carbonyls Laboratory Instrument Calibration and Calibration Verification.... 86 B7.1.2 Calibration and Calibration Verification for Speciated VOCs by Auto-GC 86 B7.1.3 Calibration and Calibration Verification for True NO2 Analyzers 87 B7.1.4 Calibration and Calibration Verification for Meteorology Instruments ... 87 B7.2 Calibration Support Equipment 87 B8 Inspection/Acceptance of Supplies and Consumables 89 B8.1 Acceptance of Standard Materials 90 B8.2 Acceptance of Sampling Media - Carbonyls 91 B9 Non-direct Measurements 91 B9.1 Historical PAMS Data and Supplemental Measurement Data from Other Monitoring Sites 92 B10 Data Management 92 C ASSESSMENT AND OVERSIGHT 93 CI Assessments and Response Actions 93 ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 16 of 145 Cl.l Types of Assessments 93 C1.1.1 Instalment Performance Audit 95 C1.1.1.1 Carbonyls Instrument Performance Audit 95 C1.1.1.2 Meteorology Instrument Performance Audits 95 CI. 1.2 Technical Systems Audit 96 C1.1.2.1 Shakedown Audits 97 C1.1.3 Audits of Data Quality 97 CI.1.4 Proficiency Testing 98 C1.1.5 Performance Evaluation 98 C1.2 Corrective Actions 99 C2 Reports to Management 100 C2.1 Assessment Reports 100 D DATA VALIDATION AND USABILITY 101 D1 Data Review, Verification, and Validation Requirements 101 Dl.l Data Verification and Validation Responsibilities 101 D1.2 Data Verification 102 Dl.2.1 Routine (Self) Review 102 Dl.2.2 Technical (Peer) Review 104 D1.3 Data Validation 105 D1.4 Reporting of Validated Data to AQS 107 D1.4.1 Reporting Values Below Method Detection Limits (Carbonyls and Speciated VOCs) 107 D2 Data Verification and Validation Methods 108 D2.1 Data Verification Methods 108 D2.2 Data Validation Methods 108 D2.2.1 Data Visualization Methods 109 D2.2.2 Statistical Methods 109 D2.2.3 Examination of Supporting Data 109 D2.2.4 Treatment of Deviations from Requirements Ill D2.2.4.1 Identifying Compromised Data in AQS Ill D2.2.4.2 Corrective Action Process 114 D2.2.4.3 Notification of EPA or Other Stakeholders 114 D3 Reconciliation with User Requirements 115 D3.1 Reconciling Results with DQOs 115 D3.2 Interim Corrective Actions 115 REFERENCES 117 ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 17 of 145 Tables Table A5-1. Required Sites in CBSAs with a Population Greater than 1,000,000 28 Table A5-2. PAMS Required Sites Covered by this QAPP 30 Table A6-1. Measurements and Associated Instruments for PAMS Required Sites 31 Table A6-2. PAMS Required Site Activity Annual Milestones 36 Table A7-1. PAMS DQIs and Associated MQOs 40 Table A7-2. Minimum Monitor Separation Distance from Roadways 43 Table A9-1. Pertinent Documents and Records for PAMS Required Site(s) 54 Table B1-1. PAMS Required Site Sampling Schedule by Parameter 60 Table B1-2. Carbonyls Sampling Schedule 61 Table B2-1. Priority and Optional PAMS Required Site Chemical Parameters 64 Table B2-2. Meteorological Parameters 66 Table B5-1. Carbonyls Field Quality Control Parameters 71 Table B5-2. Speciated VOCs Field Quality Control Parameters 73 Table B5-3. True NO2 Quality Control Parameters 76 Table B5-4. Quality Control Parameters for Meteorology Measurements 78 Table B5-5. Carbonyls Laboratory Quality Control Parameters 79 Table B6-1. Routine Instrument Maintenance Activities 84 Table B7-1. Calibration Requirements for Critical Support Instruments 88 Table B8-1. DNPH Cartridge Lot Blank Acceptance Criteria 91 Table Cl-1. PAMS Required Site Assessments 94 Table Dl-1. Routine Review Activities and Associated Frequency 103 Table Dl-2. Dataset Durations (Sizes) for Validation 107 Table D2-1. AQS Qualifiers and Null Codes for PAMS 112 Figures Figure A4-1. PAMS Required Site Network Communication and Responsibility Structure 22 Appendices APPENDIX A: SLT MONITORING AGENCY QAPP APPROVAL APPENDIX B: EXAMPLE QUALITY BULLETIN APPENDIX C: EXAMPLE CHAIN-OF-CUSTODY FORM APPENDIX D: EXAMPLE STAFF PROFICIENCY TRAINING FORM APPENDIX E: EXAMPLE SITE VISIT CHECKLIST APPENDIX F: GUIDANCE FOR PAMS MONITORING AGENCIES TO INCORPORATE PAMS REQUIREMENTS INTO ANNUAL MONITORING NETWORK PLANS ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 18 of 145 A2 Acronyms and Abbreviations ADQ audit of data quality AGL above ground level AMNP annual monitoring network plan AMTIC Ambient Monitoring Technology Information Center API Advanced Pollution Instruments AQAD Air Quality Assessment Division AQS Air Quality System ASL analytical support laboratory auto-GC automatic gas chromatograph C carbon C2 compounds containing two carbon atoms Ce compounds containing six carbon atoms C12 compounds containing twelve carbon atoms CAA Clean Air Act CAP corrective action plan CAPS cavity attenuated phase shift CAR corrective action report CAS Consolidated Analytical Systems CBSA core-based statistical area CCV continuing calibration verification standard CDOC continuing demonstration of capability CDS chromatography data system CFR Code of Federal Regulations COA certificate of analysis COC chain of custody CRM certified reference material CTS collocated transfer standard CV coefficient of variation DART Data Analysis and Reporting Tool DAS data acquisition system DDC dynamic dilution calibrator DNPH 2,4-dinitrophenylhydrazine DQA data quality assessment DQI data quality indicator DQO data quality objective DST daylight savings time EMP enhanced monitoring plan EPA Unites States Environmental Protection Agency ESMB extraction solvent method blank FEM Federal Equivalent Method FEP fluorinated ethylene propylene FID flame ionization detector FRM Federal Reference Method ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 19 of 145 GC gas chromatograph GPT gas phase titration HAP hazardous air pollutant HPLC high performance liquid chromatograph ICAL initial calibration IDL instrument detection limit I DOC initial demonstration of capability IP implementation plan IPA instrument performance audit ISO International Organization for Standardization LCS laboratory control sample LCSD laboratory control sample duplicate LIMS laboratory information management system m meter(s) MB method blank MDL method detection limit MFC mass flow controller min minute(s) MLH mixing layer height mm millimeter(s) MQO measurement quality objective MPV multi-point verification MS monitoring staff Hg microgram(s) NA nonattainment area NAAQS national ambient air quality standard NATTS National Air Toxics Trends Stations NCore National Core ng nanogram(s) NIST National Institute of Standards and Technology nm nanometer(s) NO nitrogen oxide no2 nitrogen dioxide NOy total reactive nitrogen NPAP National Performance Audit Program NWS National Weather Service 03 ozone molecule OAQPS Office of Air Quality Planning and Standards OTR Ozone Transport Region PAMS photochemical assessment monitoring station PAMSHC PAMS hydrocarbons PBLH planet boundary layer height PDMS polydimethylsiloxane PE performance evaluation PFA perfluoroalkoxy ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 20 of 145 PGVP Protocol Gas Verification Program PLOT porous layer open tubular PM particulate matter ppb part(s) per billion ppbC part(s) per billion carbon ppm part(s) per million PQAO primary quality assurance organization PT proficiency test PTFE polytetrafluoroethylene QA quality assurance QAU quality assurance unit QAIP quality assurance implementation plan QAPP quality assurance project plan QC quality control QMP quality management plan QS quality system RF response factor RH relative humidity RPD relative percent difference RSD relative standard deviation RT retention time RTS retention time standard SB solvent blank or system blank SLAMS state and local air monitoring stations SLT state, local, or tribal (monitoring organization) SOAP Secondary Organic Aerosols Precursor SOP standard operating procedure SRM standard reference material sscv secondary source calibration verification SYSB system blank TAD technical assistance document TNMOC total non-methane organic carbon TOF time-of-flight TSA technical systems audit TTP through-the-prob e UHPLC ultra-high performance liquid chromatograph UV ultraviolet VOC volatile organic compound VSL Van Swinden Laboratorium ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 21 of 145 A3 Distribution List An electronic version of this QAPP is available on EPA's Ambient Monitoring Technology Information Center (AMTIC) PAMS website at the following link: https://www.epa.gov/amtic/photochemical-assessment-monitoring-stations-pams OAQPS will distribute this QAPP via e-mail to those individuals on its PAMS Required Site Network e-mail contact list. The EPA PAMS Regional Leads will be responsible for ensuring that this QAPP is distributed to the SLT monitoring agency Program Manager or Director of each PAMS Required Network field site. SLT monitoring agencies will be responsible for distributing this QAPP to analytical support laboratories (ASLs) conducting carbonyls and/or speciated volatile organic compound (VOC) analysis, as appropriate. The EPA PAMS Regional Leads will also provide a copy of this QAPP to their Regional QA Staff. Required Distribution • EPA PAMS Regional Leads • SLT monitoring agency Program Manager or Director • PAMS Required Site Network monitoring leads • EPA Regional QA staff • PAMS Required Site Network analytical support laboratories Monitoring agencies will include the distribution list for their PAMS QAPP. A4 Project/Task Organization The PAMS Required Site Network will measure ozone, its precursors, and meteorological variables, and will do so, unless otherwise authorized by EPA OAQPS. State and local monitoring agencies are required to collect and report PAMS measurements at each National Core (NCore) site that is located in a core-based statistical area (CBSA) with a population of 1 million or more based on the latest available census figures. SLT monitoring agencies are required to collect and report PAMS measurements listed in 40 Code of Federal Regulations (CFR) Part 58 Appendix D Section 5(b). These required measurements are detailed in Section A6.1 of this QAPP. Organizations essential to the execution of the PAMS Required Site monitoring program include EPA OAQPS, EPA Regional Offices, SLT monitoring agencies and their ASL, and the PAMS Support Contractor. The PAMS Required Site Network communication and responsibility structure is depicted in Figure A4-1. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 22 of 145 r ^ EPA OAQPS • Develops National Quality System • Allocates CAA Section 105 grant monies to Regions • Provides training materials & opportunities • Develops guidance documents y* Assists in equipment acquisition l . EPA Region • Administers Quality System • Approves SLT monitoring agency quality system • Conducts audits of PAMS Required Sites and analytical support laboratories ^ -L /- -\ SLT Monitoring Agency • Acquires monitoring equipment • Provides staff resources to conduct monitoring • Calibrates and operates monitoring equipment • Validates and reports monitoring data V X % . 1 PAMS QA Support Contractor • Assists developing Quality System documents • Provides audit support for Regions without audit capability • Facilitates communication with the Network SLT monitoring agencies through conference calls and webinars Develops training modules and materials > j Analytical Support Laboratory • Handles and stores collected samples according to the SLT quality system • Analyzes collected samples (carbonyls and/or VOCs) • Provides quality assured data to the SLT monitoring agency Figure A4-1. PAMS Required Site Network Communication and Responsibility Structure A4.1 EPA OAQPS OAQPS, with assistance from the EPA Regions, is responsible for defining and developing the national quality system (QS) for the PAMS Required Site Network. OAQPS also allocates the Clean Air Act (CAA) Section 105 grant monies to the EPA Regions according to the allocation formula specified by Congress in the corresponding appropriations bill. The EPA Regions may then decide to distribute a portion of their Section 105 funds to the SLT air monitoring agencies for the execution of PAMS monitoring activities. OAQPS has the following responsibilities: • Designating OAQPS technical and QA leads for the PAMS Required Site Network • Ensuring national consistency across the PAMS Required Site Network • Participating in the PAMS Required Site Workgroup • Providing individual or group discussions with EPA Regions and SLT monitoring agencies to help them determine and/or select appropriate instrumentation and ensure consistent execution of the monitoring activities across the network • Developing and finalizing the PAMS Technical Assistance Document (TAD), this national QAPP, and other national SOPs, as needed • Organizing and conducting training course(s) for automatic gas chromatograph (auto- GC), ceilometer, and other pertinent instruments as well as technical and quality assurance activities, as needed • Developing and implementing the PAMS Technical Systems Audit (TSA) and Proficiency Testing (PT) programs • Setting TSA expectations and ensuring compliance ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 23 of 145 • Managing the performance and PAMS contractual requirements of the National Contract ASL, including: o Approving QAPPs and SOPs from the National Contract ASL o Conducting TSAs of the National Contract ASL and overseeing and approving corrective actions resulting from TSAs and/or PTs o Addressing inquiries and feedback regarding the National Contract ASL communicated by SLT monitoring agencies and/or EPA Regions OAQPS will use a support contractor to assist in the development of the quality system (QS) guidance documents, provide audit support, and coordinate conference calls. A4.2 EPA Regional Offices The EPA Regions administer the QS for the SLT monitoring agencies in their Regions, ensuring that the QS developed by each SLT monitoring agency complies with the national QS described in this document. The EPA Regional Offices are the major communication link with monitoring agencies and OAQPS; as such, they play an important role in the development and enforcement of effective policies and programs. The Regional Offices have the following specific responsibilities: • Identifying a Regional PAMS Lead • Participating in the PAMS Required Site Network Workgroup • Reviewing and approving monitoring agency PAMS Required Site Implementation Plans (IPs) and waiver requests • Reviewing and approving the national PAMS Required Site QAPP, monitoring agency specific QAPPs, and reporting approval of the monitoring agency QAPP to EPA's Air Quality System (AQS) • Performing TSAs of PAMS Required Sites and applicable ASLs or delegating TSA conduct to the support contractor (per discretion of specific Region; unless informed otherwise, OAQPS assumes that all PAMS TSAs will be conducted by the support contractor) o Attending the TSA with the support contractor, as time and EPA funding allows o Identifying and communicating audit findings to OAQPS and SLTs o Ensuring that SLTs and ASLs develop corrective action plans (CAPs) for audit (TSA and/or PT) findings and that corrective actions are taken and are effective (i.e., that findings are addressed) o Recording TSA dates (i.e., occurrence and closeout) in AQS • Providing QA oversight to PAMS Required Site monitoring agencies • Providing technical assistance to PAMS Required Site monitoring agencies • Serving as the communication liaison between OAQPS and PAMS Required Site monitoring agencies ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 24 of 145 A4.3 SLT PAMS Required Site Monitoring Agencies SLT monitoring agencies are responsible for acquiring equipment, providing and training appropriate staff, operating instruments and generating ozone precursor concentration and meteorological data, verifying the quality of the measurements, and reporting the PAMS measurements to AQS. The monitoring agencies have the following specific responsibilities: • Collecting and reporting PAMS measurements at each NCore site that is located in a CBSA with a population of 1 million or more based on the latest available census figures. • Participating in the PAMS Required Site Network Workgroup • Developing the monitoring agency's PAMS Required Site IP and submitting to the EPA Region when establishing a new required PAMS site. • Reviewing and providing input to the national PAMS QAPP, SOPs, and TAD • Preparing waivers to PAMS requirements and submitting to the EPA Region, as needed • Selecting and purchasing instruments to measure PAMS parameters • Ensuring that the monitoring agency/PQAO identifies the independent QA personnel that will oversee the QA Program of PAMS Required Site monitoring, including: o Conducting annual internal audits of field and laboratory activities [note - The national contract ASL will be responsible for ensuring internal audits are conducted at the required frequency per their EPA-approved OAPP.] o Reviewing data quality and performing data validation activities, including correcting data when nonconformant data are identified o Ensuring technical personnel are competent to perform monitoring tasks • Installing and testing equipment to meet the implementation date • Entering validated data into AQS in accordance with the protocols described in this QAPP and the AQS Coding Manual unless the entry is performed by a delegated entity (such as the national contract ASL) • Developing the monitoring agency PAMS QAPP and submitting for EPA Regional review and approval • Reviewing the monitoring agency PAMS QAPP annually and revising this document as necessary and within 5 years of previous approval • Developing the monitoring agency PAMS SOPs, reviewing them annually, and maintaining and revising these documents as necessary and within 5 years of previous approval • Reviewing SOPs for ASLs that are not part of a national contract for compliance with this QAPP • Implementing monitoring and analysis as described in the approved QAPPs and SOPs ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 25 of 145 • Ensuring the quality of the data generated by ASLs, as appropriate, as negotiated between the monitoring agency and ASL or described in national contracts • Ensuring personnel attend training courses as necessary to ensure personnel have the qualifications necessary to implement the PAMS Required Site program • Developing and implementing CAPs based on nonconformances identified in internal and EPA audits (including TSAs, audits of data quality [ADQs], PEs, and PTs) The roles and responsibilities of specific monitoring agency personnel are described in Section A6.2. A4.4 Analytical Support Laboratory The ASL is responsible for analyzing the carbonyls samples the SLT monitoring agency submits. Its responsibilities include, but are not limited to: • Complying with the PAMS Required Site SLT monitoring agency QAPP [note - the national contract ASL QS will comply with the requirements in this national QAPP per contractual requirements] • Performing QA activities o Conducting internal audits (such as TSA and ADQ) o Participating in the PAMS PT program • Following an approved SOP for receiving samples, extracting samples, and analyzing sample extracts o Notifying the SLT monitoring agency of problems with samples o Extracting and analyzing carbonyls samples o Maintaining reagents and standards for analyzing carbonyls samples o Ensuring instrument and supporting equipment calibrations for carbonyls extraction and analysis o Taking corrective action when procedural or acceptance criteria deviations occur • Reporting sample and quality control (QC) data to the SLT monitoring agency (unless contracted otherwise) o Verifying the laboratory data meet QA and QC acceptance criteria, are correct, are complete, and comply with monitoring agency validation status readiness o Flagging data with appropriate laboratory qualifiers when procedural or acceptance criteria deviations are identified • Developing and implementing CAPs based on nonconformances identified in internal and EPA audits (TSAs, ADQs, and PTs) • If the ASL is part of the national analytical support laboratory contract (i.e., which typically also serves as the National Air Toxics Trends Stations [NATTS] ASL), developing the laboratory QAPP governing PAMS carbonyls ASL support (which must comply with the requirements in this national model QAPP) and submitting to the OAQPS for approval in a timely manner, implementing the approved QAPP and SOPs, ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 26 of 145 validating data, and reporting required data to AQS per arrangement with the SLT monitoring agency. A4.5 PAMS Support Contractor A support contractor will perform specific tasks associated with the PAMS Required Site program. While the exact tasks will be outlined in an annual EPA task order, the contractor responsibilities are likely to include, but are not limited to: • Facilitating PAMS Required Site Workgroup conference calls o Developing agendas o Participating and leading technical and QA-related discussions o Summarizing conference call notes and identifying action items • Developing nationwide PAMS TSA and proficiency test (PT) programs o Submitting draft program design documents for the TSA and PT program to the OAQPS and to the PAMS Required Site Workgroup to seek stakeholder feedback o Incorporating PAMS Required Site Workgroup comments and finalizing the PT program description document and TSA checklist • Executing and participating in TSAs with EPA Regions o Providing a yearly schedule of site evaluations for the EPA Regions o Assisting Regional staff with the execution of TSAs to ensure national consistency in the audit process o Working with Regional PAMS Leads to review, evaluate, and closeout CAPs resulting from TSAs o Assisting monitoring agencies that require assistance implementing their CAPs • Facilitating and executing the PT program o Informing monitoring agencies of upcoming PTs o Generating and distributing PT samples o Collecting and reporting results to OAQPS, Regional staff, and monitoring agencies o Reporting PT results to AQS A4.6 PAMS Required Site Workgroup The PAMS Required Site Workgroup was formed to address the technical and QA aspects of the PAMS Required Site Program. Members of the group include personnel from the OAQPS, EPA Regions, the monitoring agencies, and EPA's support contractor. The PAMS Required Site Workgroup convened in May 2016 to start a dialogue on the aspects of the PAMS Required Site Network and the steps necessary to ensure a national QS are in place by the June 2021 implementation date for the PAMS Required Site network. The workgroup meets approximately monthly to discuss various technical and QA issues. The PAMS Required Site Workgroup will have the following responsibilities: • Participating in the development and review of the PAMS TAD, national QAPP, and national SOPs • Participating in the development and review of the PAMS TSA and PT programs ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 27 of 145 • Assisting in the development of training and initial and continuing demonstration of capability (IDOC and CDOC) programs • Discussing PAMS Required Site network implementation • Participating in the iterative data quality objective/data quality assessment (DQO/DQA) process for QS improvement It is expected that the workgroup will meet regularly to discuss issues, best practices, and items pertinent to the PAMS Required Site Program to augment the overall quality system. The frequency of meetings will be determined by the workgroup based on the stakeholder needs. A5 Problem Definition/Background Ozone is formed by the reaction of certain VOCs with oxides of nitrogen in the presence of solar radiation. Reducing tropospheric ozone pollution requires reducing or eliminating emission sources of VOCs and oxides of nitrogen. Modelers predict production of ground-level ozone by running complex models which are continually refined to better estimate the ozone concentration forecast under various meteorological conditions. Modelers assess model skill and refine model functionality by comparison of model outputs to actual chemical and meteorological measurements taken at PAMS sites. Modelers prefer the error in the collected measurement data to be less than the error in the associated models. The primary objective of the PAMS air monitoring program is to provide data to evaluate and support the development of air quality models and measurement quality objectives (MQOs) were developed with this objective in mind. The data will be used for other important purposes including tracking trends in ozone precursor concentrations to aid ongoing efforts to attain the ozone National Ambient Air Quality Standard (NAAQS). The PAMS program began in 1993 and was revised in 2006 by the EPA to permit PAMS to be more customized and aligned with the needs of the responsible air quality agencies. On October 1, 2015, EPA further revised the implementation of the PAMS program. The final rule in its entirety may be found elsewhere.1 The following are the highlights of the changes that occurred to the PAMS program as a result of the promulgation of the new regulations: • Network Design - The first part of the network design change involved EPA requiring PAMS measurements during the PAMS (summer) sampling season, defined as June 1 through August 31, at all NCore sites in CBS As with a population of 1 million people or more. The final network design will result in approximately 40 PAMS Required Sites, 14 of which are existing PAMS sites as shown in Table A5-116. The final requirements have waiver provisions which allow monitoring agencies to make PAMS measurements at alternative locations such as existing PAMS sites or at existing NATTS sites and to avoid being required to make PAMS measurements in areas with historically low O3 concentrations. Therefore, the final site locations and network size may differ from what is shown in Table A5-1. The second part of the network design requires states with moderate or above ozone nonattainment areas and states in the Ozone Transport Region (OTR - includes Connecticut, Delaware, the District of Columbia, Maine, Maryland, Massachusetts, New Hampshire, New Jersey, New York, Pennsylvania, Rhode Island, Vermont, and Virginia) ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 28 of 145 to develop and implement Enhanced Monitoring Plans (EMPs) for additional monitoring of ozone precursors and meteorological conditions. These EMPs are intended to provide monitoring agencies with the flexibility to implement enhanced monitoring to suit the needs of their area. EMPs will not be further described within this document. If agencies are conducting EMP activities, those details may be added to the agency specific PAMS QAPP for EMPs. Additional information may be found in the following documents: o Summary of Final Photochemical Assessment Monitoring Stations (PAMS) Network Designs. September 25, 20152 ° Federal Register. Environmental Protection Agency. October 26, 2015. 40 CFR Parts 50, 51, 52, 53, and 58; [EPA-HQ-OAR-2008-0699; FRL-9933-18-OAR]; RIN 2060-AP3 8 National Ambient Air Quality Standards for Ozone1 ° U.S. Census Bureau. Metropolitan and Micropolitan Statistical Areas Population Totals and Components of Change: 2020-202116 Table A5-1. Required Sites in CBSAs with a Population Greater than 1,000,000 Region State AQSID CBSA Population (as of July 1,2021) 1 MA 25-009-2006 Boston-Cambridge-Newton, MA-NH 4,899,932 1 NH 33-015-0018 Boston-Cambridge-Newton, MA-NH 4,899,932 1 RI 44-007-1010 Providence-Warwick, RI-MA 1,675,774 2 NJ 34-013-0003 New York-Newark-Jersey City, NY-NJ-PA 19,768,458 2 NY 36-081-0124 New York-Newark-Jersey City, NY-NJ-PA 19,768,458 2 NY 36-055-1007 Rochester, NY 1,084,973 3 DE 10-003-2004 Philadelphia-Camden-Wilmington, PA-NJ-DE 6,228,601 3 DC 11-001-0043 Washington-Arlington-Alexandria, DC-VA-MD 6,356,434 3 MD 24-033-0030 Washington-Arlington-Alexandria, DC-VA-MD 6,356,434 3 PA 42-101-0048 Philadelphia-Camden-Wilmington, PA-NJ-DE 6,228,601 3 PA 42-003-0008 Pittsburgh, PA 2,353,538 3 VA 51-087-0014 Richmond, VA 1,324,062 4 AL 01-073-0023 Birmingham-Hoover, AL 1,114,262 4 FL 12-011-0034 Miami-Fort Lauderdale-Pompano Beach, FL 6,091,747 4 FL 12-057-3002 Tampa-St. Petersburg-Clearwater, FL 3,219,514 4 GA 13-089-0002 Atlanta-Sandy Springs-Alpharetta, GA 6,144,050 4 KY 21-111-0067 Louisville/Jefferson County, KY-IN 1,284,566 4 NC 37-119-0041 Charlotte-Concord-Gastonia, NC-SC 2,701,046 4 NC 37-183-0014 Raleigh-Cary, NC 1,448,411 4 TN 47-157-0075 Memphis, TN-MS-AR 1,336,103 5 IL 17-031-4201 Chicago -Naperville -Elgin, IL -IN- WI 9,509,934 5 IN 18-097-0078 Indianapolis-Cannel-Anderson, IN 2,126,804 5 MI 26-163-0001 Detroit-Warren-Dearborn, MI 4,365,205 ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 29 of 145 Region State AQSID CBSA Population (as of July 1,2021) 5 MI 26-081-0020 Grand Rapids-Kentwood, MI 1,091,620 5 MN 27-003-1002 Minneapolis-St. Paul-Bloomington, MN-WI 3,690,512 5 OH 39-061-0040 Cincinnati, OH-KY-IN 2,259,935 5 OH 39-035-0060 Cleveland-Elyria, OH 2,075,662 6 OK 40-143-1127 Tulsa, OK 1,023,988 6 TX 48-113-0069 Dallas-Fort Worth-Arlington, TX 7,759,615 6 TX 48-201-1039 Houston-The Woodlands-Sugar Land, TX 7,206,841 7 KS 20-209-0021 Kansas City, MO-KS 2,199,490 7 MO 29-510-0085 St. Louis, MO-IL 2,809,299 8 CO 08-031-0025 Denver-Aurora-Lakewood, CO 2,972,566 8 UT 49-035-3006 Salt Lake City, UT 1,263,061 9 AZ 04-013-9997 Phoenix-Mesa-Chandler, AZ 4,946,145 9 AZ 04-019-1028 Tucson, AZ 1,052,030 9 CA 06-019-0011 Fresno, CA 1,013,581 9 CA 06-037-1103 Los Angeles-Long Beach-Anaheim, CA 12,997,353 9 CA 06-065-8001 Riverside-San Bernardino-Ontario, CA 4,653,105 9 CA 06-073-0003 San Diego-Chula Vista-Carlsbad, CA 3,286,069 9 CA 06-067-0006 Sacramento-Roseville-Folsom, CA 2,411,428 9 CA 06-085-0005 San Jose-Sunnyvale-Santa Clara, CA 1,952,185 9 NV 32-003-0540 Las Vegas-Henderson-Paradise, NV 2,292,476 10 HI 15-003-0010 Urban Honolulu, HI 1,000,890 10 OR 41-051-0080 Portland-Vancouver-Hillsboro, OR-WA 2,511,612 10 WA 53-033-0080 Seattle-Tacoma-Bellevue, WA 4,011,553 EPA modelers are the primary data users; however, it is expected that the chemical and meteorological measurements will aid SLTs in identifying potential sources of ozone precursors and will help inform emissions reduction strategies. The updated PAMS Required Site network is spatially diverse, covering a variety of urban areas with varied and unique geographic, topographic, and meteorological conditions. The resulting dataset will result in a better understanding of ozone formation and emissions reductions that will be most impactful for a specific area so as to increase the likelihood that ozone concentrations will come into attainment with the ozone NAAQS. A5.1 Monitoring Agency PAMS Required Site(s) The monitoring agency will include the PAMS Required Sites covered by this QAPP in Table A5-2. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 30 of 145 Table A5-2. PAMS Required Sites Covered by this QAPP Site AQS ID Site Name Site Location (Address) County XX-XXX-XXXX A6 Project Task/Description This section provides a summary of the work to be performed and the schedule for implementation, including ambient air measurements, collecting samples, acquiring samples; performing chemical analysis; carrying out QA/QC procedures to achieve data quality goals; and meeting the schedules for continued network implementation, operation, and data reporting. A6.1 Required Measurements SLT monitoring agencies will operate and maintain the instruments and equipment needed to make meteorological and chemical measurements for the PAMS Required Site program. Instruments and methods are listed in Table A6-1. The monitoring agency will specify the instrument models in its PAMS IP within its annual network monitoring plan. An example IP suitable for documenting instruments to be deployed is included in Appendix F. The required measurements are listed in 40 CFR Part 58 Appendix D Section 5 and are reproduced below: • Hourly averaged concentrations of speciated VOCs; • Three sequential 8-hour average concentrations of carbonyls determined on a l-in-3-day schedule (refer to Table B1-2), or hourly averaged formaldehyde; • Hourly averaged concentrations of O3 (not covered in this QAPP); • Hourly averaged concentrations of nitrogen oxide (NO), "true" nitrogen dioxide (NO2), and total reactive nitrogen (NOy) (NO and NOy are not covered in this QAPP); • Hourly averaged ambient temperature; • Hourly vector-averaged wind direction; • Hourly vector-averaged wind speed; • Hourly average atmospheric pressure; • Hourly averaged relative humidity (RH); • Hourly precipitation amount; • Hourly averaged mixing layer height (MLH); • Hourly averaged intensity of solar radiation; and • Hourly averaged intensity of ultraviolet (UV) radiation. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page31of 145 This QAPP covers the use of continuous GCs and meteorological measurements at the PAMS site location only. Refer to 40 CFR Part 58 Appendix D Section 5(d) and 5(e) and Appendix F of this QAPP, which describe options, with waivers, for collecting speciated VOCs using canisters and using meteorological data from nearby locations (such as airports). The monitoring agency will be required to submit alternative QAPP documentation to cover the options described in the waiver. Table A6-1. Measurements and Associated Instruments for PAMS Required Sites Measurement Parameter Instrument and/or Method Speciated VOCs auto-GC with thermal desorption and dual FID Carbonyls Carbonyls-specific sampler capable of three sequential 8-hour samples - Collection and analysis per EPA Compendium Method TO-11A ASL will require a high-performance liquid chromatograph (HPLC) or ultra- high performance liquid chromatograph (UHPLC) as described in Method TO-11A and in PAMS TAD Revision 3 Section 5.0 Ozone Federal Reference Method/Federal Equivalent Method (FRM/FEM) ozone analyzera True NO2 FRM/FEM True NO2 analyzer - photolytic conversion with chemiluminescent detection or by cavity attenuated phase shift spectroscopy NO/NOv NOv analyzer3 Ambient Temperature thermometer or thermistor Wind Direction cup and vane, propeller and vane, or sonic anemometer Wind Speed cup and vane, propeller and vane, or sonic anemometer Atmospheric Pressure aneroid barometer, pressure transducer Relative Humidity hygrometer Precipitation tipping bucket Mixing Layer Height ceilometer Solar Radiation pyranometer Ultraviolet Radiation pyranometer a Ozone and NO/NOy are described in the appropriate monitoring agency criteria pollutant monitoring QAPP. A6.2 Personnel to Accomplish Tasks Monitoring agencies are expected to be organized with positions and roles (however named) to accomplish PAMS monitoring tasks. Monitoring agencies will identify those individuals participating in the PAMS Program within the monitoring agency PAMS Required Site QAPP. An organization chart should be included that delineates the reporting structure. NOTE: Monitoring agencies will identify personnel responsible for implementing the OA Program in the monitoring network on the approval form in Appendix A. Such individuals include the program lead, the OA lead, and monitoring staff receiving the approved OAPP. Regardless of the organization of the monitoring agency, the roles are expected to be assigned per the following, or similar, convention: ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 32 of 145 Monitoring Agency Director (e.g., Program Director or similar): The Director has the overall responsibility for managing the office according to monitoring agency policy. This individual maintains overall responsibility for the management and administrative aspects of the technical and QA programs; as such, he or she is responsible for establishing QA policy and for resolving QA issues identified through the QA program. The Director has "stop work authority" and will make final decisions regarding monitoring issues. Major responsibilities include, but are not limited to: • Managing and reviewing budgets, contracts, grants, and proposals • Reviewing, overseeing, and evaluating overall air monitoring activities • Assuring that the office develops and maintains a current QS • Acquiring resources sufficient to enable the collection of required environmental data • Maintaining an active line of communication with monitoring staff supervisor(s) • Ensuring there are sufficient staffing resources to conduct the PAMS measurements and supporting data processing activities • Serving as the arbiter on final data quality/validity determinations and corrective action effectiveness Monitoring Staff Supervisor: The Monitoring Staff (MS) Supervisor reports to the Director and serves as monitoring liaison to the EPA Region. The MS Supervisor consults with the Director on monitoring and makes recommendations, when appropriate. The MS Supervisor's duties include, but are not limited to: • Supervising the activities of monitoring staff • Communicating with EPA Regional personnel on issues related to routine monitoring and QA activities • Maintaining overall responsibility for the monitoring network design, review, and assessment • Maintaining oversight of QA/QC activities, which includes ensuring staff correctly implement and complete regulatory and QS requirements as described in the approved QAPP and SOPs, along with verifying that DQOs and MQOs prescribed in the approved QAPP are met • Documenting deviations from established procedures and methods • Directing staff to implement corrective actions based on audit outcomes • Developing and maintaining this QAPP • Training staff in the requirements of the QAPP and supporting SOPs • Facilitating technical training on instrument operations, maintenance activities, and data management to ensure staff remain proficient and are cognizant of updates to program requirements ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 33 of 145 • Ensuring timely and appropriate updates to the QAPP and SOPs • Assisting in acquiring equipment and maintaining equipment inventories • Overseeing preventive maintenance and equipment certification activities are completed in accordance with the schedules specified in the QAPP and SOPs • Coordinating and reviewing collected data, which includes performing data quality assessments and flagging suspect data • Providing support for monitoring agency databases and data reporting to EPA AQS • Reviewing AQS data QA/QC files to ensure overall data accuracy and completeness • Generating AQS reports to verify successful and accurate upload of monitoring data • Reviewing budgets, contracts, and proposals related to monitoring Monitoring Staff (Site Operators): Staff calibrating and operating instruments and equipment generating data for the PAMS Required Site Network must have the necessary training commensurate with their job duties. Due to the complexity of the instruments needed for the required measurements, site operators must be well-organized and capable of critical thinking to successfully operate, maintain, and troubleshoot the instruments needed for PAMS measurements. Monitoring agency monitoring staff consist of site operators, instrument technicians, and support staff who conduct routine monitoring operations. Monitoring staff report directly to the MS Supervisor and are responsible for implementing the PAMS Required Site QS as described in this QAPP and the supporting SOPs. Responsibilities include, but are not limited to: • Maintaining proficiency with procedures applicable to their assigned duties • Seeking training opportunities and attending training where needed • Installing, calibrating, maintaining, and operating monitoring instruments • Authoring, reviewing, and revising monitoring agency SOPs • Reading, reviewing and contributing to the development of the monitoring agency QAPP • Following SOPs required to implement job responsibilities • Documenting deviations from established SOPs, the QAPP, and monitoring agency policies • Recording monitoring activities promptly and traceably including instrument calibration, maintenance, sample handling, and chain of custody • Documenting unusual events that may impact measurement data • Handling sampling media and instruments to maintain their integrity and avoid contamination • Verifying instrument calibrations by conducting ongoing QC checks ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 34 of 145 • Taking and documenting corrective action when acceptance criteria are exceeded and when nonconformances are identified whether in routine operations or during a TSA, instrument performance audit (IPA), or audit of data quality (ADQ) • Communicating site problems with the MS Supervisor • Working with internal QA staff and external auditors to conduct TSAs, IP As, PEs, and ADQs • Ensuring a sufficient supply of resources such as spare parts, reference standards, sampling media, and consumables are available to facilitate instrument repairs and to minimize down time • Performing first level review of measurement data and flagging suspect data • Retrieving and shipping collected samples (carbonyls) • Ensuring data from automated instruments are recorded and backed up to assure redundancy Quality Assurance Staff: Monitoring agencies/PQAOs will have QA personnel consisting of staff independent of routine monitoring tasks. QA staff will include an overall lead (QA manager, coordinator or officer) and possibly staff members who will report to the monitoring agency Director or similar level of management, minimally two levels above the staff responsible for routine monitoring activities. QA staff will typically be responsible for overseeing the QA functions for numerous monitoring networks operated by the monitoring agency. QA staff members will have the authority to independently report technical and QA issues to management, identify audit findings, and oversee corrective actions on findings affecting data quality. QA staff member (however named - specialists, auditors, officers, etc.) duties include, but are not limited to: • Ensuring that all QS documentation meets programmatic needs and is reviewed and approved prior to the start of data collection • Scheduling and performing internal TSAs on PAMS Required Site monitoring activities. TSAs involve interviewing site operators and data validators, observing processes to assess compliance with the approved QAPP and SOPs, and ensuring siting requirements of the monitoring equipment are met • Scheduling and performing internal IP As and PEs on monitoring agency sampling equipment with reference standards independent of those employed to routinely calibrate and verify calibration of the sampling instruments • Scheduling and performing internal ADQs to assess the accuracy of data collection, data transformation, data reduction, and data reporting operations to AQS, which involves verification of the validity of a representative amount of collected measurement data • Reviewing PT results and ensuring corrective actions are taken for nonconformances • Documenting the outcomes of internal IP As, PEs, TSAs, and ADQs and reporting the outcomes to management ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 35 of 145 • Managing the document control system • Evaluating the quality of measurement data for compliance with the established DQO (if any/as applicable) and MQOs for the various data quality indicators (DQIs) • Ensuring corrective actions are taken as a result of QS nonconformances • Assessing effectiveness of corrective actions and conducting follow-up audits to demonstrate return to conformance • Maintaining QA-related documents, files, and records Data Validators: Monitoring agency data validation staff will have sufficient training to be familiar with the PAMS measurement system data outputs, quality control of the measurement systems, typical variations in measurement values, interactions and relationships between of PAMS measurements (e.g., expected ratios of concentrations of various VOCs), chemical constituents of greatest concern, and tools used to evaluate and investigate the technical validity of PAMS measurement data. Data validators may consist of monitoring agency technicians, QA staff, or other qualified individuals depending on what level of data validation is occurring. Final validation must take place by personnel independent of technical monitoring staff. Data validators will ultimately report to the monitoring agency Director, however named. Analytical Support Laboratory (ASL): ASL staff will comply with the portions of this QAPP which apply to the laboratory analysis of carbonyls and/or speciated VOCs in canisters. The specific employee reporting hierarchy requirements of the ASL is outside of the scope of this QAPP; however, each ASL will minimally have a structure similar to the monitoring agency whereby there is a Director or Manager, an analyst and/or technician to perform laboratory activities, and a QA staff member with authority to independently review and assess laboratory operations for the PAMS Required Site program work. ASL technicians calibrating and operating data generating laboratory instruments and equipment for the PAMS Required Site Network will have the necessary training commensurate with their job duties. Due to the complexity of the instruments needed for the required measurements, technical staff must be well-organized and capable of critical thinking to successfully operate, maintain, and troubleshoot the laboratory instruments needed for PAMS measurements. ASL QA staff will similarly have experience and training necessary to properly perform independent assessment of the instrument calibration and operation, data reduction, data verification, and data reporting processes. The monitoring agency will identify the ASL within this QAPP and will identify the ASL QAPP (or equivalent), QMP, and SOPs to be followed for the ASL fulfilling the PAMS Required Site program carbonyls analysis or VOC requirements. These documents may be indicated by reference. If not identified within the ASL QAPP, the monitoring agency will identify in their PAMS QAPP those individual(s) at the ASL responsible for: - Performing analyses Verifying data - Providing QA oversight and assessments - Providing overall oversight of the ASL's support to the PAMS Required Site monitoring agency Communicating with the monitoring agency director, however named. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 36 of 145 A6.3 Schedule for PAMS Required Site Activity Milestones The monitoring agency will conduct the PAMS Required Site activities to meet the milestones as described in Table A6-2. Note that start and completion dates for activities listed are specified for agencies monitoring solely during the June 1 to August 31 PAMS season, and the dates may be adjusted to accommodate agencies monitoring for periods extending beyond the default PAMS season. Agencies intending to monitor following a schedule outside the three-month PAMS season should adjust the dates in the table below to ensure activities are completed in advance of the monitoring period. Table A6-2. PAMS Required Site Activity Annual Milestones Activity Start Date Completion Due Date Details Pre-sampling Season Instrument and Support Equipment Maintenance As needed to ensure completion by June 1 annually Prior to June 1 annually Complete annually prior to beginning annual monitoring - Preventive maintenance for measurement instruments, sample collection instruments, support equipment Reference Standards Acquisition, Certification, or Recertification As needed to ensure instruments are calibrated prior to June 1 annually Prior to June 1 annually Complete annually prior to beginning annual monitoring - Reference standard materials (calibration stock gases or carbonyls standards) and reference standard instruments will be acquired, certified, or recertified, as appropriate Instrument warm up, conditioning, and calibration Prior to June 1 annually for all measurement systems Prior to June 1 annually (to be completed prior to receipt of PTs for speciated VOCs and carbonyls) Shakedown period for each instrument to ensure stable and accurate instrument performance by the start of PAMS season on June 1 - particularly important for sites operating instruments only for PAMS season Quality Systems Review and Revision Once data are validated and reported to AQS from the previous year, approximately March 31, if not earlier April 15 annually Review of the PAMS Required Site QAPP and supporting SOPs to ensure policies and procedures are accurate and current - completed once validated data from the previous year are reported to AQS and prior to beginning monitoring for the calendar year Demonstration of Capability As convenient to ensure completion and approval prior to June 1 - or earlier if PAMS monitoring begins prior to beginning monitoring for the calendar year Prior to June 1 - or earlier if PAMS monitoring begins prior to beginning monitoring for the calendar year Approval by monitoring agency management (i.e., immediate supervisor) of the instrument operators, data validators, and auditors to perform their assigned duties - staff will complete training and management will approve by signature (Refer to example training form in Appendix D) ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 37 of 145 Activity Start Date Completion Due Date Details Shakedown Audit Prior to June 1 annually Prior to June 1 annually - prior to PAMS season for sites monitoring earlier than June 1 readiness assessment to determine areas requiring resources or correction to ensure systems are online and calibrated prior to commencing PAMS monitoring Proficiency Test (PT) for Speciated VOCs and Carbonyls Phase 1 - Prior to June 1 annually (for VOCs) Phase 2 - August 15 annually (for VOCs) Prior to June 1 annually (for VOCs) August 31 annually (for VOCs) Sample with concentrations of target speciated VOCs and carbonyls blind to the site operator and/or support laboratory - VOCs conducted prior to and toward the end of each PAMS season. Carbonyls conducted prior to PAMS seasons. PAMS Monitoring June 1 annually August 31 annually Beginning and ending of Monitoring as Required in 40 CFR Part 58 Appendix D Section 5 and described in Section A.7.3.1.1 of this QAPP - monitoring agencies may monitor outside of these dates if their ozone problem begins earlier and/or lasts beyond this period Internal Technical Systems Audit (TSA) June 1 annually August 31 annually Review of monitoring agency compliance with PAMS Required Site program requirements, QAPP, SOPs, and best practices - conducted by monitoring agency QA - conduct of the TSA will occur during active monitoring for agencies conducting monitoring beyond June 1 to August 31 Performance |igust 31 annual| Conduct of the PE will occur durirB_ Evaluation (PE) l| True NO2 active true NO2 monitoring for agencies conducting monitoring beyond June 1 tc August 31 Challenge of the true NO2 measurement system with known NO2 concentrati^I produced by GPT - conducted by monitoring agency QA or independent PQAO sl;B Instrument Performance Audit (IP A) June 1 annually August 31 annually Conduct of the IPA will occur during active monitoring for agencies conducting monitoring beyond June 1 to August 31 Measurement of the carbonyls sampling unit flow with a certified reference flow transfer standard - conducted by monitoring agency QA Assessment of meteorological measurements by comparison to a certified reference standard - conducted by monitoring agency QA ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 38 of 145 Activity Start Date Completion Due Date Details Audit of Data Quality (ADQ) Not before data are reported to AQS Prior to review and revision of PAMS QA documents for the following year's monitoring Review of a representative amount of PAMS measurement data for accuracy from instrument calibration, sample measurement, and final reporting to AQS Data Verification and Validation June 8 annually Prior to data reporting to AQS Data verification and validation begins approximately one week after start of data collection to ensure data meet acceptance criteria and ensure the workload is manageable. Data Reporting to AQS Not before data validation is completed Within 180 days of the end of the calendar quarter in which the measurement data were collected Input of validated measurement data to AQS. Upload of all PAMS parameter data to AQS and verification that data were uploaded correctly A6.4 Summary of Assessment Techniques The monitoring agency and ASL will assess the performance of the PAMS Required Site activities by conducting independent assessments. The monitoring agency and ASL QA staff will perform these assessments as detailed in Section C.l.l. A7 Quality Objectives and Criteria The primary objective of the PAMS Required Site network is to provide data of known quality for use by EPA modelers and scientists. A7.1 Data Quality Objectives DQOs are qualitative and quantitative statements derived from the DQO Planning Process that clarify the purpose of a study, define the most appropriate type of information to collect, determine the most appropriate conditions under which to collect that information, and specify tolerable levels of potential decision errors. DQOs define the quality of and the acceptable levels of uncertainty in the measurements and their associated uncertainty that can be tolerated to make decisions regarding the measurements. Stated another way, DQOs are statements describing "how good" the measurements need to be to provide data to control decision risk(s) meet the project outcomes within a known certain levels of confidence and to ensure that collected data are of sufficient quantity and quality to be fit for the stated purpose to objectively assess the risk in the decisions to be made. Although a formal DQO process was not undertaken on the PAMS Required Site Network to determine a PAMS Required Site DQO, EPA solicited input on data needs from PAMS monitoring agencies and EPA modelers, i.e., from the primary users of the PAMS information. Measurement quality objectives (the MQOs) for the various data quality indicators (DQIs) were established based on the expertise of EPA modelers and data analysts and their data quality needs for ozone and ozone precursor model evaluation and model inputs. Modelers compare their model outputs to observed concentrations. For such comparisons the measured concentrations are considered to be the true value thus minimizing bias and imprecision was ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 39 of 145 determined to be most important for the improvement of model skill. Monitoring agencies measuring PAMS parameters and other experts in PAMS measurements reviewed the proposed MQOs to ensure they were reasonable and attainable. Additionally, if more sensitive or accurate measurement methods become available and are deemed to be necessary to meet modelers' needs, the MQOs may be modified and refined to accommodate the updated methods. A7.2 Data Quality Indicators The DQIs of representativeness, completeness, precision, bias, and sensitivity are the characteristics describing how good the data must be to meet the DQO. The DQIs are characterized by prescribing an associated MQO for each DQI that details the specific criteria to be met. These DQIs and associated MQOs are detailed further in Sections A7.3.1 through A7.3.5. A7.3 Measurement Quality Objectives The MQOs for each of the DQIs are shown in Table A7-1. Since O3 and NO2 are criteria pollutants and are used for designating compliance with the NAAQS, the MQOs in Table A7-1 duplicate those listed in the validation templates of the EPA QA Handbook Volume II. Note that an MQO for precision is not specified for meteorology measurements. Precision for meteorology would involve either measuring the same event with two separate instruments (collocation) or measuring a standard condition in replicate. It is not practical to operate a full-time collocated meteorology station due to the additional expense and logistics required to install a separate meteorology tower, and challenging the meteorology instruments in situ to acquire replicate measurements of a controlled meteorology condition is impractical. Additional details on the various checks used to measure and assess the DQIs may be found in the Quality Control Measurements Section B1.2. EPA technical staff, their QA support contactors, monitoring equipment vendors, and the monitoring agencies also provided feedback on the MQOs for various DQIs that would be considered achievable under field conditions. These MQOs were then discussed with monitoring agencies and other PAMS measurement subject matter experts to ensure that the MQOs were attainable and reasonable, and if not, the MQOs were further refined as listed in Table A7-1. EPA modelers found these to be acceptable. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 40 of 145 Table A7-1. PAMS DQIs and Associated MQOs Method or Parameter DQI Chemical Measurements Representativeness (Sampling Frequency)3 Bias (%) Precision (%) Sensitivity (Detection Limit) Completeness (%) Auto-GC speciated VOCs Continuous, hourly average <25b <25c < 0.5 ppbC >75 True NO2 and NO/NOy Continuous, hourly average <±15.1% or ± 1.5 ppbd whichever is greater < 15.1% or 1.5 ppbc whichever is greater <0.001 ppm >75 Ozone Continuous, hourly average < ± 7.1% or ± 1.5 ppbd whichever is greater <7.1% or 1.5 ppbc whichever is greater < 0.002 ppm > 90% (avg) daily max available in O3 season with min of 75% in any 1 year1 TO-11A (carbonyls) Three sequential 8- hour samples every 3rd daye>f <25g < 15h <0.25 (ig/m3 >85 Meteorology Representativeness (Sampling Frequency)3 Bias Precision Sensitivity (Resolution) Completeness (%) Ambient Temperature Continuous, hourly average < ± 0.5 °C not specified <0.1 °C >75 Relative Humidity Continuous, hourly average < ± 5% RH not specified < 0.5% RH >75 Barometric Pressure Continuous, hourly average < ± 3 hPa not specified <0.1 hPa >75 Wind Speed Continuous, hourly average < ± 0.2 m/s or ± 5%, whichever is greater not specified <0.1 m/s >75 Wind Direction Continuous, hourly average <±5 degrees not specified < 1 degree >75 Solar Radiation Continuous, hourly average <±5% not specified < 1 Watt/m2 >75 UV Radiation Continuous, hourly average <±5% not specified < 0.01 Watt/m2 >75 Precipitation Continuous, hourly average <± 10% not specified <0.25 mm/lir >75 Mixing Layer Height Continuous, hourly average Not ApplicableJ not specified < 10 m >75 a Spatial representativeness is addressed in monitor siting as specified in Section A7.3.1.2. b Assessed with twice-annual PT samples and across the entire PAMS season as the upper bound of the mean absolute value of the percent differences across all single-point QC checks. For functional form of the calculation, see 40 CFR 58 Appendix A Section 4.1.3, Equations 3, 4 and 5. 0 Measured as the upper bound of the coefficient of variation (CV) across all single-point QC checks in the PAMS season. For functional form of the calculation, see 40 CFR 58 Appendix A Section 4.1.2, Equation 2. Acceptance criteria listed here for criteria pollutants duplicate those in the EPA QA Handbook validation templates. Changes to the QA Handbook requirements will supersede those criteria listed here. d Measured as the upper bound of the mean absolute value of the percent differences across all single-point QC checks in the PAMS season. For functional form of the calculation, see 40 CFR 58 Appendix A Section 4.1.3, Equations 3, 4, and 5. Acceptance criteria listed here for criteria pollutants duplicate those in the EPA QA Handbook validation templates. Changes to the QA Handbook requirements will supersede those listed here. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 41 of 145 e Carbonyls sampling by TO-11A may be substituted with continuous formaldehyde monitoring and reporting of the hourly average. MQOs for continuous formaldehyde monitors have not been established at the time this document was written. f Carbonyls sampling will follow the l-in-3 day sampling schedule as prescribed in Table B1-2 and the national sampling calendar available at the following link on AMTIC: https://www.epa.gov/amtic/sampling-schedule- calendar g Assessed with twice-annual PT samples. h Measured as the coefficient of variation of the RPDs across, as applicable, all (i) duplicate/collocated field- collected cartridges; duplicate laboratory control samples (LCS), and (iii) replicate laboratory analyses in the entire PAMS season. See Sections 2.5.1 and 2.5.2 of the NATTS 2011-2012 Quality Assurance Annual Report available here: https://www3.epa.gov/ttnamtil/files/ambient/airtox/NATTS201120120AARfinal.pdf 1 Refer to 40 CFR Part 50 Appendix U, Section 4 J Agencies are not required to calculate bias for the mixing layer height. EPA reserves the right to revise the prescribed MQOs as needed. Any such adjustments will be communicated to the PAMS Required Site Network stakeholders and documented in a revised QAPP. A 7.3.1 Representativeness A 7.3.1.1 Temporal Representativeness To adequately characterize the concentrations of ozone and ozone precursors during PAMS season (defined by default as June 1 to August 31 - though the period at a given site when ozone production becomes problematic may be extended to begin before June 1 and end after August 31), the sampling frequency for each of the required parameters is prescribed as follows. The sampling frequency for ozone, true NO2, NOy, speciated VOCs, and meteorological parameters is for sampling to occur continuously daily, and the collected data averaged for each hour. Ozone and NO/NOy measurements at the PAMS Required Site will be described in and comply with the monitoring agency QAPP governing the NCore measurements of criteria pollutants at the site. Due to the labor-intensive aspects of manual sample collection onto cartridge media and the difficulty in achieving adequate sensitivity, carbonyls sampling is not required hourly, but instead is required on a l-in-3-day schedule consisting of three sequential 8-hour samples (refer to the sampling schedule in B 1.1.1 for start and stop times). Carbonyls samples will be collected per the national sampling calendar available at the following link on AMTIC: https://www.epa.gov/amtic/sampling-schedule-calendar Carbonyls collection onto 2,4-dinitrophenylhydrazine (DNPH) cartridges may be substituted with continuous formaldehyde measurements for which the concentration data are reported as the hourly average (note that the QA requirements have not been established for continuous formaldehyde measurements). Monitoring agencies will specify the frequency and schedule for collection of VOCs if it has a waiver to collect VOCs in canisters for laboratory analysis. The average hourly measurement of ozone precursors collected continuously (with the exception of the required compromise presently required for carbonyls) provide a sufficient number of data points at a sufficient time resolution to ensure that the measurements characterize the concentration patterns over the course of the PAMS season at a given PAMS Required Site. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 42 of 145 Incorporating the meteorological measurements reported as an hourly average provides a robust dataset representative of the conditions at the site. Monitoring agencies will specify the monitoring schedule for each monitoring method (such as during the June 1 to August 31 PAMS season, year round, or other appropriate schedule). A 7.3.1.2 Spatial Representativeness - Chemical Measurement Probe Siting Criteria Sampling inlet probes and equipment must comply with the siting criteria in 40 CFR Part 58 Appendix E to ensure the collected atmosphere is representative of the ambient air in the geographic area of the site. If there are any issues with meeting the requirements, the monitoring agency must consult with the EPA Regional office to request a waiver. The probe must be at least 1 meter vertically or horizontally away from any supporting structure, walls, parapets, penthouses, etc., and away from dusty or dirty areas. Inlet probes must have unrestricted airflow in a continuous 270-degree arc and the predominant wind direction must be included in this arc. To the extent feasible, inlet probes must not be located on the side of a building. However, if such is unavoidable, then the inlet must be located on the windward side of the building or wall relative to the prevailing wind direction during PAMS season and must have unrestricted airflow in an arc of at least 180 degrees. As most of the PAMS Required Sites will be located at existing NCore sites, EPA does not expect that probes will be mounted on the side of a building. Inlet Probe Heights: Inlet probes must be placed at the following heights: PAMS VOCs 2 to 15 m above ground level (AGL) PAMS carbonyls 2 to 15 m AGL True NO2 2 to 15 m AGL (neighborhood or larger spatial scale) Obstructions: The inlet probe must be minimally twice the distance from the potential obstruction as the potential obstruction extends above the inlet probe. For example, if a wall extends 2 meters above the inlet probe, the inlet probe must be 4 meters or more from the wall. Spacing from Trees: Trees can provide surfaces for O3 or NO2 adsorption or reactions and may prevent the accurate measurement of other PAMS parameters when of a sufficient height and leaf canopy density to interfere with airflow. To avoid such interferences, inlet probes must be minimally 10 meters, and should preferably be 20 meters when measuring NO2, from the dripline of the nearest tree. Spacing from Roadways: Mobile sources represent a significant source of ozone precursors; therefore, it is important to ensure that monitoring site inlet probes are sufficiently displaced from roadways where they can be unduly impacted by motor vehicle emissions. Minimum separation distances for monitor inlet probes from roadways assume PAMS sites are urban scale and therefore must comply with Table E-l of 40 CFR Part 58 Appendix E, reproduced below in Table A7-2. Note that these minimum separation distances must also be maintained from other motor vehicle traffic areas such as parking garages and parking lots. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 43 of 145 Table A7-2. Minimum Monitor Separation Distance from Roadways Roadway average daily traffic (ADT), vehicles per day Minimum distance a (meters) Minimum distance a'b (meters) < 1,000 10 10 10,000 10 20 15,000 20 30 20,000 30 40 40,000 50 60 70,000 100 100 > 110,000 250 250 a Distance from the edge of the nearest traffic lane. The distance for intermediate traffic counts will be interpolated from the table values based on the actual traffic count. b Applicable for ozone monitors whose placement has not already been approved as of December 18, 2006. A 7.3.1.3 Spatial Representativeness - Meteorology Siting of meteorology equipment for the required measurements is specific to each instrument type. General siting criteria for the meteorology instruments follows. Wind Speed and Wind Direction: The standard height for surface layer wind measurements is 10 m AGL.4-6-7 The location of the site for the wind measurements must ensure that the horizontal distance to obstructions (e.g., buildings, trees) is at least 10 times the height of the obstruction.4-7 An obstruction may be man-made (e.g., a building) or natural (a tree). A wind instrument must be securely mounted on a mast on the tower that will not twist, rotate, or sway. Sensor height and its height above the obstructions, as well as the character of nearby obstructions, must be documented in the site characterization documentation. An open lattice tower is the recommended structure for monitoring of meteorological measurements at the 10-m level. In the case of wind measurements, certain precautions are necessary to ensure that the measurements are not significantly affected by turbulence in the immediate wake of the meteorological tower. To avoid such tower effects, the wind sensor will be mounted on a mast a distance at least one tower width above the top of the tower, or if the tower is higher than 10 m, on a boom projecting horizontally from the tower. In the latter case, the boom will extend a distance at least twice the diameter/diagonal of the tower from the nearest point on the tower. The boom will project into the direction which provides the least distortion for the most important wind direction (i.e., into the prevailing wind). Ambient Temperature and RH: The standard height for surface layer ambient temperature and RH measurements is 2 meters AGL.6 Higher mounting is permitted; if a tower is used, the temperature sensor will be mounted on a boom which extends at least one tower width/diameter from the tower. The measurement will be made over a uniform plot of open, level ground at least 9 m in diameter centered on the sensor. The surface will be covered with non-irrigated or un- ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 44 of 145 watered short grass or, in areas which lack a vegetation cover, natural earth. Concrete, asphalt, and oil-soaked surfaces and other similar surfaces must be avoided to the extent possible. The sensor will be at least 30 m horizontally from any such paved area. If these siting criteria (open ground and distance from paved surfaces) cannot be achieved, it will be identified in site characterization documentation. Other areas to avoid include extraneous energy sources (subway entrances, rooftops, electrical transmission equipment), large industrial heat sources, roof tops, steep slopes, hollows, high vegetation, swamps, snow drifts, standing water, tunnels, drainage culverts, and air exhausts. The distance to obstructions for accurate temperature measurements will be at least four times the obstruction height.8 Solar Radiation and Ultraviolet Radiation: Solar and UV radiation measurements will be taken in a location with an unrestricted view of the sky in all directions. Locations where there are obstructions that could cast a shadow or reflect light on the sensor, such as light-colored walls or artificial sources of radiation, must be avoided. The elevation to the horizon as viewed from the pyranometer must not exceed 5 degrees. Sensor height is not critical for pyranometers; consequently, tall platforms or roof tops are typical locations. Barometric Pressure: Barometric pressure instruments will be located in a ventilated shelter about 2 m above ground level. The height of the station above mean sea level and the height of the pressure sensor AGL will be documented in the site characterization records. Precipitation: Precipitation gauges will be located on level ground in an open area. Obstructions will not be closer than two times their height from the instrument. The area around the precipitation gauge should be covered with natural vegetation and should not be located on a paved or hard surface (e.g., the roof of a monitoring shelter) to minimize splashing. The mouth of the gauge will be level and will not be lower than 30 cm above ground level (to avoid being covered with snow). To ensure accessibility for technicians, the instrument should be mounted not higher than 2 m above ground level. A wind shield/wind screen (such as an Alter-type wind shield consisting of a ring with approximately 32 free-swinging separate metal leaves) will be employed to minimize the effects of high wind speeds. Mixing Layer Height (MLH): The ceilometer for determining MLH measurements is intended for more macro-scale application than are the surface meteorological measurements. Consequently, the location of the ceilometer need not be associated with any particular PAMS surface site. Factors that will be considered in selecting a site for the MLH monitor include whether the upper-air measurements for the proposed location are likely to provide the necessary data to characterize the meteorological conditions associated with high ozone concentrations, and the extent to which data for the proposed location of the ceilometer may augment an existing upper-air network. The ceilometer must be securely installed on a stable level surface such as a concrete pad or wooden platform suitably located to provide an unobstructed view of the sky. A wide-open location is recommended where there are no tall trees, overhead lines, or antennas nearby. Proximity to powerful radars should also be avoided. Any object in the cone projecting upward created by an angle of 25° from vertical will impede the ability of the ceilometer to properly measure atmospheric backscatter. Common interfering objects would include powerlines, tree branches, tower support guidewires, flagpoles, or similar features which may be permanently or transiently present above the ceilometer. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 45 of 145 A 7.3.2 Completeness Generation of a dataset sufficient to characterize the daily concentrations of ozone, ozone precursors, and parameters of interest to PAMS requires that a minimum number of the intended measurements are valid. Completeness is defined as the percentage of the number of valid data values compared to the number of values intended to be collected. The MQOs for completeness are specified for each parameter as detailed in Table A7-1. For continuous measurement methods reported as the hourly average, uncollected or invalidated measurement results are lost, and cannot be made up. For hourly measurements, 45 minutes will be considered a valid hour and 18 hours a valid day. Note that due to limitations with the instrument cycling for sample collection and measurement, a valid sampling hour for speciated VOCs is 40 minutes of sampling for the hour, for which 30 minutes of this 40-minute period must occur during the sampling hour. The overall completeness listed in Table A7-1 will be based on acquiring data for the entire PAMS season determined as the total valid samples out of the samples possible. For continuous measurements, this will be based on approximately 2208 hours. For carbonyls samples, the total possible sampling days is 30 or 31 days, depending on the sampling calendar for the year. For carbonyls sample collection, if a sample day is missed, a null code "AF" (scheduled but not collected) will be reported to AQS for the sample run date; if the sample is invalidated for a particular reason, an appropriate null code will also be reported to AQS for the sample run date. A make-up sample must be collected as soon as practical according to the make-up sampling policy below. Carbonyls Make-Up Sample Policy: For invalidated or missed carbonyls sampling events, a make-up sampling event will be conducted. As soon as a sampling issue is known, a replacement carbonyls sample set (three 8-hour samples) will be collected as close to the original sampling date as possible, should not exceed two weeks from the originally scheduled collection date, and will be collected within PAMS season barring extenuating circumstances such as equipment failure or if the sampling event is the last of the season, etc. Make-up samples will be collected according to the following: 1. Before the next scheduled sampling date 2. Within two weeks of the missed collection date, with preference given that the rescheduled date occurs on a weekday or weekend day to match that of the original schedule Recognizing that the laboratory analyses and/or reporting of carbonyls sample data may occur after this period, make-up samples will most likely be collected for cartridge or instrument issues that the site operator is able to identify soon after the original sampling date. A 7.3.3 Precision Precision is a measure of agreement among repeated measurements of the same property under identical, or substantially similar, conditions. The lack of precision (imprecision) represents the random component of error. Precision for Continuous Measurements of Ozone and NOy: Precision assessments for NOy and ozone are addressed in the monitoring agency NCore or State and Local Monitoring Stations (SLAMS) QAPP for criteria pollutant monitoring. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 46 of 145 Precision for Continuous Measurements of true NO2: Precision for true NO2 is assessed by calculating the upper 90% confidence limit (CL) for the coefficient of variation (CV) across all single-point QC checks measured annually (or during PAMS monitoring if NO2 monitoring is limited to PAMS season). For functional form of the calculation, see 40 CFR 58 Appendix A Section 4.1.2, Equation 2. Precision for Speciated VOCs: Precision is assessed by analysis of replicate calibration verification standards. A sequential (back-to-back) analysis of the continuing calibration verification (CCV) is performed for the speciated VOCs precision check. As an overall MQO, the precision is evaluated as the upper bound of the coefficient of variation (CV) across all single-point CCVs in the PAMS season. For functional form of the calculation, see 40 CFR 58 Appendix A Section 4.1.2, Equation 2. Within run precision is evaluated by comparing replicate measurements in a pair-wise fashion to determine the relative percent difference (RPD) between the two measurements which must be < 25% for each assessed target compound. RPD is calculated by dividing the absolute value of the difference between the two measurements by the average of the two measurements. Precision will be further evaluated on an ongoing basis for groups of CCVs by calculating the relative standard deviation (RSD) which is found dividing the standard deviation of the measurements by the average of the measurements. RSD for n > 2 replicate measurements must be < 25%. When determining RSD for speciated VOCs, all measurements in the desired time window (e.g. including the precision CCVs for one month, two months, or all of PAMS season) will be included unless there is a valid reason for exclusion (such as instrument problem or other documented technical issue). Ambient sample data for target analytes failing precision criteria will be appropriately qualified or invalidated, as appropriate, when reported to AQS. Monitoring agencies must take corrective actions for precision acceptance criteria failures of priority compounds and should take corrective actions for optional compounds failing precision criteria, though they are not required. Monitoring agencies should evaluate precision on an ongoing basis to determine whether precision criteria are in jeopardy and take corrective actions to ensure precision across the monitoring season does not exceed criteria. Precision for Meteorology Measurements: As discussed in Section A7.3, precision for meteorological measurements is not practical and will not be assessed for the PAMS Required Site Program. Precision for Carbonyls: Field sampling precision must be assessed for carbonyls at minimally 10% of the PAMS Required Network Sites. Such precision assessments entail collection of duplicate samples (a pair of samples collected through a common inlet probe) or collocated samples (a pair of samples each collected through independent inlet probes) concurrently with the primary sampling events. The monitoring agency can choose to assess precision by either the duplicate or collocated method. Duplicate or collocated cartridges will be collected at a rate of minimally 10%, equivalent to three per month. Precision of duplicate and collocated samples is assessed as the RPD of the concentrations measured for the collocated or duplicate pair and must be < 20% for samples for which both cartridges measure >0.5 |ig/cartridge. Duplicate or collocated samples for which one or both cartridges measure < 0.5 |ig/cartridge are not required to meet this acceptance criterion. Duplicate or collocated results that do not meet the precision acceptance criterion will be qualified when entered in AQS and will prompt the ASL and field ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 47 of 145 operations to perform corrective actions to investigate the precision sample result discrepancy for priority compounds. Corrective actions should be taken for precision failures for optional carbonyl compounds, but they are not required. Precision of laboratory extraction and analysis procedures is to be assessed by preparation and analysis of duplicate laboratory control samples (LCS) consisting of a pair of blank DNPH cartridges spiked with target compounds at the laboratory and extracted and analyzed with collected field samples. Precision of the LCS and LCS duplicate (LCSD) is assessed as RPD which must be < 20%. An LCS/LCSD pair is to be prepared, extracted, and analyzed minimally twice quarterly. Ambient sample results associated with LCS/LCSD results that do not meet the precision acceptance criterion will be qualified when entered in AQS and will prompt the ASL to perform corrective actions to correct the discrepancy for priority compounds. Corrective actions should be taken for LCS/LCSD precision failures for optional carbonyl compounds, but they are not required. Precision of laboratory analysis is assessed by replicate analysis of an extract from a field- collected cartridge (not a trip or field blank). Precision of the replicate analysis is assessed as RPD which must be < 10% for samples that measure >0.5 |ig/cartridge. A replicate analysis is to be performed with each analysis batch (defined as a sequence of samples extracted as a single group over a finite time interval, typically 20 field-collected cartridges). Failures of priority compound replicate sample results will prompt the ASL to take corrective action which should include reanalysis of the sample extract to confirm the failure. If the analytical precision failure cannot be corrected, associated ambient sample results will be qualified when entered in AQS for affected compounds. Corrective actions should also be taken for replicate analysis failures for optional carbonyl compounds, but they are not required. The network MQO for carbonyls is based on an evaluation of the entire PAMS season's data. In all cases a CV of < 15% must be met. For more information on how the CV is calculated, see the 2011-2012 NATTS Quality Assurance Annual Report, available at the following link: https://www3.epa.gov/ttnamtil/files/ambient/airtox/NATTS20112012QAARfinal.pdf Note that this precision MQO is different than the precision acceptance criteria for the individual pairs of duplicate or collocated samples, the imprecision of which are permitted to exceed 15%. Such method-specific precision requirements apply to comparing two measurements and do not apply to larger (N > 2) sample sets. A 7.3.4 Bias Bias, the systematic (nonrandom) deviation of a measurement from a known or accepted value, is minimized by using calibrated instruments and equipment, by checking that instruments remain calibrated over time, and by minimizing sources of background contamination. All instruments must be suitably calibrated before PAMS season and thereafter their calibration must be periodically demonstrated to remain valid by comparison with a known traceable certified reference standard or instrument. For chemical measurements, once calibration is established for an instrument, the calibration is to be immediately verified against a known traceable certified standard, typically a second source standard. The required frequency for periodic ongoing checks for PAMS instruments is described below. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 48 of 145 Bias of continuous chemical analysis parameters is evaluated by challenging the instruments with a known standard on a frequent basis, daily for VOCs and minimal^pve^B4 daj for N02, typically during nighttime hours when ambient concentrations of the target analytes are lower and the measurements are less critical in predicting ozone levels for the following day. The known standard is analyzed to demonstrate the instrument calibration remains within tolerance and is typically followed by a blank or "zero" immediately following the calibration check to demonstrate that the instrument signal returns to background levels in the absence of target analyte. The overall bias MQOs for the continuous parameters for the entire PAMS season are shown in Table A7-1. The nightly continuing calibration checks and zero background checks for the auto-GC and true NO2 analysis are described in Sections B5.1.2 and B5.1.3, respectively. For carbonyls, bias resulting from field activities is assessed and minimized by a combination of pre-deployment bias checks and flow calibration and calibration verification for sample collection instruments and by periodic collection of field and trip blanks. Laboratory bias is minimized by calibration and verification of detector response for the HPLC analysis instrument. Following annual maintenance and prior to field deployment at the beginning of each PAMS season, a positive bias verification and flow calibration are performed on the carbonyls sampling unit. The positive bias verification is briefly described in Section B5.1.1 and is detailed in Revision 3 of the PAMS TAD (https://www.epa.gov/amtic/photochemical-assessment- monitoring-stations-pams) and in the carbonyls field sample collection standard operating procedure (SOP). The positive bias verification procedure will be described in the agency carbonyls field sample collection SOP and must demonstrate that the sampling unit contribution for each target carbonyl is < 0.2 |ig/cartridge. This is evidenced by measurement of target compounds on a challenge cartridge collected with humidified zero air being < 0.2 |ig/cartridge greater than the co-collected reference cartridge for each individual target carbonyl compound. The sampling unit must meet this specification before field deployment. Note: Monitoring agencies are encouraged, but not required, to take corrective action to eliminate apparent contamination from samplers even if the 0.2 jug cartridge threshold is not exceeded. Sampling unit flow rates must be verified before field deployment and monthly thereafter against a National Institute of Standards and Technology (NIST)-traceably certified reference flow transfer standard. Indicated flow rates must be within ± 10% of the flow transfer standard. If the flow is not within ±10%, ambient sample data since the most recent passing flow check will be qualified or invalidated. Laboratory bias is controlled by establishing a multi-point calibration curve with subsequent analysis of a CCV standard every 12 hours of analysis. This CCV must demonstrate the instrument calibration remains within ±15% of the original response. If this criterion is exceeded, corrective action will be performed to demonstrate appropriate calibration response and the extracts since the last passing CCV will be reanalyzed. If reanalysis cannot be performed, ambient sample data for affected target analytes will be qualified when reported to AQS. The CCV is followed by a solvent method blank when additional samples are to be analyzed to demonstrate that the instrument has returned to a stable baseline and that there is no carryover or significant interferences in the instrument system. Poor or infrequent instrument or instrument inlet maintenance will also cause bias in reported concentrations for speciated VOCs and carbonyls. Instrument maintenance is described in Section B6.4 of this QAPP and in the supporting instrument SOPs. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 49 of 145 Bias of speciated VOCs and carbonyls will be assessed annually just prior to PAMS season and VOCs will also be assessed toward the end of PAMS season through analysis of PT samples. Bias of speciated VOCs measurements will be additionally assessed by evaluation of the ongoing single-point QC checks. For the functional form of this calculation, refer to 40 CFR Part 58 Appendix A, Section 4.1.3, Equations 3, 4, and 5. Bias of true NO2 measurements will be independently assessed by conducting an annual performance evaluation (PE) described in 40 CFR Part 58 Appendix A, Section 3.1.2. Additional PE assessments will be conducted minimally every 5 years by EPA as part of the National Performance Audit Program (NPAP) as described in 40 CFR Part 58 Appendix A, Section 2.4. Bias of meteorological measurements is controlled by ensuring instruments are appropriately calibrated prior to field deployment and by performing periodic comparison checks to a known calibrated instrument exposed to the same conditions (whether controlled or ambient) or to known reference conditions. Once calibrated, meteorological instrument calibration bias will be verified annually. Note that this calibration verification is separate from the annual instrument performance audit described in Section CI. 1.1.2. Bias assessment for meteorological instruments is described below: • Wind anemometers - bias is assessed for mechanical instruments by rotating the anemometer shaft at several known rotational speeds and verifying the instrument output is within the tolerance specified by the instrument manufacturer. The bias of sonic anemometers is determined by collocation with a calibrated reference anemometer. Measurement bias will be maintained to within ± 0.2 m/s or ± 5%, whichever is greater. • Wind vanes - bias is assessed by ensuring the orientation pin is set within specification to the compass azimuth of true north and that instrument outputs for several orientations around the 360° compass are within ± 3° of the true setting; this requires determining true north to within ±1° accuracy. The combined error in the system must be kept to < 5°. True north can be determined by referencing the current magnetic declination. The National Oceanic and Atmospheric Administration offers a current magnetic declination calculator at the following website: https://www.ngdc.noaa.gov/geomag-web/ • Temperature probes - bias is assessed by comparison to a NIST-traceably certified thermometer or thermistor. The calibration check is performed at three different temperatures spaced across the range of expected temperatures experienced at the site. The temperature probe is to be within ± 0.5°C from the certified reference standard at each comparison level. • Precipitation gauges - bias is assessed by adding a known volume of water with a volumetrically certified device (such as a graduated cylinder) and verifying the instrument is reporting to within ± 10% of the known added volume. • Hygrometers - bias is assessed by comparison of the hygrometer to a reference standard at minimally two (typically four) different humidity levels covering a typical range of 35 to 90% RH. The dew point provided by the hygrometer must be within ± 1.5°C of the reference standard for RH > 40% and within ± 5% for RH < 40%. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 50 of 145 • Pyranometers - bias is assessed by comparison of the pyranometer to a NIST-traceably certified pyranometer for one diurnal cycle and must be within ± 5% of the reference standard for both solar radiation and UV radiation. • Barometers - bias is assessed by comparison of the barometer to a NIST-traceably certified barometer or pressure transducer over the course of several consecutive hours. The average measurements from the barometer over the comparison period must be within ± 3 hPa of the reference standard. • Ceilometers - bias is assessed by qualitative review of the derived data products through visual plots and local user knowledge of expected meteorological conditions and expected ranges in MLH/PBLH. Such an assessment can quickly identify functional issues with the ceilometer, which would most likely be visible in unusual variations in the aerosol backscatter profile plots. Acceptably low bias in the measurements from each of the individual meteorological instruments will be verified as described in Section B5.1.4. Note that instrument bias will be additionally verified independently through assessments (instrument performance audits - IP As) such as those described in Section CI. 1.1. These assessments do not replace the routine bias checks described in this section. A 7.3.5 Sensitivity Sensitivity must be established for each of the chemical measurements (speciated VOCs and carbonyls) by experimentally determining the method detection limit (MDL). For true NO2, there are limitations in the ability to properly generate suitable concentration standards for monitoring agencies to experimentally determine the MDL; however, monitoring agencies are encouraged to experimentally determine the MDL when feasible. The MDL for speciated VOCs1 and carbonyls is to be established annually by analysis of replicate standard samples prepared at a concentration approximately two- to five-fold the expected MDL. MDLs should be determined for each measurement method as described in Revision 3 of the PAMS TAD in Sections 4.3, 5.6, and 6.2.9 for speciated VOCs, carbonyls, and true NO2, respectively; the procedure is described briefly below. MDLs are determined according to the Method Update Rule revision of the MDL procedure described in 40 CFR Part 136 Appendix B by analyzing a series of low concentration standard sample replicates and a series of blanks. The spiked samples and blanks are prepared and analyzed over the course of three or more different dates and an average and standard deviation are calculated from the resulting spike data and blank data. The calculated spike standard deviation is multiplied by an appropriate Student's T statistic according to the number of spiked samples to calculate an MDL for the spikes, MDLsp. The blank standard deviation is multiplied by an appropriate Student's T statistic according to the number of blanks and added to the average blank value to calculate an MDL for the blanks, MDLb. The higher of the MDLsp and MDLb is reported for the site MDL for the target analyte. Determined MDLs will be determined annually prior to PAMS season and may not exceed those listed in Table A7-1. Note that for 1 It is understood that CAS auto-GC users will not be able to calculate MDL values without an external calibration system, and should instead default to the manufacturer MDL of 0.5 ppbC. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page51of 145 sites that operate year-round or extended monitoring seasons, the MDL will be determined each year and applied to the subsequent measurements. Meteorological instruments will meet the resolution specifications listed in Table A7-1. Sensitivity for meteorology instrument measurements is fundamentally different than for chemical measurement instruments for which the lowest concentration differentiable from background is useful. For ambient meteorology measurements, sensitivity is better understood as resolution, or the ability to differentiate between two similar measurements, since the conditions to be quantified are not challenging to detect in the same way that low concentrations of a target chemical analyte are. For example, the ability to discern between temperatures of 24.2°C and 24.6°C is important; however, it is not important to be able to measure the lowest temperature possible since such is not a concern for ambient monitoring. A8 Special Training/Certifications Individuals conducting ambient measurements resulting in data generation (site operators, laboratory analysts), data verification and validation, and audits/assessments must possess the skills and education or experience to perform activities for which they are responsible. Specific requirements are described in the following sections. Management, by way of signature approval of training records, or equivalent, must verify that staff are competent to conduct all such activities. Monitoring agencies will detail in this QAPP the requirements and certifications for staff carrying out the duties described in Section A6.2. Individuals operating instruments, performing data transformations, and conducting oversight (such as quality assurance and management personnel) must minimally have read and documented attestation of compliance with the appropriate quality system documents. Training can consist of attendance at seminars, courses provided by instrument vendors, online training courses, training videos, and time spent working with instruments with the intent to become familiar and learn the instruments and associated software. Monitoring agency staff must comply with all applicable quality system requirements and will attest in their training records that they have read and will comply with pertinent quality systems documents, such as the monitoring agency PAMS QAPP and SOPs describing the duties for which they are responsible (refer to Section A9). As PAMS monitoring is not typically conducted year-round, site operations staff should dedicate time during the non-sampling season prior to PAMS season to refamiliarize themselves with the pertinent procedures and operation of instruments and equipment. Staff will review and, as necessary, revise quality systems documents, perform maintenance on equipment, seek training to maintain skills and proficiency, and must demonstrate continuing proficiency to execute the activities for which they are responsible. A8.1 Site Operator Training Site operators require special training to calibrate, operate, maintain, and troubleshoot instruments and support equipment needed to make PAMS measurements. Each site operator will possess the appropriate skills and education to perform their assigned tasks. At the discretion of the monitoring agencies, instrument vendors may train site operators on how to set up, calibrate, and operate auto-GCs, carbonyls samplers, and ceilometers during installation. Site operators will receive training materials and will attend training sessions and online training ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 52 of 145 webinars provided by instrument vendors, EPA, and/or experts. Any such training will be documented (such as program completion certificates, course attendance records, etc.) and maintained in the staff training records. Management will document their approval of the staff member's competency to perform their assigned tasks as part of an IDOC process. The IDOC must be completed before data collection activities may begin. A member of management (supervisor or similar) and/or QA unit will observe the site operator performing the procedures as described in the applicable SOP as part of the approval process. Annually thereafter, and before the beginning of PAMS season, a member of management and/or a QA staff person will observe site operators performing the procedures to complete a CDOC. An example training form is included in Appendix D. Calibration, operation, and maintenance for the various instruments require expertise gained through training and practice. The operation of the auto-GC and associated equipment is complex and requires an operator familiar with the fundamentals of gas chromatography and a thorough understanding of the instrument systems to operate, maintain, and troubleshoot the auto-GC. Staff will more quickly adapt to the intricacies of the auto-GC if they have prior experience operating GC systems, generating and evaluating chromatographic data, and working with VOCs. Auto-GC operators are encouraged to spend time prior to PAMS season with the instrument and chromatography data system (CDS) to become familiar with the general operation, calibration procedures, data outputs, and data handling. The level of training required for conducting carbonyls sampling and operating ceilometers is less rigorous than for auto-GC operation. Site operators will need to be familiar with the instrument operation including troubleshooting, software menu navigation, data retrieval, maintenance, and calibration routines. Operation of other meteorological instruments requires site technicians to be familiar with instrument operation, maintenance, and typical data outputs. Meteorological instruments require little intervention aside from regular inspection for proper operation and lack of interferences (e.g., presence of bird or insect nests) and occasional maintenance for cleaning or alignment. Maintenance requirements are listed in Table B6-1. Once site operators are trained and approved by management to perform their assigned tasks, they may train other staff members to perform similar tasks. Training new site operators will involve a three-step process consisting of: 1. The trainee observing a trained staff member performing the task, 2. The trainee performing the task under the supervision and assistance of the trained staff member, and 3. The trainee performing the task independently under observation of the trained staff member. As the PAMS Required Site network matures and evolves, procedures and equipment are expected to be updated and refined. Site operators will seek opportunities for continuing education and refinement of their skills to maintain competency in their assigned tasks. EPA will conduct monthly calls and/or webinars in prior to and including the PAMS 2021 season with PAMS Required Site network monitoring agencies during which training on technical issues and questions may be covered and individuals may pose questions to the group and seek assistance in instrument start up, shakedown, and troubleshooting. These training calls and/or webinars may ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 53 of 145 be continued in out years following implementation based on training needs indicated by the PAMS Required Site workgroup. A8.2 Auditor Training Monitoring agency quality assurance staff performing assessments (described in Section C) will not need to be proficient in operating PAMS instruments; however, will be familiar with the equipment and procedures employed to generate measurement data and with software and procedures with which data are reviewed, verified, and validated. Auditors will read and understand the quality system documents, minimally consisting of the monitoring agency PAMS QAPP and SOPs governing the processes to be assessed, and will complete written attestation signifying compliance with the quality system (an example form is provided in Appendix D). EPA intends to provide training materials, audit checklists, and training sessions for auditors prior to the 2021 implementation. Auditors will attend minimally one training session for PAMS auditing, subject to training session availability. Staff performing audits need not be intimately familiar with the operations of the instruments and software functions for generating, evaluating, and validating measurement data; however, such staff must be able to follow the described procedures and determine whether the activities as carried out comply with the established procedures described in the QS documents. Auditors will maintain documentation for attendance of training sessions (e.g., training classes, webinars, vendor training) and for materials reviewed (e.g., audit checklists, instrument manuals, and training videos). EPA expects to develop checklists for conducting TSAs of the PAMS sites and ASLs. These checklists in concert with TSA training sessions (that EPA is expected to conduct) will be a resource for auditors to build confidence in conducting PAMS TSAs, IP As, and ADQs. A8.3 Analytical Support Laboratory Analyst Training Once the ASL staff member has read the relevant QAPP and SOPs, and documented the completion and intention of compliance with them, the staff member must demonstrate proficiency prior to conducting analyses to generate PAMS program data. Individuals conducting laboratory extraction and analysis for carbonyls will have demonstrated proficiency by conducting an IDOC prior to performing the applicable laboratory activities. The IDOC will consist of preparing a set of at least four LCSs and performing the extraction, calibration, and analysis procedures under observation of a member of QA staff, management (direct supervisor, or similar), or other trained analyst familiar with the procedure. The observer will ensure that the procedures were performed properly and review the analysis results to ensure that each LCS meets spike recovery acceptance criteria (±15% of nominal). The observer will document the acceptable performance and laboratory management will approve the analyst to independently perform the analysis by approval signature on the IDOC (checklist, approval form, or similar). Once the IDOC is completed, the analyst will demonstrate continued proficiency with the method on an annual basis by performing a CDOC. The CDOC will be met by the analyst in one of three ways: achieving recovery within the method bias specification (±15% of nominal) for analysis of an LCS (spiked cartridge) whose concentration of target analytes is blind to the analyst; acceptable performance on all target analytes for a PT sample; or achieving recovery within method bias specification (±15% of nominal) for all target analytes on four consecutive LCSs. Laboratory management will approve the analyst CDOC by approval signature. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 54 of 145 A9 Documentation and Records The monitoring agency will establish and maintain document control procedures for the timely preparation, review, revision, approval, issuance, use, retirement, and archival of documents and records. The categories and types of records and documents that are applicable to the PAMS Required Site Program are presented in Table A9-1. NOTE: Monitoring agencies can use this information if applicable but will add and/or reference their specific document control policies and procedures in this section. Documentation and records generated and maintained include: 1. Monitoring agency PAMS QAPP 2. PAMSSOPs 3. Sample collection records in electronic and written format 4. Logbooks and data sheets in electronic and written format 5. Training records 6. Instrument and equipment calibration information 7. Quality assurance documentation (for example, outcomes of TSAs, IP As, and ADQs; and corrective action plans and reports) in electronic and written format 8. Documentation that supports data review, validation, and certification activities. Recorded data, whether hand recorded in ink on paper or through electronic entry or captured through a computer system, will be maintained such that the activities can be reconstructed. The monitoring agency will have an SOP, combination of SOPs, or similar controlled document that describe how to execute routine procedures, including, but not limited to, instrument operation, maintenance, sample collection, and analysis for each of the PAMS measurement methods, data verification/validation/reporting, corrective action, training, and data management. As applicable, each SOP will include information on equipment and instruments required, calibration, quality control activities and acceptance criteria, calculations, and typical corrective actions for routine nonconformances. Where activities involve a potential physical hazard, safety precautions will be addressed. Table A9-1. Pertinent Documents and Records for PAMS Required Site(s) Category Record/Document Type Management and Organization Personnel qualifications and training Quality management plan Document control policy/procedure Records retention and archival policies Site Information Site characterization file Site maps/photographs Annual siting re-evaluation ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 55 of 145 Category Record/Document Type Environmental Data Operations (Field and Lab) QA Project Plan(s) (QAPPs) Standard operating procedures (SOPs) IDOC and CDOC records Field and laboratory notebooks Sample handling and management, incl. holding time/storage/number of samples to be collected, etc. Instrument inspection/maintenance records Raw Data Original data (routine and QC) Sample collection forms Chain of custody forms Electronic instrument data (raw, processed, and reprocessed) Certificates of analysis for standards materials Calibration certificates for transfer standards Original observations as recorded in field and laboratory notebooks Instrument calibrations Data Management Validation of data collection, transformation, and reduction algorithms Data management plans/flowcharts Transformed and reduced data Data review, verification, and validation documentation Data Reporting AQS data submission summary reports AQS data verification reports Quality Assurance Control charts Calibration data, MDL/IDL data etc. Audit reports for: IPAs, TSAs, ADQs Corrective action reports and supporting documentation Network reviews The monitoring agency will maintain a system (such as a controlled electronic document in an access-controlled network folder, internal website, or similar) that will list the most current version of quality system documentation containing the information given in Table A9-1. Superseded versions of controlled QS documents must be inaccessible such that only the most up-to-date procedures are performed. All previous versions of QS documents will be archived and maintained to ensure that measurement data are traceable to the policies and procedures in place at the time the data were generated, transformed or reduced, and reported. As the PAMS Required Site Network matures, the national QS documents will require revision to accommodate lessons learned and best practices. Revisions to the national QS documents will be handled in a manner that ensures only current approved procedures are available. In order to ensure that PAMS Required Site monitoring agency and EPA Regional staff are aware of the changes if a revision to the document cannot be completed and approved in a timely manner, a quality bulletin (refer to Appendix B) or similar memorandum will be distributed to the PAMS Required Site stakeholders as described in Section A1.2 to announce the changes and indicate when the changes are effective. When revisions to the national PAMS Required Site guidance and QS documents are announced, monitoring agencies will revise their QS documents accordingly, where applicable. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 56 of 145 A9.1 Recording of Data Activities conducted to generate reported measurements will be documented in sufficient detail such that the measurements reported to AQS are traceable (i.e., an independent assessor can trace a reported value back through collection of the data, transformation of the data, and the certified standards used to calibrate the instruments). Instrument operators, data validators, and QA personnel will record data within bound logbooks, on dedicated forms, or within electronic logs, as appropriate per the monitoring agency document control program. Monitoring agencies will include the document control program details here or include a reference to their location. A9.1.1 Paper Records Documentation requirements for the PAMS Required Site network will follow general good scientific data recording practices. Observations will be recorded in sufficient detail to reconstruct the activities and such that original data records are maintained and not obliterated or erased when corrections or changes are made. Measurements, observations, and activities will be recorded promptly in indelible ink and will be attributable to the individual making the entry by signature or initials and include the date the entry was made. Corrections must be by single line strikeout and must be dated and initialed. Bound logbooks with consecutively numbered pages or forms specific to the intended use (e.g., chain of custody form, field sample collection form, flow verification form, etc.) will be utilized to ensure the requisite information is captured and recorded. Such forms will be controlled documents. A9.1.2 Electronic Records Original raw data acquired by electronic systems (e.g., instrument acquired raw area counts for an auto-GC sample collection and analysis), data transformed or reduced within electronic systems (e.g., adjusting integration parameters for carbonyls analysis by HPLC, or data reduced within an electronic spreadsheet), and data recorded within electronic logbooks (such as is available in some data acquisition systems) will be maintained so activities may be reconstructed and calculations or transformations independently verified.9 Data recorded, transformed, or reduced in electronic systems will be attributable to the individual recording or evaluating the data and will indicate the date on which the activity was performed (and recorded, if different). If so equipped, audit trails will be enabled on software systems in order to ensure modifications to electronic records are recorded and that the original data are not overwritten. A9.2 Chain-of-Custody Records Samples collected for analysis that are packaged and transported to another location (carbonyls samples) will be accompanied by a chain-of-custody (COC) form that documents how such media are handled and tracks the integrity of the collection media through the various stages of transportation and receipt. COC procedures will be described in SOPs specific to the media type and the approved COC form will be a controlled document within the monitoring agency or laboratory document control system. Completed COC forms (or a copy thereof) will be retained by the laboratory as part of the official analytical record. COC procedures and requirements are detailed in Section B3.1.1. An example COC form (specific to PAMS carbonyls samples) is included in Appendix C. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 57 of 145 A9.3 QA/QC Records In addition to documenting routine operations, QA and QC activities must also be appropriately documented. Such QA/QC activities include: • Instrument maintenance, calibration, and calibration verification • Standards certification, recertification, or calibration • IP As • TSAs • ADQs • PEs • Supplies and equipment acceptance testing • Corrective actions • Data verification and validation The outcomes of these QA/QC-related activities must be recorded on hard copy forms, in electronic spreadsheets, electronic pdfs, in data management software systems, or by another appropriate means as defined in the monitoring agency-controlled document (e.g., QMP, QAPP, or SOP) governing the activity. Documentation methods include spreadsheets, worksheets, and data management systems, whether electronic or hard copy. Records for some of the QA/QC activities described above may only be available as hard copies. Where possible, these hard copy records will be scanned so that electronic versions can be filed and maintained with associated electronic air monitoring records. A9.4 Records Archival and Retention Records described in Sections A9.1 through A9.3 will be retained minimally for three years as per the statute of limitations codified in 2 CFR 200.333 and further clarified in Section 5.0 of the EPA QA Handbook.10 This statute states that records will be maintained for a minimum of three years from the date the grantee submits the final expenditure report unless otherwise noted or if the records involve a legal action. Monitoring agencies may prescribe more stringent records retention schedules provided they minimally meet the requirements in 2 CFR 200.333. PAMS Required Site Network QAPPs and supporting SOPs will be archived for minimally 10 years following the date that they are superseded. Electronic data such as databases, raw and processed electronic instrument data, electronic logbooks, etc., will be backed up minimally monthly to a physically separate storage device (separate hard drive, server, or similar). Archived electronic data will be stored in a manner such that they are protected from inadvertent alteration (e.g., password protected, access limited). Once archived, archived data are reviewed or tested minimally annually to ensure complete records are maintained and data have not been corrupted. An individual or individuals will be assigned responsibility for records archival, and the person or persons will be listed here. A9.5 Sample Retention The PAMS measurement methods are continuous and do not involve the collection of samples on to discrete media except for carbonyls. Therefore, sample retention applies only to carbonyls samples. Once carbonyls samples are extracted, the spent cartridge is no longer useful and can be ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 58 of 145 discarded. To afford reanalysis in the event there are problems with the analysis, sample extracts will be maintained in refrigerated storage until the analysis data are validated and approved or the 30-day extract holding time has been exceeded. Expired extracts are of little value; however, in the event expired extracts are analyzed, results reported from such expired extracts require qualification as "QX" when reported to AQS. Extracts will not be archived and will be disposed of properly according to hazardous waste procedures established by the laboratory. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 59 of 145 B DATA GENERATION AND ACQUISITION B1 Sampling Process Design (Experimental Design) The objective of the PAMS experimental design is to provide an air quality database for use in ozone prediction model evaluation and refinement. A secondary objective is to characterize ozone precursor concentrations and temporal patterns and associated meteorological conditions to assist state and local air pollution control agencies in evaluating, tracking the progress of, and if necessary, refining control strategies for attaining the ozone NAAQS. The rationale and description for the sampling design of the approximately 40 Required PAMS sites can be found in Section 1 of the PAMS Required Site Quality Assurance Implementation Plan (QAIP) available at the following link on AMTIC: https://www.epa. gov/ sites/default/files/2019- 11/documents/pams monitoring network and emp plan guidance.pdf The QAIP describes procedures approved by EPA OAQPS and Regions for applying for waivers. Waivers, if applicable to the monitoring agency, will be described in the monitoring agency QAPP and approved by the Region. An example monitoring agency IP including an example waiver is included in Appendix F. The following parameters will be measured at PAMS Required Sites. This QAPP describes the QS for those parameters in bold: • carbonyls • meteorological parameters: • ambient temperature • vector-averaged wind direction • vector-averaged wind speed • atmospheric pressure • relative humidity • precipitation • mixing layer height • solar radiation • UV radiation • speciated VOCs • true NO2 (note that this parameter may be eliminated from this QAPP if QA requirements are described in another QAPP) • NO/NOy • ozone NO/NOy and ozone are described simply for convenience; however, the QS for these criteria pollutant gases is covered under the appropriate monitoring agency QAPP which details gaseous criteria pollutant monitoring for the NCore network. The submittal and approval dates of the appropriate QAPP can be found in AQS. The approved QAPPs are to be maintained by the monitoring agency and a copy is to be kept on file at the EPA Regional office. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 60 of 145 Bl.l Sample Collection Schedule Sampling at PAMS Required Sites will be conducted June 1 through August 31 of each year, at a minimum. Monitoring agencies may elect to extend monitoring for PAMS parameters to begin before June 1 and end later than August 31 and will detail the monitoring period in Section A7.3.1.1 Parameters will be measured according to the schedule shown in below in Table Bl-1. Continuous instrument measurements (meteorology, speciated VOCs, O3, trueNCh, and NO/NOy) will operate continually to measure ambient conditions except during QC checks or maintenance. Note that meteorology instruments do not typically require ongoing daily QC checks. However, for the continuous chemical measurement methods, automated routine QC checks will be performed during the overnight hours and should rotate between specific times to ensure that there will be a representative ambient measurement for each of the daily 24 one-hour periods across all days of the week. For example, the nightly auto-GC CCV and blank require two hours to perform. If always performed from 01:00 to 03:00, there will not be representative ambient data for that two-hour period. An example rotation schedule would start the QC checks on Monday at 23:00, Tuesday at 00:00, Wednesday at 01:00 and so on. An example schedule is described in Section 4.6 of Revision 3 of the PAMS TAD and in the national auto-GC SOPs. Table Bl-1. PAMS Required Site Sampling Schedule by Parameter Parameter Sampling Duration and Frequency Value Reported Ozone a Continuously, daily Hourly average True NO2 Continuously, daily Hourly average NO/NOv a Continuously, daily Hourly average Speciated VOCs by auto-GC Hourly 40-minute sample, daily Hourly average Carbonyls (TO-11A) 3 sequential 8-hour samples on a l-in-3 days schedule 8-hour average Formaldehyde (Continuous) b Continuously, daily Hourly average Meteorological Parameters Continuously, daily Hourly average a Monitoring for ozone and NO/NOy are not covered in this QAPP. Please refer to the monitoring agency criteria pollutant QAPP for associated requirements. b Continuous formaldehyde monitoring with hourly average concentration reporting can be substituted for the carbonyl sequential collection of three 8-hour samples every 3rd day. Note that several manufacturers were developing continuous formaldehyde monitoring instruments at the time of publication of this QAPP. The time reported for the sample collection is to be the local standard time at the start of sample collection or the start of the averaged hour, not adjusted for daylight savings time (DST). Hourly averaging periods will include the beginning of the hour through the beginning of the following hour. For example, the hourly average represented for 9:00 a.m. covers 09:00:00 through 09:59:59. B 1.1.1 Carbonyls by TO-11A Note: For the purposes of this OAPP, it is assumed that PAMS Required Sites will perform time- integrated sampling for the measurement of carbonyls and will not perform near-real time continuous monitoring. Instruments capable of continuous measurements are not yet commercially available for routine monitoring. Further, OA criteria have not been established ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 61 of 145 for these instruments for use at PAMS Required Sites. EPA will develop OA OC for continuous formaldehyde monitors once such are available and have demonstrated appropriate comparability with Compendium Method TO-11A for formaldehyde measurements. Carbonyls samples will be collected as three sequential 8-hour samples every third day per the national sampling calendar available at the following link on AMTIC: https://www.epa.gov/amtic/sampling-schedule-calendar These primary sequential carbonyls samples will be collected according to the schedule shown in Table B1-2: Table Bl-2. Carbonyls Sampling Schedule Sequential Sample Collection Start Time (local standard time) Collection End Time (local standard time) A 04:00 12:00 (noon) B 12:00 (noon) 20:00 C 20:00 04:00 (the following day) This schedule aims to characterize the morning commute in sample A, the evening commute in sample B, and most of the overnight period in sample C, and will allow for the shifting of the commuting periods due to DST at sites where DST is observed. Each 8-hour sample will be collected for 8 hours ± 20 minutes and must begin and end within fifteen minutes of the designated sampling start or stop time. In cases where samples and/or sample results are invalidated, a replacement primary carbonyls sample set (three 8-hour samples) will be collected as described per the make-up policy in Section A7.3.2. Target carbonyls analytes are those identified in bold and noted as "carbonyls" in Table B2-1. All sites will measure and report formaldehyde and acetaldehyde (the two priority carbonyl compounds) and are encouraged to analyze for benzaldehyde and acetone (optional compounds). Note that the only exception to this is for sites operating continuous formaldehyde monitors reporting hourly averages; in such instances only formaldehyde must be measured. Bl.1.2 Speciated VOCs by Auto-GC To ensure that 75% of each sample is collected during the scheduled hour, at least 30 minutes of the 40-minute sampling period will occur during the hour. Sample collection should commence at the beginning of the hour but must commence no earlier than 10 minutes before the beginning of the hour and no later than 30 minutes after the beginning of the hour. For example, for sample collection of the 10:00 hour, sample collection must commence between 09:50 and 10:30 for the sample to be valid for the 10:00 hour. Sample collection beginning between 30 minutes and 50 minutes after the hour, between 10:30 and 10:50 in this example, must be invalidated. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 62 of 145 Target speciated VOCs analytes are listed in Table B2-1 and are classified as olefin, aromatic, paraffin, halogenated, monoterpene olefin, alkyne, or alcohol. The site will measure and report all compounds listed as priority compounds as well as total non-methane organic carbon (TNMOC). Sites are encouraged to analyze and report the compounds listed as optional. Sites will indicate in Table B2-1 which optional compounds will be measured and reported. Bl.1.3 Continuous Measurement Methods Data collection for continuous true NO2 and meteorological methods will include minimally 45 minutes of ambient data collection during the respective hour (75% of the hour) to be valid. Hours with fewer than 45 minutes of data collection will not be considered valid hours for data reporting. B 1.1.3.1 TrueN02 Ambient true NO2 will be measured continuously except when the NO2 analyzer is undergoing periodic QC checks (span/zero/precision checks), maintenance, and performance audits. During these periods, the instrument may be taken offline or data may be flagged to indicate that the measurements must not be reported as ambient measurement data. Bl.1.3.2 Meteorological Instruments Meteorological instruments will record ambient measurements continuously except when an instrument is undergoing QC checks, maintenance, or performance audits, for which the instrument will be taken offline or data may be flagged to indicate the measurements must not be reported as ambient measurement data. QC checks or performance audits for which the instrument is left in situ and continues to measure ambient conditions may be reported as valid data; however, if a probe's conditions are altered from the typical measurement configuration, the measurements will be invalidated. B1.2 Quality Control Measurements QC samples are collected and/or analyzed for the chemical measurement parameters (carbonyls, speciated VOCs, and true NO2), and may be positive controls or negative controls. Positive controls consist of a sample with a known amount of target analyte for challenging the measurement method (instrument), such as CCVs, span and precision checks, secondary source calibration verification (SSCV) standards, and LCS spikes. Negative controls challenge the measurement method to demonstrate the instrument response remains sufficiently low in the absence of the target analyte; negative controls include zero air blanks, solvent blanks, and field QC blank samples such as field blanks and trip blanks. Both positive and negative controls are prepared and analyzed to demonstrate that the measurement system remains in control on an ongoing basis; that is, that the measurement system is acceptably calibrated and that interferences and contamination are acceptably low. QC activities and associated acceptance criteria are detailed in Section B5 and in Tables B5-1, B5-2, B5-3, B5-4, and B5-5 for carbonyls field sample collection, speciated VOCs, true NO2, meteorology, and carbonyls laboratory analysis, respectively. SLT monitoring agencies and ASLs are encouraged to track QC sample performance with QC charting. Inspection of QC charts permits the identification of trends or drifts in performance ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 63 of 145 which can be addressed before an out-of-control condition occurs (before blanks are unacceptably high, before positive control recoveries are unacceptably low, etc.). B2 Sampling and Measurement Methods This section describes the sampling instruments, procedures for collecting samples, identifies the sampling methods and equipment including sample preservation requirements, and specific method and instrument performance requirements such as maximum allowable sample pickup times for carbonyl cartridges. Also described are actions to take when a failure in the sampling or measurement system occurs, who is responsible for corrective action, and how corrective action will be documented. The monitoring agency will provide a list of makes and models for the measurement parameters listed in Section Bl. This list can be included here or included by reference (such as an annual network plan). NOTE: This OAPP will refer to national SOPs developedfor the PAMS Required Site Network. Monitoring agencies will follow these reference SOPs and or specify and submit the SOP(s) they plan to use for the program daring the OAPP approval process. Monitoring agencies will detail the SOPs the agency and ASL will follow within this OAPP, either within the body of the OAPP or within a reference document or an appendix to this OAPP. B2.1 Chemical Parameters This section describes ambient air sample field collection methods and automated analyzers/methods used for conducting measurements of chemical parameters in the field (i.e., in situ). These parameters are listed below in Table B2-1. Three types of chemical parameters are listed in the table: criteria pollutant gases (italicized), carbonyls (bolded), and speciated VOCs to be measured by auto-GC (remaining unitalicized and unbolded). Ambient air samples will be collected through one or more inlet probes. The materials comprising, the siting of, and the configuration of the inlet probe will comply with 40 CFR Part 58 Appendix E and Section A7.3.1.2 of this QAPP to ensure the sampled atmosphere is representative of the ambient air in the geographic area intended to be represented by the site. Briefly, the inlet probe(s) will be constructed of borosilicate glass or polytetrafluoroethylene (PTFE) or perfluoroalkoxy (PFA) Teflon® for criteriaB>ollutantJases|For carbonyls and VOCs, inlet probe(s) will be of borosilicate glass or chromatographic grade stainless steel, or their equivalent. Fluorinated ethylene propylene (FEP) Teflon® is prohibited as a probe material in 40 CFR Part 58 Appendix E Section 9(b); however, PTFE and PFA Teflon are not specifically prohibited and are permitted for carbonyls sample collection. Monitoring agencies are strongly discouraged from employing Teflon® in their sampling inlet pathways for speciated VOCs. Additional guidance for inlet probe siting is included in Section 3.3.1.2 of Revision 3 of the PAMS TAD. The air monitoring instrument inlet can be connected to an inlet probe dedicated to the instrument or can be connected to an inlet manifold with connections for multiple instruments. Consideration will be given to the length of the sampling inlet pathway (including the manifold, if so equipped) and flow rate such that the sample residence time is kept to 20 seconds or less. Consideration will also be given to minimize intrusion of particulate matter (PM) and condensed water into the sampling inlet; one method for controlling the latter is by inverting the terminus of ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 64 of 145 the inlet and installing a rain shield (such as inverted funnel) on the inlet probe. Air monitors may be connected to any port on a manifold. Additional sample introduction and collection guidance is included in Revision 3 of the PAMS TAD, Sections 4.2.2.1, 5.7.2, and 6.2.8 for speciated VOCs, carbonyls and true NO2, respectively. Monitoring agencies will describe the inlet composition and configuration for these measurements within this QAPP or within the specific SOPs. B2.1.1 Carbonyls by TO-11A Sampling methods for the collection and analysis of carbonyl compounds by TO-11A are described in detail in the national PAMS SOPs. The target carbonyl compounds are shown in bold in Table B2-1. For this method, ambient air is pulled by a vacuum pump through an ozone denuder to remove ozone. The sampled air scrubbed of ozone is then passed through a silica gel sorbent cartridge impregnated with DNPH where carbonyls in the air stream react with DNPH to form hydrazone derivatives. These hydrazones are maintained within the sorbent bed until extraction at the analysis laboratory. Carbonyls sampling for the PAMS program involves collecting three consecutive 8-hour samples on a l-in-3-day schedule as described in Table Bl-2. It is preferable that samples are retrieved as soon as possible after the end of collection; however, cartridges must be retrieved within 72 hours of completion of the last of the three sequential samples. Samples must be stored and transported cold (< 4°C) and protected from light. B2.1.2 Speciated VOCs by Auto-GC Auto-GC systems will be used for the measurement of speciated VOCs. The auto-GC collects and preconcentrates VOCs from the sampled atmosphere and subsequently separates the VOCs for detection via a pair of flame ionization detectors (FIDs). Procedures for the setup, calibration, operation, maintenance, and shut-down of auto-GCs are described in the following national PAMS SOPs, which are intended to provide instruction for properly trained instrument operators: • SOP for the Analysis of PAMS VOCs in Ambient Air via the Consolidated Analytical Systems (CAS)/Chromatotec AirmOzone Auto-GC-FID • SOP for the Analysis of PAMS VOCs in Ambient Air via the Markes Unity-XR Thermal Desorber with Agilent 7890B Auto-GC-FID • SOP for the Analysis of PAMS VOCs in Ambient Air via the PerkinElmer TurboMatrix TD300 Thermal Desorber with Clarus 580 Auto-GC-FID Additional details on auto-GC sampling methods, including technical guidance regarding moisture management, are provided in Section 4.2.3 of Revision 3 of the PAMS TAD. Table B2-1. Priority and Optional PAMS Required Site Chemical Parameters Priority Chemical Parameters (Required)1 AQS Parameter Code Compound Class Optional Chemical Parameters AQS Parameter Code Compound Class 1,2,3-trimethylbenzene 45225 aromatic 1,3,5-trimethylbenzene 45207 aromatic 1,2,4-trimethylbenzene 45208 aromatic 1-pentene 43224 olefin 1-butene 43280 olefin 2,2-dimethylbutane 43244 paraffin ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 65 of 145 Priority Chemical Parameters (Required)1 AQS Parameter Code Compound Class Optional Chemical Parameters AQS Parameter Code Compound Class 2,2,4-trimethylpentane 43250 paraffin 2.3,4-trimethylpentane 43252 paraffin Acetaldehyde 43503 carbonyl 2,3-dimethylbutane 43284 paraffin Benzene 45201 aromatic 2,3-dimethylpentane 43291 paraffin eis-2-butene 43217 olefin 2,4-dimethylpentane 43247 paraffin ethane 43202 paraffin 2-methylheptane 43960 paraffin ethylbenzene 45203 aromatic 2-methylhexane 43263 paraffin ethylene 43203 olefin 2-methylpentane 43285 paraffin formaldehyde 43502 carbonyl 3-methylheptane 43253 paraffin isobutane 43214 paraffin 3-methylhexane 43249 paraffin isopentane 43221 paraffin 3-methylpentane 43230 paraffin isoprene 43243 olefin acetone 43551 carbonyl m&p-xylenes 45109 aromatic acetylene 43206 alkyne m-ethyltoluene 45212 aromatic cis-2-pentene 43227 olefin n-butane 43212 paraffin cyclohexane 43248 paraffin n-hexane 43231 paraffin cyclopentane 43242 paraffin n-pentane 43220 paraffin isopropylbenzene 45210 aromatic o-ethyltoluene 45211 aromatic m-diethlybenzene 45218 aromatic o-xylene 45204 aromatic methylcyclohexane 43261 paraffin p-ethyltoluene 45213 aromatic methylcyclopentane 43262 paraffin propane 43204 paraffin n-decane 43238 paraffin propylene 43205 olefin n-heptane 43232 paraffin styrene 45220 aromatic n-nonane 43235 paraffin toluene 45202 aromatic n-octane 43233 paraffin trans-2-butene 43216 olefin n-propylbenzene 45209 aromatic ozone 44201 criteria pollutant gas n-undecane 43954 paraffin true NO2 42602 criteria pollutant gas p-diethylbenzene 45219 aromatic total non-methane organic carbon 43102 total VOCs, non- methane trans-2-pentene 43226 Olefin a-pinene 43256 monoterpene olefin fS-pinene 43257 monoterpene olefin 1,3 butadiene 43218 olefin benz aldehyde 45501 carbonyl carbon tetrachloride 43804 halogenated ethanol 43302 alcohol tetrachloroethylene 43817 halogenated 1 Bold indicates a carbonyl and italics indicates a criteria pollutant gas. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 66 of 145 B2.1.3 True NO2 by CAPS or Photolytic Conversion to NO with Chemiluminescent Detection An FRM/FEM analyzer will be employed for measurement of true NO2 per the PAMS National SOP: • Standard Operating Procedure for the Analysis of True Nitrogen Dioxide (NO2) in Ambient Air for the Photochemical Assessment Monitoring Stations (PAMS) Network EPA has designated the following instrument methods as FEMs for NO2 analysis: ¦ FEM EQNA-0514-212 - Teledyne Advanced Pollution Instruments (API) Model T500U CAPS NO2 Analyzer ¦ FEM EQNA-1013-210 - Environnement S.A. AS32M CAPS N02 Analyzer ¦ FEM EQNA-0217-242 - Ecotech Serinus 60 CAPS N02 Analyzer ¦ FEM designation available from supplier - Aerodyne Research, Inc. CAPS NO2 Monitor ¦ FEM EQNA-0320-256 - Teledyne API Model N500 CAPS N02/N0x/N0 Analyzer ¦ FEM EQNA-0512-200 - Teledyne API Model T200UP Photolytic Conversion NO2 Analyzer The CAPS true NO2 analyzer ingests a sampled air parcel and using a specific wavelength of light, determines the concentration of NO2 in the air parcel relative to the loss of signal in the instrument optical cell. For photolytic conversion instruments, the instrument employs two channels, one channel that converts NO2 to NO at a precise wavelength of light efficient for converting NO2 to NO with few interferences, and one channel without conversion, and measures the concentration of NO2 by difference using a chemiluminescent detector. B2.2 Meteorology Meteorology measurements will include the parameters listed in Table B2-2. Table B2-2. Meteorological Parameters Parameter AQS Parameter Code Duration AQS Duration Code Example Reported Unit3 AQS Unit Code3 Ambient Temperature 62101 hourly average 1 °C 17 Relative Humidity 62201 hourly average 1 % relative humidity 19 Barometric Pressure 64101 hourly average 1 millibar (hPa) 16 Wind Speed 61103 hourly average 1 m/s 11 Wind Direction 61104 hourly average 1 degrees compass 14 Solar Radiation 63301 hourly average 1 Watt/m2 79 Ultraviolet Radiation 63302 hourly average 1 Watt/m2 79 Precipitation 65102 hourly average 1 mm 29 Mixing Layer Height 61301 hourly average 1 m 58 a Listed units are one of several standard units accepted by AQS for the given parameter. Monitoring agencies may report measurement data in any standard unit accepted by AQS. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 67 of 145 These measurement methods will meet the criteria specified in Table 0-1 of Quality Assurance Handbook for Air Pollution Measurement Systems. Volume IV - Meteorological Measurements (EPA-454/B-08-002) available at the following link: https://www.epa. gov/ sites/default/files/2021 - 04/documents/volume iv meteorological measurements.pdf Results will be measured continuously and reported as the hourly average. Mixing layer height is currently not covered in Table 0-1 of Quality Assurance Handbook for Air Pollution Measurement Systems. Volume IV - Meteorological Measurements (EPA-454/B-08-002). At the time of publishing this document, EPA is finalizing a QAPP for ceilometers and anticipates revising the meteorological measurements handbook soon. B3 Sample Handling and Custody Sample handling procedures apply to chemical parameter measurements and must be consistently followed to ensure reported concentrations meet the MQOs. Chemical analysis methods for the PAMS Required Site measurements are continuous with the exception of carbonyls by TO-11 A; therefore, custody requirements only apply to carbonyls sample collection, handling, and analysis. Sample custody procedures are required to avoid misplacement of samples or confusion of one sample with another, and to provide documentation to assist in identification and resolution of instances where sample identity or integrity is called into question. A sample is considered to be in custody if it is in one's actual physical possession or stored in a secured area restricted to authorized personnel. Monitoring agencies will specify the sample handling and custody policies and procedures in their individual QAPP or will include by reference. B3.1 Carbonyls by TO-11A New cartridges will be stored at < 4°C upon receipt. New Waters cartridges are typically shipped at ambient temperature and Supelco cartridges are typically shipped at sub-ambient temperatures. Both cartridge types are typically provided sealed individually in a foil pouch. To maintain cartridge integrity and limit potential contamination, the sealed foil cartridge storage pouch will not be opened until the cartridge is to be used in the field or laboratory. Moreover: • Cartridges should only be handled with gloved hands (chemicals from hand sanitizers, lotions, etc., can contaminate sample cartridges). • Markers containing volatile solvents (e.g., permanent markers such as Sharpie®) will not be used for marking on foil storage pouches. Ball-point pens or printed stick-on labels are preferred. • Cartridges will be labeled in such a manner to uniquely identify the cartridge, i.e., to permit the identification of the sampling date, time, and whether it is a primary sample or field QC sample (precision sample [such as collocated or duplicate], field blank, or trip blank). • Cartridge storage areas will be free of carbonyls. Climate-controlled storage units will not be used for storage of solvents or carbonyl-containing solutions or standards. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 68 of 145 Upon retrieval, each field-collected cartridge must be sealed in its individual foil pouch, and placed immediately in refrigerated storage (e.g., refrigerator onsite or cooler with ice packs). Collection details will be documented appropriately on the sample collection form (whether hard copy or electronic) and sample storage information will be recorded on the COC form or similar form or database (such as a laboratory information management system [LIMS]). To ensure that samples arrive at the laboratory under refrigeration, samples will be hand-carried or shipped by overnight courier/shipper. Experience has shown that extended shipping times will result in samples arriving at the laboratory at elevated temperatures (> 4°C). B3.1.1 Chain of Custody Blank cartridge media may originate at the analysis laboratory; therefore, COC procedures may be prescribed by the ASL. Regardless of the origin of the new cartridge media, each cartridge, whether an ambient sample or field QC sample (such as a trip blank or field blank) will be listed on a COC form documenting the transfer of the sample cartridges from their origin, through collection, and transport to and receipt by the analysis laboratory. The following information must minimally be recorded on the COC form (an example form is included in Appendix C): • Origin of cartridges (e.g., analysis laboratory or field office) • Transfer of cartridges between individuals - dates, times, and signatures of individuals relinquishing and receiving cartridges o Relinquishing cartridges to site operator (either by handoff or shipment by courier) o Receipt of cartridges by site operator o Relinquishing of sampled cartridges by site operator following retrieval (for handoff to analysis laboratory or shipment with courier) Note: Shipping couriers are not expected to sign COC forms. The individual relinquishing the samples to the shipper/courier will indicate relinquishment to the shipper/courier on the COC form. Custody is presumed to be with the courier until received at the laboratory. o Receipt of field-collected cartridges by analysis laboratory • Unique identifier(s) for each sample, sample collection date(s), and site(s) location information • Storage of cartridges at each point during transfer between individuals, including during shipment o Storage of field-collected cartridges at the monitoring site, if applicable (e.g., stored at < 4°C in onsite refrigerator, etc.) o Shipping conditions (e.g., on ice packs) and associated information for tracking or evaluating the shipping conditions - such as thermometers placed in a shipping cooler o Upon receipt at the laboratory - document thermometer used for measuring temperature as received and location for storage within laboratory (e.g., uniquely identified refrigerator) ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 69 of 145 Note that the convention for recording custody information for the samples can include recording transfers and storage on the field collection data sheet; however, it may be more convenient to include a separate COC form for each shipment that encompasses all samples in the shipment. A separate dedicated COC form reduces the number of instances where staff transferring cartridge custody are required to sign (sample custodians need only sign one or two COC forms rather multiple field collection forms). Laboratory sample custodians, or designated individuals responsible for assuring sample custody, will ensure that sample custody documentation is complete. Site operators will be contacted, as appropriate, to complete missing information. COC documentation will be maintained in accordance with Section A9. B4 Analytical Methods The analytical methods to be employed for the PAMS Required Site Network covered by this QAPP include methods for the determination of carbonyls, speciated VOCs, and true NO2. B4.1 Carbonyls by TO-11A Samples collected for carbonyls analysis (refer to Section B2.1.2) will be extracted and analyzed per EPA Compendium Method TO-11A and will meet the performance specifications listed in Table B5-5. This method is described in the national SOPs for the collection of analysis of carbonyls for the PAMS Required Site Network, which describe the procedures for solvent extraction of derivatized carbonyl-hydrazones collected on the DNPH cartridge samples, analysis of these extracts by HPLC or UHPLC with UV detection, and the necessary QC procedures. Ambient air and QC samples must be extracted for analysis within 14 days of collection. Extracts are then analyzed by HPLC or UHPLC with UV at 360 nanometers (nm) within 30 days of extraction and the carbonyl concentrations in the ambient air sample calculated from the measured concentrations in the sample extracts and the volume of air sampled onto the cartridge. Alternative detectors (such as time-of-flight [TOF]) and alternative wavelengths (e.g., 365 nm) may be employed, if method performance criteria (listed in Table B5-5) are met. B4.2 Speciated VOCs by Auto-GC Auto-GC systems will be used for the analysis of VOCs. The auto-GC systems collect and preconcentrate VOCs from the ambient atmosphere and subsequently separate the VOCs for detection by FID. Procedures for the setup, calibration, operation, and shutdown of auto-GCs are described in PAMS Required Site SOPs listed in Section B2.1.2. Analysis of speciated VOCs by auto-GC is considered a continuous method, therefore there are no discrete samples collected on media which may be retained. Additional details on auto-GC sampling methods, including technical guidance regarding moisture management, are provided in Section 4.2.3 of Revision 3 of the PAMS TAD. B4.3 True NO2 by FEM True NO2 analyzers approved as FEMs will be employed for the analysis of true NO2. The analyzers continuously sample ambient air routed through an in-line particulate matter (PM) filte r; therefore no discrete samples are collected on media which may be retained. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 70 of 145 The analyzers are calibrated for NO2 response by providing the analyzer with a zero- concentration gas and an upscale concentration of NO2 of approximately 80% of the desire measurement range. A multi-point verification (MPV), which involves analysis of a ze: concentration point and four upscale standard NO2 concentrations, is needed before an instrument. desired zero tnd to establish "as-found" and "as-left" conditions of the Following minimally every 14 days thereafter, the analyzer is subject to a zero/span check to verify ongoing instrument calibration. See Table B5-3 for QC acceptance criteria B5 Quality Control QC is the overall system of technical activities that measures the performance of an ongoing process against established standards to verify that such performance meets the stated requirements established by the data user or stakeholder. In the case of the PAMS Required Site Network, QC activities ensure that the quality objectives and criteria for measurement data, as discussed in Section A7, are maintained so that the PAMS Required Site Program DQO can ultimately be met. QC checks and procedures will be performed at a frequency sufficient to ensure data of adequate quality are obtained while minimizing loss of data when nonconformances occur. B5.1 Quality Control for Field Activities QC for field activities relate to carbonyls sample collection, speciated VOC analysis, true NO2 analysis, and meteorological parameters. B5.1.1 Quality Control for Carbonyls Sample Collection Carbonyls sample collection QC includes the performance of quality checks on the sampling instrument to ensure the instrument is not imparting a positive bias (i.e., contaminating) to the collected samples, the instrument flow control is accurate, and the instrument clock is accurate. Carbonyl field QC samples include, as described in Table B5-1 and in the carbonyls sample collection SOP, field blanks and trip blanks, which characterize the level of contamination attributable to sample handling and transportation, and duplicate and/or collocated samples, which characterize the precision between samples collected from the same air mass. For flow controller calibration verification and clock accuracy, corrective action will be taken immediately when nonconformances are observed. When clock setting deviations are noted, the clock should be reset and the offset should be applied to the sample start and stop times. For example, if the carbonyls sampler clock shows 11:06 a.m. when the time is 10:59 a.m., the operator should reset the clock and subtract seven minutes from the sample start and stop times recorded in the sample collection records. For the positive bias challenge (as described in Section A7.3.4), compliance with acceptance criteria must be attained prior to deploying the sampling instrument for sample collection. A positive bias challenge is recommended if instrument contamination is suspected (such as would be indicated by poor precision for duplicate or collocated samples or if unusually elevated concentrations are reported). The need for follow up corrective action for field blank, trip blank, or collocated or duplicate sampling criteria failures will not be apparent until analysis results are completed. Root cause analysis will be performed as soon as possible for field QC sample nonconformances, and efficacy of corrective actions will be evaluated by collection of follow-up field QC samples. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 71 of 145 Table B5-1. Carbonyls Field Quality Control Parameters QC Parameter Detail Required Frequency Acceptance Criteria Recommended Corrective Action Positive Bias Challenge (zero air challenge) Collection of an 8- hour sample of humidified zero air to investigate contamination contributed by the sampler Prior to the beginning of every PAMS season following instrument maintenance (ozone denuder recharge/ replacement, particulate filter change, etc.) All target compounds <0.20 |ig/cartridge greater than co-collected reference sample for acetaldehyde and formaldehyde Repeat bias challenge following further cleaning which could include flushing with humidified zero air, replacement of flow path components, etc. Mass Flow Controller Calibration Establishment of the MFC slope and intercept by comparison to a flow transfer standard Annually (preferably at the beginning of each PAMS season) and when flow verification checks fail criteria Flow verification immediately following calibration must be within ±10% of flow transfer standard Recalibrate flow controller. If problem persists, investigate for leaks, blockage in flow path, etc. May require replacement of MFC or other instrument parts. Mass Flow Controller Calibration Verification Verify sampling flow of each channel at the sampling flow setting Minimally every 30 days during PAMS season Within ±10% of flow transfer standard Recalibrate flow controller and verify within proper specification. Qualify all previous samples since the last acceptable flow check or calibration as "W" and "LK" (reported concentration biased high for flow verification results biased low) or "LL" (reported concentration biased low for flow verification results biased high) as appropriate in AQS. Clock Accuracy Verify clock accuracy against a known accurate time standard Each sampling event Within ±5 minutes of the true reference time Reset clock to correct time. Apply offset to sample start/stop times. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 72 of 145 QC Parameter Detail Required Frequency Acceptance Criteria Recommended Corrective Action Field Blank Blank cartridge installed in a sampling channel for five to ten minutes Twice monthly (approximately every 14 days) during PAMS season Measured mass per cartridge (|ig/cartridge): - Acetaldehyde < 0.40 - Formaldehyde < 0.30 - Acetone < 0.75 - Sum of other compounds <7.0 Investigate sources of contamination in handling and transport. Qualify associated field collected samples as "FB" in AQS. Associated samples are those in the shipment with the field blank and since the most recent acceptable field blank. Trip Blank blank cartridge accompanying collected samples to and from the field site Not required, recommended monthly - monitoring agencies will specify intent and frequency for collecting trip blanks Measured mass per cartridge (|ig/cartridge): - Acetaldehyde <0.10 - Formaldehyde < 0.15 - Acetone < 0.30 - Other individual compounds <0.10 Investigate sources of contamination in handling and transport. Qualify associated field collected samples as "TB" in AQS. Associated samples are those in the shipment with the trip blank. Sample Retrieval samples are retrieved, capped, protected from light, and stored at < 4°C each sampling event within 72 hours of end of 3rd sequential sample (whose sampling is nominally completed at 4:00 a.m.) Qualify associated data as "HT" in AQS. Duplicate Sample Collection collection of a separate cartridge through a common inlet probe concurrently with a primary 8-hour sample Optional - 10% of primary sampling events - monitoring agencies will specify intent and frequency for collecting duplicate samples Relative percent difference < 20% for compounds >0.5 Hg/cart ridge Qualify both samples as estimated "QX" in AQS. Collocated Sample Collection collection of a separate cartridge through an independent inlet probe concurrently with a primary 8- hour sample Optional - 10% of primary sampling events - monitoring agencies will specify intent and frequency for collecting collocated samples Relative percent difference < 20% for compounds >0.5 Hg/cart ridge Qualify both samples as estimated "QX" in AQS. B5.1.2 Quality Control for Speciated VOCs Collection and Analysis QC processes for speciated VOC collection and analysis, as described in Table B5-2 and replicated in the speciated VOCs measurement SOP, are designed to demonstrate that the instrument is sufficiently free of contamination and interferences; to establish the carbon response calibration of the two FIDs within the instrument; to independently verify the calibration for compounds representing the molecular weight range of the PAMS priority VOCs; and to confirm that the ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 73 of 145 instalment's performance is acceptable on an ongoing basis. System performance QC checks involve verifying the bias criteria are met for representative compounds across the molecular weight range and ensuring that instrument contamination and carryover are sufficiently low. PAMS VOCs in ambient air are typically measured at concentrations less than 2 ppbC, therefore, it is important for the calibration to include a low concentration level (approximately 1 ppbC) to properly characterize the instrument response at such low concentration. The next highest concentration will be approximately 5 ppbC. While approximately 25 ppbC should be sufficient to capture the majority of measured PAMS VOCs, agencies have latitude to select the concentration of the high calibration standard. Table B5-2. Speciated VOCs Field Quality Control Parameters QC Description Required Acceptance Recommended Corrective Parameter Frequency Criteria Action Initial Multi-point Initially at the Linear regression Prepare new calibration. It may be calibration calibration of the beginning of with non-zero necessary to investigate for system (ICAL) auto-GC with PAMS season. y-intercept must contamination or interferences minimally a after maintenance show r2 of > 0.99. resulting in suppression or representative (such that response Also enhancement of analytes. System hydrocarbon for each is impacted). intercept/slope leaks and trap degradation may GC column-FID following failing < l.OppbC, impede a proper calibration as well combination (e.g. continuing whichever is lower. as carryover from samples or propane and calibration checks. RSD of determined standards. Improperly conditioned benzene). Minimum and at the RFs must be <10%. traps may contribute of three conclusion of Each standard level chromatographic artifacts. PAMS concentrations monitoring each evaluated against data must not be reported unless covering PAMS season. the calibration curve calibration meets criteria. approximately 1.0 to Agencies may must be within 20% 25 ppbC. At their analyze the of the nominal discretion, agencies primary calibration concentration. If all may use other high- standard weekly as of the above criteria level concentrations an additional check (r2. (e.g., 50 or 80 to monitor system y-intercept/slope, ppbC).3 performance - not required. RF RSD, and standard ±20% of nominal) are met, the calibration may utilize the average RF. Measurements exceeding the calibration range will be qualified as "EH". System Analysis of Prior to ICAL, and All target VOCs Analyze another blank, if possible. Blank (SB) humidified zero airb every 24 ± 4 hours must be < the to investigate potential carryover to ensure the system of operation determined MDL or from high concentration sample. is sufficiently clean following or 0.5 ppbC, whichever Investigate system for for continued preceding the CCV is lower. contamination. Unless technical analysis. (preference is to follow the CCV to ensure absence of carryover before justification is provided to explain nonconformance, qualify as "LB" in AQS all samples for affected compounds since the last passing ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 74 of 145 QC Parameter Description Required Frequency Acceptance Criteria Recommended Corrective Action analyzing ambient samples). SB. Second Source Calibration Verification (SSCV) Analysis of a known standard prepared from a stock gas including target analytes across the molecular weight range from a supplier different from the stock gas (primary standard) for preparing the ICAL. This check independently verifies the quality of the ICAL for compounds across the molecular weight range. Immediately following ICAL and minimally weekly thereafter - may serve as the CCV.C All primary calibration target VOCs must recover within ±30% of the expected nominal concentration. Analysis cannot commence if propane (or butane) or benzene (or toluene) fail in the SSCV immediately following the ICAL. Investigate for discrepancy between ICAL and SSCV. Investigate chromatogram for retention time shifts which may result in peak misidentification. Investigate for instrument contamination resulting in co-eluting peaks. Investigate for system leaks or trap malfunction resulting in low recovery. Unless technical justification is provided to explain nonconformance, minimally qualify as "QX" and potentially invalidate as "AS" samples for affected compounds since the last acceptable SSCV. Clock Accuracy Verify clock accuracy against a known accurate time standard Weekly, recommended to check each site visit Within ±5 minutes of the time standard Reset clock to correct time. Adjust data timestamp accordingly where possible. Ensure adjusted sampling start times are no earlier than 10 minutes before the hour and no later than 30 minutes after the hour. Invalidate sample hours that do not conform. Continuing Calibration Verification (CCV) Analysis of a known standard containing compounds representing the molecular weight range & prepared within the calibration curve to demonstrate the instrument calibration remains within tolerance. Can include multi-analyte calibration gas or single-analyte permeation tubes. Concentration of CCV should be approximately 2-5 ppbC for target analytes. Every 24 ± 4 hours of operation All target VOCs must recover within ±30% of the expected nominal concentration. Investigate chromatogram for retention time shifts which may result in peak misidentification. Investigate for instrument contamination resulting in co- eluting peaks. Investigate for system leaks or trap malfunction resulting in low recovery. Unless technical justification is provided to explain nonconformance, qualify as "QX" in AQS all samples for affected compounds since the most recent passing CCV. Invalidation as "AS" may be required at analyst discretion if compound recovery is exceptionally high or low. Retention Analysis of a 59- Minimally weekly All target VOCs Review previous week's ambient ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 75 of 145 QC Parameter Description Required Frequency Acceptance Criteria Recommended Corrective Action Time Standard (RTS) component blend of VOCs in the ~2 to 60 ppbC range to verify established retention time windows. must be within the established retention time windows. and QC check sample data to evaluate events resulting in retention time shift. May require reassigmnent or adjustment of retention time windows and reprocessing of data collected since the most recent CCV or RTS. Unless technical justification is provided to explain nonconformance, associated ambient sample data will be invalidated as "BH" for compounds whose identities cannot be confirmed. Precision check Replicate analysis of the CCV to evaluate the reproducibility of the analysis - replicates are analyzed sequentially (back to back). Weekly Absolute relative percent difference for each target VOC must be < 25% on a week- to-week basis. Investigate system for carryover, contamination, leaks, or suppression, as indicated by trends in compound behavior. Qualify ambient sample data for affected compounds since the last passing precision check as "QX" in AQS. a For CAS auto-GC users, it is suggested to use some combination of 4-, 5-, 7-, 9-, and 15-minute calibration gas injections to meet the three minimum concentrations and stay within the required 1-25 ppbC concentration level. Users will likely see the best results by performing blanks in between each calibration level. b CAS auto-GC users should not humidify zero air and calibration gas streams, per manufacturer specification. 0 If using the SSCV source for CCV, only review CCV analytes. While FID response has been established to be linear over large concentration ranges, instrument preconcentration capture and desorption of the target compounds do not behave linearly at low and high concentrations, particularly for very volatile (e.g., ethane, ethylene) compounds and those with higher boiling points (1,2,4-trimethylbenzene, dodecane). Nonlinear performance may be more pronounced when trap materials have aged. For this reason, the daily CCV will include a suite of compounds representing the molecular weight range (C2 to C10). Several analytes are known to be problematic (recovered less than 70% of the theoretical concentration) with the carbon-response calibration method. Acetylene, alpha-pinene, and beta-pinene are known to exhibit degradation in standard cylinders and/or suffer poor preconcentration performance. Additional compounds that show poor integration include m & p-diethylbenzene, 1,2,3-trimethylbenzene, 1,3,5-trimethylbenzene, cis-2-butene, and 1,3-butadiene. Styrene is known to show poor correlation with the certified concentration in standard cylinders. Instrument operators need not take stringent corrective action if QC samples exhibit low recovery for these four compounds. The agency will document the low recovery of these compounds and will qualify the associated ambient concentration data when reporting to AQS. B5.1.3 Quality Control for True NO2 Analysis True NO2 analysis QC includes the performance of quality checks on the true NO2 analyzer sampling instrument to ensure the analyzer calibration is within the defined specifications, the ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 76 of 145 zero setting of the analyzer has not drifted outside the acceptance window, and that the flow controllers, and, if so equipped, the ozone generator, of the dynamic dilution calibrator (DDC) employed to calibrate the analyzer are operating properly and within the prescribed tolerances. True NO2 QC activities include, as described in Table B5-3 and in the true NO2 analysis SOP, an VIPV, zero/span checks, and zero/span/precision checks for the NO2 analyzer and flow verification checks and ozone generator calibration verifications for the DDC. Table B5-3. True NO2 Quality Control Parameters QC Parameter Description Required Frequency Acceptance Criteria Recommended Corrective Action Calibration Setting zero and span levels on the true NO2 analyzer by introducing zero air and an NO2 standard at 80% of the desired measurement range covering the expected range of ambient measurements (e.g., 160 ppb NO2 for a measurement range of 0 to 200 ppb NO2) Initially when deployed, minimally every 365 days, following maintenance to the instrument expected to alter the instrument response, following operation interruption of several days (e.g., 48 hours), and following failing span check or zero check None. Verified by MPV. Repeat calibration if indicated by MPV. It may be necessary to investigate for system contamination or interferences resulting in suppression or enhancement (check filters, perform leak checks, clean mirrors, etc.) Multi-point Verification (MPV) Introduction of a zero and four upscale NO2 concentration points covering the measurement range, (e.g., 0, 175, 125, 75, and 25 ppb) Immediately following establishing a new calibration. Linear regression of the measurements plotted against the theoretical must show r2 of > 0.995 and have an x-intercept within ± 0.2 ppb NO2 of the origin. Percent difference of each standard measurement must be within ±15% of the theoretical concentration. Repeat verification. It may be necessary to investigate for system contamination or interferences resulting in suppression or enhancement of analytes. Recalibration may be necessary. Zero/Span Check Analysis of zero air and span NO2 standard (-80% of measurement range) to Reauired evervM days. More frequent chccfl Zero drift must be less than ± 0.3 ppb. Repeat zero and span checks to confirm. Investigate svstem for ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 77 of 145 QC Parameter Description Required Frequency Acceptance Criteria Recommended Corrective Action monitor for drift in zero and span levels. Checks are performed on analyzer in as-is condition before modifying instrument settings. are recommended. Span level must be within ±15% of the theoretical concentration. contamination, leaks, or other causes of drift. Qualify or invalidate data since the last passing QC check. Perform calibration and MPV. Opti Be Zero/Span/Precision Check Verification performed by analyzing a zero and two standard NO2 concentration levels - span point at approximately 80% of the measurement range and a precision point in the lower 1/3 of the measurement range (e.g., 160 and 50 ppb, respectively for a measurement range of 0 to 200 ppb) ional commend minimally ever 14 days or mor frequently. Zero drift must be less than ± 0.3 ppb. Span and precision levels must be within ±15% of their theoretical concentration. Repeat Zero/Span/Precision Verification to confirm. Investigate system for contamination, leaks, or other causes of drift. Qualify or invalidate data since the last passing QC check. Perform calibration and MPV. Dynamic Dilution Mass Flow Controller (MFC) Check Verification of diluent gas and standard gas channel MFC calibration against a NIST-traceably certified flow transfer standard Quarte™ 90 days) (every Flows covering the 10 to 90% of each MFC (or bracketing range of flows employed) must be within ±2% of the flow transfer standard Recalibrate (adjust) the slope and intercept of the MFC per the manufacturer instructions and repeat verification. If verification still cannot meet acceptance, MFC may require repair DDC Ozone Generator Calibration Verification Verification of ozone generator calibration against a Level 1 or Level 2 ozone standard Quarterly (every 90 days). Required only when conventior of generation of N02 standard ga is accomplish by gas pha titration (GPT) ( ozone with NO. Ozone generator performance will be described in QAPP governing ozone monitoring. Recalibrate (adjust) the ozone generator slope and intercept per the manufacturer instructions and repeat verification. If verification still cannot meet acceptance, ozone generator may require repair. B5.1.4 Quality Control for Meteorology Meteorological instruments require minimal intervention and maintenance once configured and calibrated, therefore it is anticipated that meteorology parameters will be measured at each PAMS Required Site year-round. QC procedures for meteorology measurements consist of the initial calibration and an annual calibration check. These calibration checks and the associated acceptance criteria are shown in Table B5-4, which are replicated in the appropriate SLT monitoring agency SOPs. For all measurements, if the indicated acceptance criteria are exceeded, the instrument calibration will be adjusted to match the reference standard. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 78 of 145 Note: Table B5-4 is consistent with EPA's Quality Assurance Handbook for Air Pollution Measurement Systems, Volume IV-MeteorologicalMeasurements. EPA recognizes that this handbook was last revised in 2008 and may not be representative of current meteorological instrumentation. Air agencies should consult with their EPA Regional Office regarding any potential deviations from these acceptance criteria until the handbook is revised. Table B5-4. Quality Control Parameters for Meteorology Measurements Meteorology Parameter Calibration Check Standard Required Frequency Acceptance Criteria Recommended Corrective Action Ambient Temperature Verification in a water bath or dry well against a NIST- traceable thermistor or thermometer at three points bracketing the temperature range of use Semi-annually < ± 0.5°C at each of the three temperatures checked Inspect instrument for damage or worn components. Correct data where possible (e.g. wind direction). Recalibrate instrument. Qualily all collected data since the most recent calibration or acceptable calibration check as "QX" in AQS, as applicable. Potentially invalidate data since last most recent calibration or acceptable calibration check. Relative Humidity Compared to a NIST-traceable psychrometer or standard solutions Semi-annually < ± 5% RH of the hourly average from the certified standard over the duration of comparison Barometric Pressure Compared to a NIST-traceably certified barometer or pressure transducer over the course of several consecutive hours Semi-annually < ± 3 hPa Wind Speed Compared to a NIST-traceable synchronous motor or CTSa method Semi-annually < ± 0.2 m/s or± 5%, whichever is greater Wind Direction Compared to solar noon, GPS, magnetic compass, or CTSa method Semi-annually < ± 5 degrees Solar Radiation Compared to a NIST-traceable pyranometer Semi-annually < ± 5% b UV Radiation Compared to a NIST-traceable radiometer Semi-annually < ± 5% b Precipitation Add water at a constant rate such that the gauge tips every 15 seconds and measure output with a graduated cylinder Semi-annually < ± 10% of input volume a CTS = collocated transfer standard b Comparison should be made during sunny conditions. B5.2 Quality Control for Laboratory Activities QC procedures for laboratory activities cover laboratory extraction and analysis of carbonyls cartridges as identified in Table B5-5, which are replicated in the ASL SOP. Laboratory QC samples consist of extraction batch QC (extraction solvent method blanks [ESMB] and DNPH media method blanks [MB] and known standard spikes - LCS/LCSD) and analysis batch QC samples including solvent blanks (SB), SSCV standards, continuing CCV, and replicate analysis of an extract. Other QC processes include establishing HPLC instrument calibration and adhering to proper cartridge storage conditions and holding times. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 79 of 145 Table B5-5. Carbonyls Laboratory Quality Control Parameters QC Parameter Detail Required Frequency Acceptance Criteria Recommend Corrective Action Solvent Blank (SB) Analysis of acetonitrile solvent to demonstrate the HPLC is sufficiently clean Prior to ICAL, prior to first daily CCV and after each CCV when additional samples are to be analyzed Target analyte concentrations < MDLsp Analyze several SBs and pump mobile phase to flush system. If contamination or interference persists, further investigation of source of contamination is necessary. Initial Calibration (ICAL) Analysis of five or more different calibration standard solutions covering the concentration range of interest Prior to PAMS season, after failed continuing calibration verification, and after changing instrument components or maintenance which impacts calibration response r > 0.999, back- calculated concentration of each standard level within ± 20% of nominal, intercept/slope < MDLSp Review chromatography for co-eluting peaks or improper integration. If problem is not found, repeat calibration. If still unable to meet criteria, prepare new calibration standards and reanalyze. Analysis cannot commence until calibration meets criteria. Second Source Calibration Verification (SSCV) Analysis of a known standard prepared from a stock solution sourced from a vendor independent of the primary calibration stock standard; verifies the quality of the ICAL Immediately following ICAL Target analyte concentrations within ± 15% of nominal Review preparation records, calculations, procedures, and chromatography to investigate discrepancy with ICAL. If root cause not found, prepare new SSCV and/or ICAL and reanalyze extracts analyzed since the last passing SSCV. Analysis cannot commence until SSCV following ICAL meets criteria. Continuing Calibration Verification (CCV) Analysis of a known standard solution to verify the instrument calibration remains valid At the beginning of each day's analysis when an ICAL is not performed and after every 12 hours of analysis Target analyte concentrations within ± 15% of nominal Review chromatography for co-eluting peaks or improper integration. If problem is not found, establish new ICAL and reanalyze extracts analyzed since the last passing CCV. If associated samples cannot be reanalyzed, and unless technical justification is provided to explain nonconformance, qualify all samples since most recent acceptable CCV as "QX" in AOS. Holding Times Maximum duration from end of sample collection for sample extraction Maximum duration from sample extraction to analysis All field-collected and laboratory QC cartridges 14 days from end of sample collection to extraction 30 days from sample extraction to analysis Qualify samples exceeding holding times as "HT" in AQS. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 80 of 145 QC Parameter Detail Required Frequency Acceptance Criteria Recommend Corrective Action DNPH Lot Blank Analysis Extraction and analysis of a representative amount of each lot of DNPH cartridge media to demonstrate acceptably low background With each new lot of DNPH cartridge media - 3 cartridges per lot or 1%, whichever is larger Measured mass per cartridge (|ig/cartridge): - acetaldehyde <0.10 - formaldehyde <0.15 - acetone <0.30 - other individual compounds <0.10 Reject media lot and return to vendor. If media must be used, qualify results for compounds with exceedances as "LB" in AQS. Method Blank (MB) Blank cartridge from the lot of co-extracted field-collected samples - extracted to assess cleanliness of media and reagents One per extraction batch of 20 or fewer field- collected samples Target analyte concentrations < MDL Review preparation records, chromatography, and procedures for sources of contamination. Unless technical justification is provided to explain nonconformance, qualify all sample results in the extraction batch as "LB' in AQS. Laboratory Control Sample (LCS) Blank cartridge spiked with a known amount of target analytes and extracted Minimally twice quarterly, recommended each extraction batch of 20 or fewer field- collected samples Formaldehyde recovery within 80 to 120%, all other target analytes recovery within 70 to 130% ' Review preparation records, chromatography, and procedures for sources of contamination or suppression. Unless technical justification is provided to explain nonconformance, qualify sample results in the extraction batch as "QX' in AOS. Laboratory Control Sample Duplicate (LCSD) Duplicate blank cartridge spiked with a known amount of target analytes and extracted to assess precision of the extraction and analysis method Minimally twice quarterly, recommended each extraction batch of 20 or fewer field- collected samples Formaldehyde recovery within 80 to 120%, all other target analytes recovery within 70 to 130%; precision with LCS as RPD < 20% Review preparation records, chromatography, and procedures for sources of contamination or suppression. Unless technical justification is provided to explain nonconformance, qualify sample results in the extraction batch as "QX' in AOS. Extraction Solvent Method Blank (ESMB) Aliquot of solvent lot used for extraction contained within a volumetric flask used for extraction Each extraction batch of 20 or fewer field- collected samples Target analyte concentrations < MDLsp Review preparation records, chromatography, and procedures for sources of contamination. Qualify sample results in the extraction batch as "LB' in AQS. Replicate Analysis Repeat analysis of a routine sample extract One each day of analysis Relative percent difference < 10% for compounds >0.5 Hg/cart ridge Reanalyze extracts to confirm disparate results. If confirmed, qualify sample results in the analysis batch as "QX' in AOS. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 81 of 145 QC Parameter Detail Required Frequency Acceptance Criteria Recommend Corrective Action Field Blank Blank cartridge installed in a sampling channel for five to ten minutes As submitted to the laboratory by field site(s) measured mass per cartridge (|ig/cartridge): - acetaldehyde < 0.40 - formaldehyde <0.30 - acetone <0.75 - sum of other compounds < 7.0 Investigate sources of contamination in handling and transport. Unless technical justification is provided to explain nonconformance, qualify associated field collected samples as "FB" in AQS. Associated samples are those in the shipment with the field blank and the samples since the most recent acceptable field blank. Trip Blank Blank cartridge accompanying collected samples to and from the field site As submitted to the laboratory by field site(s) measured mass per cartridge (|ig/cartridge): - acetaldehyde <0.10 - formaldehyde <0.15 - acetone <0.30 - other individual compounds <0.10 Investigate sources of contamination in handling and transport. Unless technical justification is provided to explain nonconformance, qualify associated field collected samples as "TB" in AQS. Associated samples are those in the shipment with the trip blank. Sample Storage Cartridges stored refrigerated and protected from light All samples Storage in foil pouch at <4°C If temperature is exceeded, qualify results as "TT" in AOS." Extract Storage Sample extracts stored refrigerated and protected from light All extracts Storage in amber vials at < 4°C If temperature is exceeded, qualify results as "TT" in AOS." Duplicate Sample Analysis Analysis of a separate sample cartridge collected concurrently with a primary 8-hour sample through a common inlet probe As submitted to the laboratory by field site(s) Relative percent difference < 20% of the associated primary cartridge for compounds >0.5 ng/cartridge Unless technical justification is provided to explain nonconformance, qualify both samples as "QX" in AQS. Collocated Sample Analysis Analysis of a separate sample cartridge collected concurrently with a primary 8-hour sample through an independent inlet probe As submitted to the laboratory by field site(s) Relative percent difference < 20% of the associated primary cartridge for compounds >0.5 ug/cartridge Unless technical justification is provided to explain nonconformance, qualify both samples as "QX" in AQS. B6 Instrument/Equipment Acceptance, Testing, Inspection, and Maintenance Instrumentation used to conduct PAMS measurements or to calibrate PAMS equipment will be maintained in accordance with the manufacturer's guidelines regarding routine maintenance of the specific instrument/equipment. Inspection and maintenance procedures will be followed as described in the approved instrument SOPs. Routine instrument maintenance activities and their prescribed frequencies are shown in Table B6-1. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 82 of 145 B6.1 Instrument Acquisition for New Required PAMS Sites SLT air agencies are required to establish and begin operating additional PAMS networks resulting from a new census (see 40 CFR 58.14(b)). EPA recommends that new field-related equipment and samplers/monitors be installed by the October prior to the site's first PAMS season for shakedown, testing, and training so as to be ready for full implementation before the start of the season on June 1. Monitoring agencies will work with the Regional Representatives to communicate issues or delays in installing or readying instruments or measurements. If there are delays in instrument acquisition or measurement implementation, monitoring agencies are expected to conform with the monitoring agency QAPP once the instruments are operational and suitable for monitoring. Details and approvals will be described within the monitoring agency QAPP or in a separate document and indicated by reference. Monitoring equipment (e.g., auto- GCs, carbonyls samplers, true NO2 analyzers, and ceilometers) necessary to outfit the PAMS Required Site will be selected and purchased so as to ensure sufficient time to receive, inspect, install, calibrate, and become familiar with the operation of the instruments. While training on instrument use will continue after the beginning of PAMS season, monitoring agencies will plan for site operators and auditors to attend training sessions, when available, in the months leading up to PAMS season. B6.2 Instrument Acceptance Testing and Shakedown The instruments and support equipment for PAMS monitoring are complex and typically require a testing, conditioning, and shakedown period of minimally several weeks to ensure that instrument operation is stable and that monitors are suitably free of contamination and ready for the collection and analysis of the trace levels of pollutants in ambient air. Once equipment is received and inspected and proper operation is verified, instruments require calibration and independent verification of the calibration. Depending on instrument installation status, the monitoring agency will plan to perform instrument conditioning and shakedown with sufficient time prior to the 2021 PAMS season to ensure instruments are functioning properly and are calibrated. During this shakedown period, site operators will treat the data as a "dry run" for generating PAMS measurement data to work out instrument and data transformation problems and become accustomed to the instrument operation and data outputs. Each monitoring agency will conduct a shakedown assessment (a TSA) prior to the first PAMS Required Site monitoring season and annually thereafter prior to PAMS season (unless the instruments are operated year- round). Monitoring agencies will not report data to AQS during the shakedown period. B6.2.1 Initial Instrument Acceptance and Shakedown Once monitoring instruments and equipment are purchased and have been received, the instruments and equipment will be inspected within one month of receipt (earlier if possible) to ensure they are in good condition and include the necessary components required for installation. Vendors will be contacted immediately if issues are discovered during this initial inspection. Instruments will be installed in the monitoring shelter or laboratory (by the vendor, site operator, or other qualified individual or 3rd party provider of such services), as appropriate, and monitoring agencies will condition the instruments and ensure their proper functionality, which may include: • Checking and documenting the diagnostics of the instrument, looking for error messages or warnings ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 83 of 145 • Ensuring that parameters such as sample flow rate, pressure, temperatures, etc., are within specifications per instrument manuals • Performing leak checks on the instrument Once proper instrument operation has been confirmed, site operators will calibrate or verify the calibration of the instruments, as appropriate, as part of the instrument shakedown. Known aspects of instrument and support equipment operation which require several days to weeks to complete include, but are not limited to, the purging and conditioning of zero air generators (for auto-GC use); passivation and conditioning of calibration standard gas regulators, lines, and calibrators; and flow calibration of carbonyls sampling instruments. This initial shakedown and testing period will occur minimally three months prior to the 2019 PAMS season, preferably earlier, to ensure that problems and related troubleshooting and corrective actions can be resolved prior to beginning required monitoring. B6.2.2 Annual Instrument Shakedown The monitoring agency may elect to operate all or some of the instruments year-round. In such cases, the maintenance schedule prescribed for each instrument is to be followed and suitability for each measurement will be evidenced by the QC procedures and checks required for PAMS Required Site measurements. If, however, the monitoring agency opts to shutdown PAMS monitoring at the conclusion of PAMS season, instruments will go through shakedown such that the instruments are online, calibrated, and stable minimally four weeks prior to the start of PAMS season and in sufficient time to demonstrate proper operation as evidenced by acceptable performance in PTs. Note that auto-GCs and supporting equipment are typically less prone to operational problems when operated year-round. B6.3 Equipment Inspections In general, the following routine inspections will be conducted: • Monitoring shelters, sample inlets, and equipment facilities (such as pump or compressor housings) must be inspected monthly to ensure conditions do not adversely affect instrument operation or data integrity. • Data collection and data quality are reviewed each business day to inspect for trends or signs of problems. Data trends that indicate a need for further inspection include issues such as identical ("frozen") numbers for several consecutive hours or erratic spikes or dips in the measured concentration values. • Equipment will be inspected during site visits to ensure instruments are in appropriate working order. Site visit checklists will be developed and used to ensure a consistent level of inspection for site operators. An example site visit checklist detailing typical items inspected is included in Appendix E. B6.4 Instrument Maintenance Preventive maintenance minimizes instrument downtime and associated data loss. Routine preventive maintenance will be conducted in accordance with the manufacturer's operation manuals and applicable maintenance bulletins or updates issued by the manufacturer and ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 84 of 145 according to procedures and frequencies described in the approved PAMS instrument SOPs. Additional information on instrument maintenance can be found in Revision 3 of the PAMS TAD. PAMS instrument and support equipment maintenance activities will be performed per the frequency detailed in Table B6-1. Note the information in Table B6-1 is generic and that monitoring agencies will update the information in the table below to specify the activities and associated required frequencies in their QAPP specific to their instruments. Monitoring agencies will maintain an appropriate supply of critical spare parts and ensure tools are available prior to conducting routine maintenance. Components known to fail or require frequent replacement should be readily available to address unforeseen events. A list of these supplies will be detailed in the specific equipment SOPs. Table B6-1. Routine Instrument Maintenance Activities Instrument Maintenance Activity Frequency Auto-GC Maintenance activities are prescribed in the associated SOP. They include replacing the Nafion dryer (if so equipped), replacing preconcentrator trap(s), servicing zero air generator, calibrating standard dilution measurement equipment Performed annually prior to PAMS season Carbonyls Sampler Maintenance activities are prescribed in the associated SOP. They include recharging/replacing the ozone denuder, replacing the particulate filter, and performing positive bias challenge Performed annually prior to PAMS season True NO2 Analyzer Maintenance activities are prescribed in the associated SOP. These include replacement of particulate filter, servicing zero air generator, calibrating standard dilution equipment Performed annually prior to PAMS season Precipitation Gauge Weighing gauges: Routine visual check. Clean gauge by soaking and wiping with a clean cloth and soapy water. Change chart, chart pen, wind clock, or change batteries Each site visit, or as recommended by the manufacturer Tipping Bucket Gauge: Visually inspect and clean apparatus of dirt and debris, as needed. Manually tip bucket 10 times and verify that 10 tips were recorded by the instrument. Visually inspect during each site visit; perform operational check if necessary during each site visit, or as recommended by the manufacturer Wind Speed/Direction Instrument Cleaning and lubricating per manufacturer recommendations Annually during calibration verification Thermometer Inspect and clean radiation shield. Verify paint reflective integrity. Minimally every six months or more frequently depending on site conditions Barometer Inspect wiring integrity and instrument housing for proper ventilation - remove dust from indoor sensors Each site visit Hygrometer Inspect and clean radiation shield. Verify paint reflective integrity. Replace screen as needed Minimally every six months or more frequently depending on site conditions Radiometer (pyranometer) Clean dome lens, verify level, and review data to verily diurnal pattern, inspect and replace desiccant - realign after servicing Clean lens and inspect level, unit, and data each site visit, or as recommended by the manufacturer - replace desiccant monthly ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 85 of 145 Instrument Maintenance Activity Frequency Ceilometer Check for alarms and warnings and confirm that the ceilometer computer is recording data. If an air agency uploads data to the Unified Ceilometer Network, confirm that the data are being properly transferred. Maintenance activities are prescribed in the associated SOP. Clean laser window, check window blower operation, check and clean (as needed) door gasket. Each site visit Each site visit, or as recommended by the manufacturer HPLC for carbonyls analysis Maintenance activities are prescribed in the ASL QAPP and associated SOP. Such includes servicing pumps, replacing guard columns, replacing solvent frits, injector needles, etc. As prescribed in the ASL QAPP (or equivalent) and SOP Prior to each PAMS season, monitoring agencies will complete maintenance on the instruments and support equipment necessary for PAMS measurements. Monitoring agencies will replace worn items as needed, verify proper operation, and calibrate instruments such that the instruments are readied for collecting and reporting PAMS measurements starting no later than June 1 of each year. Note that for auto-GCs or continuous gaseous monitors, these instruments may need to be readied several weeks in advance to accommodate PT sample analysis or through-the-probe (TTP) audits as arranged with the EPA Regional representative or EPA's QA contractor. PAMS site operators will perform basic checks during each site visit which include visually examining the instruments at the site and verifying communication with the data acquisition system (DAS). An example site visit checklist is included in Appendix E. The intent of this checklist is to serve as a comprehensive list of items for operators to verify when onsite such that the risk of data loss is minimized and to demonstrate that equipment is operating normally. These checklists are valuable data inputs for data verification and validation. Agencies may choose to prepare their own checklist to capture different or additional aspects of monitoring when operators are on site. Operators should pay particular attention to instruments outdoors, such as meteorological instruments. A visual inspection will include verifying that instruments temperature shields are present, free of damage, and not blocked (such as with a bird nest, insect nest, etc.). Mechanical wind instruments should be verified to be operational if the wind is blowing and precipitation gauges should be inspected for debris. In general, site operators should compare current meteorological readings to nearby National Weather Service (NWS) site conditions or other reliable nearby readings. B7 Instrument/Equipment Calibration and Frequency Calibration is defined as the comparison of a measurement standard, instrument, or item with a standard or instrument of higher accuracy to detect and quantify inaccuracies and to report or eliminate those inaccuracies by adjustment. Instruments and devices employed at PAMS Required Network Sites will be calibrated prior to use and according to the schedule/frequency described within this section, which are duplicated in the PAMS TAD and national SOPs. Note that calibration checks which may involve verification of calibration at one or more different levels ensure the calibration remains valid, but do not involve adjustment of the instrument. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 86 of 145 Calibration verification failures require adjustment of the calibration, or re-calibration, of the instrument or monitor. Instrument calibrations will be documented in logbooks dedicated to the instrument. Electronic means of record keeping, e.g., calibration, verification forms, and datalogging programs with annotation report capabilities, can serve in place of a physical logbook. The instrument will be uniquely identified and the date of calibration, identification of standard(s) used for calibration (including certification date), calibration outcome (such as slope, intercept, or other metric indicating acceptable calibration), and any needed corrective actions will be documented in the appropriate logbook. Standards will not be used past their expiration date. B7.1 Instrument Calibration Instrument calibration instructions are specified for the beginning of and conclusion (shutdown) of PAMS season in the applicable SOPs. B7.1.1 Carbonyls Instrument Calibration Carbonyls instruments requiring calibration include field sampling instruments and laboratory instruments. B7.1.1.1 Carbonyls Field Sampling Instrument Calibration and Calibration Verification Carbonyls sampling unit flow controller(s) will be calibrated initially prior to the beginning of PAMS season and the flow calibration verified minimally monthly thereafter. Flow calibration verification will be within ±10% of the flow indicated at standard conditions of 760 mmHg and 25°C against a NIST-traceably certified flow transfer standard. B 7.1.1.2 Carbonyls Laboratory Instrument Calibration and Calibration Verification Initially, following maintenance or repair that would reasonably impact the instrument response, and following failure of CCV or SSCV, the HPLC or UHPLC will be calibrated for the target compounds by analysis of a minimum of five concentration levels covering the concentration range expected to bracket the concentrations of carbonyls in the cartridge extracts. Instruments that are not operated continually (e.g., those shut down for several months at a time) will be calibrated when returned to online status. Calibration will be verified immediately following the ICAL by analysis of an independent SSCV and every 12 hours of analysis thereafter by analysis of a CCV. The SSCV and CCV will be within ±15% of the nominal concentration or corrective action must be taken. B7.1.2 Calibration and Calibration Verification for Speciated VOCs by Auto-GC Auto-GCs for measuring speciated VOCs will be calibrated as part of initial set-up and shakedown, minimally at the start of the PAMS season, and when maintenance to the instrument is reasonably expected to alter its calibration. Calibration is established by analysis of minimally three concentration levels of a representative compound for each respective FID, typically propane or butane for the light hydrocarbon (C2 to Cr, or porous layer open tubular - PLOT column) channel and benzene or toluene for the heavy hydrocarbon (C6 to C12 or polydimethylsiloxane - PDMS column) channel. The stock calibration gas (primary standard) will be NIST-traceably certified for propane (or butane) and benzene (or toluene). [Toluene is included as an option for the heavy hydrocarbon channel in the event that the benzene response ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 87 of 145 factor is not consistent with the other hydrocarbons.] The calibration is then to be immediately verified by analysis of a NIST-traceably certified SSCV containing compounds representing the molecular weight range (C2 to C10). This SSCV is to be analyzed minimally weekly thereafter and must be within ± 30% of the nominal concentration for the target compounds. B7.1.3 Calibration and Calibration Verification for True NO2 Analyzers True NO2 analyzer instruments require calibration initially when placed into service by 12 MPV ntroduction of a zero and an upscale span point (approximately 80% of the intended neasurement range. The calibration will be verified immediately thereafter by conducting the VIPV described in Section B.5.1.3. The MPV will show the analyzer calibration response ha een effectively established through linear regression of the theoretical concentrations anc nstrument readings with a correlation coefficient of r2 > 0.995 and an x-intercept within ± 0.1 pb of the origin. Additionally, the percent difference of each standard measurement in the MP^ 11 be within ±10% of the theoretical concentration. Once the MPV meets acceptance criteria, e instrument calibration and zero must be verified minimally every 14 days. For the zero, the zero drift must be less than ±0.3 ppb and the span level (a concentration approximately 80% of the intended measurement range) must be within ±10% of the theoretical concentration. More frequent verifications are encouraged, and operators are also encouraged to conduct zero/span/precision checks which include verification of a zero concentration and two standard concentration levels - a span point of approximately 80% of the measurement range, and precision point in the lower 1/3 of the measurement range. Instruments which do not meet the listed calibration verification acceptance criteria listed in Table B5-3 will be recalibrated by adjusting the instrument response to match that of the zero and reference standard or may be replaced with a known operable, calibrated instrument. Data collected since the most recelfl acceptable MPV or zero/span check or zero/span/precision check will be qualified or invalidated, To generate calibration gas, GPT is recommended since no NIST-traceable NO2 standard gases are currently available. B7.1.4 Calibration and Calibration Verification for Meteorology Instruments Meteorological instruments require calibration initially prior to placement into service. Instrument calibration will then be verified minimally annually thereafter by conducting the calibration verification QC checks listed in Section B5.1.4. Instruments which do not meet the listed calibration verification acceptance criteria listed in Table B5-4 will be recalibrated by adjusting the instrument response (e.g., thermocouple or hygrometer) and/or orientation (e.g., for wind direction) to match that of the reference standard, or may be replaced with known calibrated instruments that meet the operational requirements given in Table A7-1. Data collected since the most recent acceptable calibration or calibration verification will be qualified or invalidated, as appropriate, when reported to AQS. B7.2 Calibration Support Equipment Calibration support equipment for PAMS measurement instruments includes, but is not limited to, flow transfer standards, reference thermometers, reference barometers, volumetric labware, and mass flow controllers. Calibration and calibration verifications will be performed by comparison to such known standards which will be traceable to NIST standards. Such NIST traceability will be evidenced on a calibration certificate by the metrology lab, standards ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 88 of 145 provider, or certification provider attesting to the accuracy or uncertainty associated with the standard. Such standard certification providers may be the manufacturer, in-house laboratory, third-party laboratory, or other suitable certifier. Such metrology certification providers typically operate under an International Organization for Standardization (ISO) quality standard or other similar performance standard which requires their certifications to be traceable to a NIST certification. Monitoring agencies will specify the certification provider, primary standards of comparison, and approved method or SOP for each appropriate support instrument. These details may be included here or may be included by reference. Support equipment requiring calibration and the associated calibration frequency and acceptance criteria are listed below in Table B7-1. Table B7-1. Calibration Requirements for Critical Support Instruments Critical Support Equipment Specifications and Acceptable Uncertainty Area of Use Calibration a Frequency Requirement Calibration Verification b Check Frequency Flow Transfer Standard < 2% of NIST-traceable standard across its range of flow rates Calibration of flow controllers for carbonyls sampling units and mass flow controllers in gas calibrators Annual per manufacturer specifications Calibration check not required Mechanical Pipette Tolerance within manufacturer specifications Delivery of known liquid volumes - preparation of carbonyls calibration standards Initially and every six months thereafter or when calibration checks demonstrate an out of tolerance condition Each day of use by weighing delivered volumes of deionized water bracketing those dispensed; Must cover the range of use Class A Volumetric Labware Meets Class A tolerances specific to the labware designated volume Measuring final volume of standard solution preparation Received with a certification of calibration Calibration check not required Volumetric Syringe Tolerance within manufacturer specifications Delivery of known liquid or gas volumes Received with a certification of calibration or initially calibrated gravimetrically at 10% and 100% of full volume Calibration check not required ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 89 of 145 Critical Support Equipment Specifications and Acceptable Uncertainty Area of Use Calibration a Frequency Requirement Calibration Verification b Check Frequency Thermometer (not for reporting meteorological ambient temperature data) 0.1°C resolution ± 0.5°C accuracy of a NIST-traceably certified standard thermometer Laboratory and site storage unit monitoring for carbonyls sample and extract storage - temperature monitoring of monitoring shelter - note this is not a thermometer for rcDortina meteorological data Annual at temperature range of use - Correction factors applied to match certified standard Annual calibration is sufficient Balance Tolerance within manufacturer specifications Laboratory - Weighing standards, calibration of pipettes Annually or when calibration checks demonstrate an out of tolerance condition Each day of use with certified calibration check weights bracketing the balance load; Must cover the range of use Certified Weights Tolerances within those assigned to the class of weights Laboratory - Calibration verification of balances Annual or as required by the manufacturer Annual calibration is sufficient Pressure Gauges or Transducers Within ± 0.5 psi or manufacturer-specified tolerance, whichever is smaller Field and Laboratory - Measure canister pressure/vacuum for standards preparation Annual Annual calibration is sufficient; Must cover the range of use Mass Flow Controller - Gas Calibrator Within ±2% of certified flow transfer standard Precise metering of standard and diluent gases for calibration of monitoring instruments Annual or when calibration checks demonstrate flows are out of tolerance Minimally quarterly (before and at the end of PAMS season), monthly recommended a Calibration refers to resetting (adjusting) the reading or setting or applying a correction factor to the instrument or standard to match a certified standard. b Calibration verification checks are a comparison to a certified standard to ensure the instrument or standard remains within a prescribed tolerance. Instruments or standards which exceed the tolerance must be adjusted to be within prescribed tolerances or must be replaced. B8 Inspection/Acceptance of Supplies and Consumables Supplies and consumables include a wide variety of materials such as calibration gas standards, particulate filters for inlets and instruments, stainless steel tubing, high pressure cylinder regulators, auto-GC preconcentrator traps, ozone photometer lamps, ozone scrubbers, etc. Where possible, supplies and consumables will be purchased from reputable vendors to ensure items purchased meet the required specifications. The list of consumables and supplies is too extensive to provide in its entirety in this QAPP; individual materials and the required specifications are ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 90 of 145 listed in the applicable SOPs for the measurement methods. Materials will be inspected and confirmed to meet the specifications detailed in the respective SOP before being used and/or placed into service. Performance of the supply or consumable will be confirmed by verifying proper instrument function or operation evidenced by meeting applicable QC criteria. Monitoring agencies will specify their processes and procedures for inspection/acceptance of supplies and consumables in their QAPPs. B8.1 Acceptance of Standard Materials On an annual basis PAMS monitoring agencies will inspect NIST-traceable transfer standard equipment that is subject to wear and tear during use (for example, temperature, pressure, and flow rate check devices). Such equipment will be returned annually to the vendor or an appropriate accredited metrology laboratory (as specified in Section B7.2) for cleaning, servicing, and recertification against NIST standards. Consult Table B7-1 for equipment requiring such annual certification. Stock gaseous standards for calibration of the PAMS analyzers will be sourced from reputable certified gas vendors. Similarly, derivatized carbonyls calibration stock materials will be sourced from reputable chemical suppliers. Standard gases and carbonyls stock materials will preferably be NIST-certified or NIST-traceably certified and must be accompanied by a certificate of analysis (COA) stating the purity (for neat materials or pure gases) or certified concentration with associated uncertainty for each component as well as the expiration. When available, standard NO2 gases for calibrating NO2 analyzers will be procured from a reputable supplier and certified concentrations must be traceable to a reference material, such as those prepared by the NIST or the Van Swinden Laboratorium (VSL). Such NO2 standard gases will be accompanied by a COA indicating the levels of impurities, which will be less than 1 ppm of residual NO. When employing GPT to calibrate NO2 analyzers, NO standard gases will be Standard Reference Material (SRM) or Certified Reference Material (CRM) quality and compliant with Protocol 2 of the EPA's Protocol Gas Verification Program (PGVP).11 Ozone generators employed to produce standard NO2 gas by GPT with excess NO will be standardized against a Level 1 or Level 2 ozone standard 12 as prescribed in the criteria gas monitoring QAPP. Note that EPA employs a national contract laboratory to independently verify the concentration of propane and benzene in speciated VOCs retention time standard (RTS) cylinders against a NIST-certified standard. The verification laboratory provides a certificate of analysis for the verification of each individual RTS cylinder, listing the average measured concentration of each compound. The average of the concentrations measured by the verification laboratory must be within ±10% of the value listed on the gas vendor certificate of analysis. The verification laboratory values indicate the cylinder concentrations are accurate to within the vendor-listed tolerance; however, these values do not indicate the measurement uncertainty or expiration and will not be referenced for determining concentrations of calibration standards or calibration verification standards. Rather, the concentrations and expiration date listed on the gas vendor certificates of analysis will be referenced for standards preparation. Expired standards may not be utilized for instrument calibration or calibration verification unless the expiration has been extended following a process approved by the Regional Representative. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 91 of 145 COAs will be maintained by the monitoring agency or laboratory and be available for inspection during TSAs. Gas standard expiration or recertification dates are typically one year or more and several vendors offer recertification services in which traceable concentrations are updated such that the useful life of the standard cylinder is extended. Recertification of standard gases may be more cost effective than purchasing new standards and can be performed during the non- sampling season (as applicable to the specific PAMS Required Site). Prior to acceptance or use of a standard material for calibration, particularly for custom-ordered materials, the COA will be inspected to ensure the correct compounds are included, that their concentrations are as requested and within requested tolerances, and that listed impurities are acceptably low. The new stock standards for VOCs analysis will be analyzed against a known acceptable instrument calibration and known stable (acetylene, styrene, and pinene isomers are not considered to be stable) compounds such as propane, benzene, toluene, ethylbenzene, and xylenes will be within the method bias specification. B8.2 Acceptance of Sampling Media - Carbonyls Prior to use in the field for sample collection, each lot of DNPH cartridges will be tested to ensure the background contamination is acceptably low. Minimally three cartridges per lot or 1% of the received lot, whichever is greater, will be extracted and analyzed to determine the average background concentration of each target carbonyl. Background concentrations vary within manufacturer lots, therefore monitoring agencies are encouraged to select cartridges from different boxes within a given lot to characterize the lot's background variability. Each tested lot blank cartridge will meet the criteria in Table B8-1. It is expected that the ASL will perform this lot blank analysis for each lot of media for use at supported sites. If the criteria in the table are not met, the lot will not be used for sampling and will be returned to the vendor. Table B8-1. DNPH Cartridge Lot Blank Acceptance Criteria Carbonyl Compound Acceptance Limit (ug/cartridge) Acetaldehyde <0.10 Formaldehyde <0.15 Acetone <0.30 All Other Carbonyl Compounds <0.10 B9 Non-direct Measurements Non-direct measurement data will be used to support data validation activities, as described in Section 10 of Revision 3 of the PAMS TAD on data verification and validation. Such data may include historical PAMS data or reported concentrations and meteorological measurements from other monitoring sites. Data acquired from non-direct measurements may also include site operator observations. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 92 of 145 B9.1 Historical PAMS Data and Supplemental Measurement Data from Other Monitoring Sites PAMS data may be compared, for the purposes of verification and validation, to measurement data from other monitoring sites including other PAMS sites, air toxics sampling sites, meteorology stations, etc., and to historical PAMS data. While the data undergoing verification and validation may be subjected to further scrutiny, adjusted by the addition of qualifiers, or invalidated due to comparison with historical and/or other supplemental data, the monitoring agency will not perform assessment (e.g., further validation) on the historical and/or supplemental data. Adjustment or validation of such data is outside the scope of this QAPP. General guidelines for data validation are given in the PAMS TAD Revision 3 Section 10 and it is recommended that users of any such data confirm the data's fitness for the intended purpose of comparison prior to use. BIO Data Management The monitoring agency will ensure that data are recorded, verified, validated, reported, managed, and archived in a manner that permits reconstruction of activities throughout the data lifecycle. The monitoring agency data management procedures will be described within this section of their QAPP or included by reference. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 93 of 145 C ASSESSMENT AND OVERSIGHT Cl Assessments and Response Actions One of the major objectives of this QAPP is to specify the policies and establish procedures necessary to ensure PAMS data are of sufficient quality and quantity to meet the Required Site Network DQOs. Site operators and laboratory staff have the responsibility to prevent nonconformances where possible and to minimize their impact to data quality and fitness for purpose once identified. Every effort will be made to anticipate and resolve potential nonconformances before the quality of PAMS data is compromised. Nonconformances impacting data quality will be reported to the appropriate monitoring agency manager who will work with the site operators and/or laboratory staff to take corrective action. Adherence to the quality policies described in this QAPP will also be ascertained by way of various ongoing assessments, as given below. Cl.l Types of Assessments As part of the PAMS Required Site Network QS, the following types of assessments will be conducted to ensure that the resulting data quality meets the PAMS DQO and user needs: IP As TSAs ADQs PTs PEs Details regarding assessments are described in Section 15 of the EPA QA Handbook, Volume II (EPA-454/B-17-001, January 2017), available by the following link on AMTIC: https://www3.epa. gov/ttn/amtic/files/ambient/pm25/qa/Final%20Handbook%20Document% 201 17.pdf Staff conducting assessments (auditors) will be independent of staff performing the functions and will have authority to inform management of nonconformances to approved, established procedures and policies. These staff members should be organized under the monitoring agency quality assurance unit (QAU) as described in Section A6.2. Auditors will have authority to suggest to management to stop work activities if nonconformances have a severe impact on the quality of collected measurements or if staff safety is in jeopardy. Refer to Table Cl-1 for a summary of PAMS Required Site assessments. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 94 of 145 Table Cl-1. PAMS Required Site Assessments Assessment Description Responsible Party Conducting Assessment Frequency Shakedown Audit (TSA and IP A) Evaluation of PAMS Required Site readiness Monitoring agency QAU Before the June 2019 implementation; additionally recommended prior to each PAMS season thereafter Technical Systems Audit (TSA) Review of compliance with PAMS Required Site Program requirements, QAPP, SOPs, and best practices Monitoring agency QAU EPA Regional Representative and National QA Support Contractor - note the triennial TSA may also include an IPA of the carbonyls sampler(s) and/or meteorological instruments Annually during active PAMS monitoring Once every three years, preferably during active PAMS monitoring Instrument Performance Audit (IPA) Measurement of carbonyls sampling unit flow with a certified flow transfer standard independent of that used for instrument calibration or verification Comparison of meteorological instrument measurements by comparison with a known certified standard independent of that used for instrument calibration or verification Monitoring agency QAU Annually during active PAMS monitoring Annually during active monitoring - during PAMS season if meteorological measurements are not made year round Audit of Data Quality (ADQ) Review of a representative amount of measurement data (-10%) from initial instrument calibration, sample analysis, and coding for reporting to AQS; includes evaluating that data in AQS were reported accurately Monitoring agency QAU and ASL QAU Annually during active PAMS monitoring and before submittal of a site's PAMS data to AQS - Monitoring agencies are encouraged to perform the ADQ as early in the monitoring season as practical to catch issues to minimize impact on data Proficiency Test (PT)' Analysis of a sample with target analytes at concentrations blind to the monitoring agency and ASL for both speciated VOCs and carbonyls analysis EPA through QA support contractor Twice annually, once prior to PAMS season and once just prior to the end of the PAMS season Performance Evaluation (PE) Analysis of known standard concentrations of target analyte Monitoring agency QAH and EPA Regional staff or EPA support contractor Monitoring agency PE to be conducted annually. EPA NO2 gas provided to the NPAP audit minimally every Halvzcr by gas phase titration through EPA 6 years ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 95 of 145 CI. 1.1 Instrument Performance Audit IP As are an independent check of instalment performance by an individual not involved in routine operation and with reference standards independent from those used to calibrate the instrument or to perform routine calibration checks. IP As involve comparing the output of an instrument to an independent reference standard and quantifying the difference between the measurement generated by the instrument undergoing assessment and the reference standard. The monitoring agency QAU will conduct IP As at PAMS Required Sites at least once per PAMS monitoring season for instruments operated only during PAMS season. Monitoring agencies are encouraged to conduct IP As during PAMS season, however, are provided latitude to conduct IP As during active monitoring. The EPA Regional Representative or delegate may conduct IP As of the pollutant and meteorology instruments, as equipment and capabilities permit, during the triennial TSA. CI. 1.1.1 Carbonyls Instrument Performance Audit Flow rate bias in ambient air sampling for carbonyls has an inverse relationship with the resulting concentration bias. That is, flow rates that are biased low result in overestimation of air concentrations whereas flow rates that are biased high result in underestimation of air concentrations. Minimally once annually (assumed to be once per PAMS season unless the PAMS carbonyls monitoring is conducted at the site outside of the June 1 to August 31 PAMS season), an individual from the monitoring agency QA group independent from routine site operations will verify the flow rate of the carbonyls sampling unit against a certified, reference flow transfer standard independent of the standard utilized to calibrate or perform monthly calibration verification of the sampling unit. This check will be performed at the flow rate at which PAMS cartridges are collected and the flow measured by the flow transfer standard must be within ±10% of the flow indicated by the sampling unit for each of the flow channels utilized for sampling. The assessor will notify the site operator in the event of a nonconformance; corrective action will be required (mass flow controller calibration, flow obstruction removed, etc.) before cartridge collection may resume and previously collected sample data since the most recent acceptable flow check will be appropriately qualified (flagged) or invalidated when reported to AQS. Corrective action is also recommended for flow calibration assessments that indicate flows are approaching, but not exceeding the appropriate flow acceptance criterion. CI. 1.1.2 Meteorology Instrument Performance Audits Typically, meteorological instruments will be operating year-round and can be audited during the year when convenient for the monitoring agency QAU. For instruments operating year-round, it is recommended that meteorological audits occur approximately six months after the annual calibration check. Each meteorological instrument will be audited by comparison to a reference standard. When possible, such IP As are best conducted with the instrument in-situ, as removal of the instrument for audit may eliminate the ability to capture specific aspects of monitoring such as wind-direction, for which the mounting position and compass alignment are critical. It may be impractical to perform in-situ IP As if instruments must be removed for assessment, such as temperature probes which are submerged in a water bath for assessment. Meteorological IP As will meet the acceptance criteria listed in Table B5-4. Monitoring agencies with existing audit programs for meteorological instruments may add reference to their existing quality documents here or by reference. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 96 of 145 CI. 1.2 Technical Systems Audit A TSA is an on-site review and inspection of a monitoring agency's ambient air monitoring program to assess its compliance with established requirements governing the collection, analysis, review, verification, validation, and reporting of ambient air quality data. 40 CFR Part 58, Appendix A, § 2.5 requires TSAs of each PQAO by the appropriate EPA Regional Office.17 Additionally, EPA Order CIO 2105.018 establishes policy and program requirements for an Agency-wide Quality System that include assessments to determine if data are "of sufficient quantity and adequate quality for their intended use." EPA will conduct a TSA at each required PAMS site once every four years unless concerns suggest that more frequent auditing is necessary.2 As described in 40 CFR Part 58, Appendix A, § 2.5, EPA Regional Offices are responsible for conducting TSAs; however, as of the date of this QAPP, EPA has delegated the TSAs at each required PAMS required site to National QA Support Contractor. Since not every site will have its own laboratory, laboratories supporting multiple PAMS sites will be subject to audit in the calendar year that the supported PAMS sites are audited, but will not be audited more than once every three years unless major concerns suggest that more frequent auditing is necessary. To increase the uniformity of TSAs, EPA has developed checklists for the PAMS Required Site program for both monitoring agency and ASL operations, incorporating elements from the PAMS Required Network TAD and national QAPP and SOPs. Monitoring agency TSAs will focus on siting criteria, adequacy of QSs, compliance with QS documents, and interviews of staff responsible for data generation, equipment and instrument calibration, day-to-day operations including sample collection (handling and custody), meteorology, and data management (such as records management and data verification, validation, and reporting). Monitoring agency QA staff will perform a TSA annually during active PAMS monitoring (this will be between the June 1 and August 31 PAMS season unless the monitoring site is monitoring outside of this period). Upon request from an EPA Regional Representative, monitoring agencies should be prepared to submit the results of this annual TSA to EPA. As an option, QA staff may also elect to perform an annual pre-PAMS season shakedown/readiness audit, as described in the section below. Laboratory QA staff will conduct a TSA on the carbonyls sample handling, extraction, and analysis procedures annually. Laboratory TSAs will focus on QSs, compliance with QS documents, performance of analytical methods, sample handling and custody, and data review, verification, and reporting. The ASL QAU will distribute the TSA report to the monitoring agencies operating sites supported by the laboratory. The laboratory will notify supporting monitoring sites of corrective actions, root cause analysis, and demonstrate return to conformance for audit findings deemed to impact data quality. Such reports will identify the affected data. The monitoring agency will subsequently notify the EPA Region of the outcomes of the annual ASL TSA, including any corrective actions taken by the monitoring agency. To reduce the personnel and cost burdens on all involved parties, EPA will attempt to schedule PAMS TSAs concurrently with NATTS TSAs, when logistically feasible. Similarly, EPA 2 At the time of this document, the National QA Support Contractor is only responsible for auditing required PAMS sites and associated laboratories; the contractor will not audit any PAMS-like site that an air agency may establish (i.e., sites installed as part of an EMP). ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 97 of 145 intends to reduce the redundancy of auditing certain parameters that overlap in the PAMS, NATTS, and criteria pollutant TSAs by: • Only auditing the sampling and analysis of data for the auto-GC, ceilometer, precipitation, atmospheric pressure, solar radiation, and ultraviolet radiation during PAMS TSAs. • Only auditing carbonyl sampling and the associated analytical support laboratories during the PAMS TSA if the air agency's carbonyls sampling and analysis processes are not audited as part of the NATTS TSA process. • Auditing the remaining required PAMS parameters (e.g., true NO2, ozone, ambient temperature, wind speed, wind direction, and relative humidity) during the EPA regional office criteria pollutant TSAs. EPA may need to modify the target parameters of an air agency's specific PAMS TSA depending on feasibility, logistics, and/or other specific concerns. Because each site is different, EPA will discuss the PAMS TSA process and clarify the target parameters with the air agency ahead of each audit. CI. 1.2.1 Shakedown Audits Prior to the June 1, 2021, implementation of the PAMS Required Site program, the monitoring agency will conduct a shakedown audit of the PAMS monitoring program to evaluate readiness for the upcoming PAMS season. This shakedown audit will consist of a TSA and include an IPA of the carbonyls sampling instrument(s). The shakedown audit will focus on the readiness of the site operators and data reviewers, the adequacy of their training, the availability of all required QS documents (QAPP, SOPs, field collection forms, COCs) and the suitability and readiness status of the instruments for officially beginning PAMS monitoring. Shakedown audits are intended as a tool to identify compliance gaps and areas where additional resources are required such that data of sufficient quality and quantity may be generated as of startup on June 1, 2021 (and the beginning of each subsequent PAMS season). Formal corrective action is not required as a result of shakedown audits. The shakedown audit is inherently different than an independent audit (TSA and/or IPA) conducted during monitoring season to assess the compliance of the PAMS operations with the monitoring agency's QS. CI. 1.3 Audits of Data Quality ADQs evaluate the methods used to collect, interpret, and report data by examination of a representative amount of measurement data. The following activities and operations are evaluated against the required procedures as given in the monitoring agency QMP, QAPP, and SOPs: • Recording and transfer of raw data • Calculations and reductions or transformations of data • Documentation of data handling procedures • Reporting procedures for inputting data to AQS ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 98 of 145 • Comparison of data contained within AQS to data intended for input Monitoring agency and ASL QA staff will conduct ADQs for PAMS minimally annually and prior to entering data into AQS for speciated VOCs, carbonyls, and meteorology parameters, for those aspects of data collection and reporting for which they are responsible. Results of the ADQ will be reported to the EPA Regional Representative. Monitoring agencies are encouraged to conduct the annual ADQ as early in the monitoring season as possible to catch issues early where their impact on subsequent data is minimized. CI. 1.4 Proficiency Testing PT is a quantitative evaluation of the bias introduced in a part, parts, or in the best-case scenario, the entirety of a measurement process. It involves the analysis of a reference material of known value and composition that is blind to the site or laboratory. The PT program will evaluate the PAMS Required Network Sites and/or ASLs for measurement bias, specifically for speciated VOCs and carbonyls. An EPA contractor will prepare VOCs and carbonyls samples for shipment to either the field site (VOCs) or to the support laboratory (carbonyls) on a biannual basis, both prior to and near the end of PAMS season. Samples are spiked with target analytes at concentrations blind to the sites and laboratories. Sites or ASLs will analyze the PT sample(s) on the auto-GC (VOCs) or via their TO-11A method (carbonyls) and will report the concentrations to the PT provider who will compile the reported concentrations for evaluation against the nominal value and against the overall PAMS Required Network mean (with statistical outliers removed). Auto-GC results for VOCs PT samples must be within ± 25% of the assigned target value for each evaluated target compound. For carbonyls, each PAMS ASL must demonstrate PT analysis results which are within ± 25% of the assigned target value for each evaluated target compound. The assigned target value will be based on the network-wide performance. Sites or ASLs that do not meet the bias acceptance criterion must take corrective action to address the cause of the nonconformance and demonstrate the corrective action is effective. Corrective action necessity will be based on the number of parameters and the severity of the unacceptable evaluations as well as other details of the PT as provided by the PT provider for interpretation of the results. These details are described in study-specific summary interpretations based on the circumstances of each PT study. CI. 1.5 Performance Evaluation A PE is a test of the measurement system performed by providing a series of known standard concentrations of NO2 gas to the monitoring station analyzer TTP and evaluating the bias of the measurements at each provided concentration. PEs are required annually as prescribed in 40 CFR Part 58 Section 3.1.2. Measured concentrations must be within ± 15% or ± 1.5 ppb, whichever is greater, of the theoretical challenge concentration. In addition to the annually required PE conducted by the monitoring agency or cognizant PQAO, the EPA will conduct an audit of the NO2 measurement system TTP minimally every six years, as prescribed in 40 CFR Part 58 Section 3.1.3. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 99 of 145 C1.2 Corrective Actions The monitoring agency will have a corrective action process in place that is executed upon discovery of nonconformances to the monitoring agency PAMS QAPP and/or applicable PAMS SOPs. Each monitoring agency will have a corrective action tracking procedure so that corrective actions are available in a single location (e.g., binder, database, etc.) and may be readily referenced. Monitoring agencies may include their corrective action process here or include it by reference. For each nonconformance, a corrective action report (CAR) will be prepared which includes the following components: • Unique CAR identifier • Identification of the individual initiating the CAR (staff person's name) • Date of discovery of nonconformance • Date of CAR initiation • Area or procedure affected (e.g., carbonyls sample collection) • Description of the nonconformance (what happened and how it does not conform) • Investigation of the nonconformance (how discovered, what is affected by the nonconforming work) • Root cause analysis (what caused the nonconformance) • Investigation for similar areas of nonconformance • Immediate and long-term (if needed) remedial corrective actions (and documentation of when completed) • Due date for remedial action completion (immediate and long-term, as needed) • Impact assessment of nonconformance (data flagging, invalidation, etc.) • Assessment of corrective action effectiveness • Demonstration of return to conformance • Follow up audit to ensure corrective actions were effective (with date completed) • Approval of closure of the CAR by the monitoring agency director and QA unit Situations that require a CAR include, but are not limited to: • Repeated calibration failure • Incorrect sample storage conditions • Persistent blank contamination • Incorrect procedures followed • Repeated QC acceptance criteria failures • Unacceptable PT results Root cause analysis will be performed as soon as possible so remedial actions may be taken to correct the problem before it affects other procedural areas or additional samples and to minimize recurrence of the problem. For problems where the root cause is not immediately obvious, a stepwise approach will be taken to isolate the specific cause(s) of the nonconformance(s). Incorrect conclusions may result if too many variables are altered at one time, rendering the corrective action process ineffective. Monitoring agencies are encouraged to ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 100 of 145 seek assistance from EPA Regions, EPA OAQPS, or instrument manufacturers in instances in which a root cause is not evident. The development and implementation of a CAP, the details of which may be captured in one or several CARs, is an integral part of the assessment process and must be completed as a follow-up to each internal and external TSA. The EPA support contractor and/or EPA Region may assist in development of the CAP for TSAs conducted by EPA Region and/or support contractor; however, the responsibility of implementing corrective actions lies with the monitoring agency. A CAP generally addressed the following points: identification of the root cause for each nonconformance immediate corrective action(s) needed to correct each nonconformance • determination of the existence of similar nonconformances elsewhere in the QS corrective actions to preclude recurrence of the specific and similar nonconformances assignment of responsibility for implementing each corrective action completion dates for each corrective action demonstration of return to conformance Documenting the follow-up activities will ensure that a subsequent assessment team will be able to track corrective activities, verify their efficacy, and confirm return to conformance. If monitoring agency sites or ASLs do not meet PT acceptance criteria, the Regions and monitoring agency may decide to perform additional PTs as part of their root cause analysis and demonstration of return to conformance. Information on root causes and corrective actions will be reported to the Regions and to OAQPS so that lessons learned may be shared and the PAMS program may be continuously improved. C2 Reports to Management Monitoring agency management will be apprised of the results of all independent assessments conducted on their sites and labs operating in support of the PAMS Required Site program. Monitoring agency QA staff will report assessment outcomes to management in a timely manner. The monitoring agency will define the required timeframe for reporting assessment outcomes in their QAPP. Network summary reports should be generated minimally and reviewed upon completion of data entry to AQS according to the requirements in 40 CFR Part 58.16. C2.1 Assessment Reports Monitoring agency QA staff will forward assessment reports to management upon completion of the report (for an internal audit) or when received from an external assessor (e.g., EPA Regional Representative or PT provider). Reports resulting from internal QA activities (e.g., TSA, IP A, ADQ, PTs, PEs, etc.) will identify operational and data quality nonconformances, resource needs (e.g., staff training, equipment), and results from relevant external assessments. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 101 of 145 D DATA VALIDATION AND USABILITY D1 Data Review, Verification, and Validation Requirements The verification and validation process determines the degree to which measurements have met applicable data quality specifications provided in Section A7. Data generated for the parameters listed in Table Bl-1 at PAMS Required Sites and associated ASLs will undergo verification and validation prior to reporting to AQS. Data verification is the process of evaluating the completeness, correctness, and conformance/compliance of data against established method, procedural, or contractual specifications; verification is meant to ensure that data accurately reflect the conditions at the site when the observations occurred. Data validation extends the evaluation of data beyond data verification to determine the quality of a specific data set. The goal of data validation is to evaluate whether the data quality goals established during the planning phase have been achieved;13 for example, to determine if season-long precision and bias met their respective MQOs. A critical component of data validation is also the comparison of the data being validated to other co-collected or historical data to identify potential anomalies in the data that may be concealed behind acceptable precision, bias, and completeness metrics (such as in cases where transient sources bias concentrations temporarily high). Only after a given dataset has been verified and validated can a DQA be performed to determine if it is fit for its intended purpose,14 which for PAMS is to assist in the development and refinement of predictive models for the formation of ground-level O3. To meet the DQO for supporting ozone modeling efforts, data must meet the MQOs and will have been verified and validated as described in Section 10 of Revision 3 of the PAMS TAD which addresses data verification and validation. Data verification and validation are described briefly in the next several sections. Monitoring agencies will define and include data verification and validation responsibilities and activities in this QAPP or in an SOP or combination of SOPs. Such responsibilities and activities will identify the responsible individuals, detail the procedures, materials, and corrective actions required at each waypoint in data verification and validation activities. Examples of aspects to define and describe include (but are not limited to): amounts of data to inspect manually (defining what comprises a data package for review, e.g., 4 complete hours for each day), explicit common issues or problems staff need to be aware of (e.g., high concentrations of a given set of analytes, known misidentified VOCs, VOCs for which automated integration parameters require frequent adjustment or modification, common background interferences, calibration drift tendencies, equipment failures, and meteorological events impacting measurements), data verification and validation tools (e.g., software to evaluate measurements and identify outliers or anomalous data, and types of visualizations to prepare, and data inputs for these tools), and documentation to be prepared at each step during the data verification and validation processes. Dl.l Data Verification and Validation Responsibilities Verification and validation of data for the PAMS Required Site Network is the responsibility of the monitoring agencies that operate the field component of the program, with input from the carbonyls ASL. The ASL will minimally verify the carbonyls data reported to ensure the data are ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 102 of 145 correct and comply with the established laboratory QAPP and SOP(s). The monitoring agency will include the ASL data verification and validation responsibilities for the PAMS Required Site carbonyls data in their QAPP. Subsequent specific verification and validation activities will be described in this QAPP or in an SOP or combination of SOPs. For activities described in the ASL QAPP or SOPs, these may be included by reference. Personnel performing data verification and validation activities will: • Be familiar with the types of data each instrument system produces and the typical measurement ranges produced by each for various parameters (e.g., typical solar radiation levels, benzene concentrations, and true NO2 concentrations). • Be familiar with typical diurnal concentration variations (e.g., the time daily maximum concentrations occur and the interrelationship of pollutants.) For example, benzene, toluene, and xylene concentrations usually increase and decrease together due to these being attributed to mobile sources, whereas ozone typically follows a diurnal cycle with a peak during the afternoon hours. • Be familiar with the types of instrument malfunctions that cause characteristic irregularities in reported data. • Recognize that cyclical or repetitive variations (at the same time each day or at periodic intervals during the day) in continuous measurements may be caused by excessive line voltage or temperature variations. Emissions from nearby sources can also cause erroneous or non-representative measurements. D1.2 Data Verification In the data verification process, PAMS measurement data will be evaluated for completeness, correctness, and conformance/compliance according to the program requirements. The goal of data verification is to ensure and document that the reported results reflect the activities performed and measurements acquired meet the prescribed method performance criteria. Any deficiencies in the data will be documented and, where possible, resolved by corrective action. PAMS data verification applies to activities in the field as well as in the ASL performing carbonyl cartridge extraction and analysis. Data verification includes routine (self) review of collected data by the instrument operator and subsequent technical (peer) review. Dl.2.1 Routine (Self) Review The instrument operator(s) will perform the initial steps of routine (self) review portion of data verification which include reviewing recorded data to ensure the records are complete and comply with the acceptance criteria in the monitoring agency SOPs. It is typically most efficient for this individual to make corrections to collected data and document these corrections such that the impact of any subsequent problem is minimized immediately. Such reviews typically cover 100% of the collected data such that transcription errors (if applicable) are minimized and that QC criteria are within acceptable limits. Recorded data (measurements, observations, etc.) will be reviewed at a frequency that minimizes the loss of data should errors or conditions be found that risk additional data loss if the problem is not corrected. This routine (self) review is typically limited in scope to a particular phase of ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 103 of 145 the data collection activities and is a first step in the overall data verification process, which covers the generation of data from the "cradle to the grave." The frequency for the various activities is specified in Table Dl-1. For example, if the site instrument operator has configured the true NO2 instrument to automatically analyze a calibration check standard every week but does not take the time to review the weekly check for several weeks, such a delay in reviewing the collected data risks losing a week or more of sampling data in the event the instrument lamp fails and the QC check does not meet acceptance criteria. Ideally depending on the measurement system, the individual will conduct a cursory review daily when data are generated, preferably in the morning (verifying nightly QC checks met criteria), to provide a status of the instrument's present performance. Table Dl-1. Routine Review Activities and Associated Frequency Verification Activity Frequency Measurements did not exceed the alarm limits set in the DAS Daily3 The rate of change observed for the analyte is consistent with ambient data trends (specific to high frequency measurements - e.g. minute data) Daily3 Measurement data that exceed the instrument calibration range Daily3 Measurement data are complete (sample collection and COC forms are not missing information, expected electronic files are recorded, and logbook entries are complete) Daily3 Samples/data were collected in accordance with the sample design and approved SOP Weekly Sample collection and handling procedures were followed correctly Weekly Data files are properly identified Weekly Computer file entries match hand entered data sheets Weekly Analytical procedures used to generate data were implemented as specified Weekly Instruments were calibrated properly (i.e., before sampling began, at the specified frequency, included the proper number of points at levels that bracketed the range of reported results) Weekly, as applicable QC check criteria were met and corrective actions are taken when criteria are not met Daily3, as applicable Chromatography is acceptable (stable baseline, adequate peak separation, etc.), integration parameters provide proper peak integration, and that analyte identification is appropriate based on the established RT windows Daily3 Carbonyls sample holding times were met and the analysis laboratory reviewed and verified carbonyl analysis data When carbonyls data are reviewed ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 104 of 145 Verification Activity Frequency Deviations from stated procedures or acceptance criteria are documented and impacted data are flagged or invalidated per monitoring agency policy Weekly Measurements that are known to be invalid because of instrument malfunctions are invalidated as per monitoring agency policy Weekly Data are substituted from a backup in the event of failure of the primary data acquisition system Weekly Corrections and changes to the data records are documented Continuously a Daily on normal business days when staff are on duty. Dl.2.2 Technical (Peer) Review Once the data have undergone routine review by the instrument operator, the data are to be comprehensively technically reviewed by an individual (a peer) not involved with the data generation. The technical review serves to verify that the routine review was completed properly and expands the routine review activities. The technical reviewer performs many of the same activities performed by the instrument operator during routine review, but does not verify instrument operation or status in real time. The technical reviewer verifies correctness of the data generation process by ensuring that documentation is clear and traceable from the sample measurement back through to the certified standards and verifies that the data comply with governing SOPs and this QAPP. The technical reviewers will perform their activities at an appropriate frequency to ensure technical reviews are completed within a month of the data collection. More frequent reviews are recommended to maintain a manageable workload. The technical reviewer will verify (where applicable): • Measurements below the MDL are reported (not censored) and flagged appropriately [note - EPA intends to add automatic flagging functions to AOS for data based on the proximity to the MDL.'] • Concentration measurements exceeding the instrument calibration range were calculated correctly and flagged appropriately • Measurement data are complete (sample collection and COC forms are not missing information, expected electronic files are recorded, and logbook entries are complete) • Samples/data were collected in accordance with the sample design and approved SOP • Sample collection and handling procedures were followed correctly • Data files are properly identified • Computer file entries match hand entered data sheets • Analytical procedures used to generate data were implemented as specified ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 105 of 145 • Instalments were calibrated properly (i.e., before sampling began, at the specified frequency, included the proper number of points at levels that bracketed the range of reported results) Calibration standards were within expiration Calibration standards and check standards preparation calculations are correct and that the nominal (known or theoretical) value is input into the instrument, as appropriate Supporting equipment to make critical measurements (mass flow controllers, adjustable pipettes, pressure transducers, etc.) are within calibration and have passed the most recent applicable calibration checks Routine QC checks met acceptance criteria Chromatography is acceptable (stable baseline, adequate peak separation, etc.) and that analyte identification is appropriate based on the established retention time (RT) windows Chromatographic integration is performed correctly and consistently, and manual integration changes are justified and appropriate Carbonyls sample holding times were met and the ASL reviewed and verified carbonyl analysis data Deviations from stated procedures or acceptance criteria are documented and impacted data are flagged or invalidated per monitoring agency policy Measurements that are known to be invalid because of instrument malfunctions are invalidated as per monitoring agency policy Data have been substituted from a data backup (such as the instrument) in the event of failure of the primary DAS Changes to the data records have been documented and are attributable to the person making the change D1.3 Data Validation Data validation is a process that investigates the individual data points within the context of other co-collected data, historical data, or data collected at a similar location in proximity to the site to determine the quality of the data relative to their expected end use. Only after a given dataset has been verified and validated can a DQA be performed to address the PAMS-specific DQO. Data validation activities build on the data verification processes described in Section D1.2 and will not be conducted on data which have not been verified. Additional data review may be required during data validation, including repeating some steps of the data verification process such as reviewing QC data, calculations, or raw data. Data validation examines the dataset for internal, historical, and spatial consistency: • Level 0 Data Validation - Includes data verification activities discussed in Section D1.2. Some of these activities can be automated by the use of pre-programmed criteria in DAS ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 106 of 145 as an initial review of data. DAS programs may include programmed qualifiers that are applied when a parameter rate of change or upper range limit is exceeded. These are various evaluations that a monitoring agency prescribes at a specified frequency (i.e., every day, once a week) and comprise the first step in the evaluation of data validity. • Level 1 Data Validation - Evaluates internal consistency of the dataset to identify values that appear atypical when compared to the values of the entire dataset. Tests for internal consistency are conducted to identify measurements that do not conform to expectations - outliers and extreme differences within the dataset that warrant further investigation. After tracing the path of the measurement, if nothing unusual is found, the value can be assumed to be a valid result with an environmental cause. Unusual values are identified during the data interpretation process as extreme values or outliers. Outliers and extreme differences can be identified and confirmed by the use of statistical tests, or may be identified by graphical and visual presentation of the data. Visualization tools (plots, graphs, charts, etc.) are powerful as they allow the user to quickly identify values that are atypically higher or lower or that do not conform to a typical or expected pattern, unlike reviewing data in tabular format. Visualization tools include scatter plots, timeseries plots, or fingerprint plots, among others, such as those listed in Section 10.4 of Revision 3 of the PAMS TAD. • Level 2 Data Validation - Data that have undergone Level 1 validation for internal consistency are then compared with historical data to evaluate temporal consistency of the dataset with previous datasets. The historical data may be recent (e.g., one week or one month prior) or may cover a longer period (e.g., the previous year or years). Simple statistical analysis and visualization tools are useful here, as they enable identification of values that do not conform to expectations. • Level 3 Data Validation - Data that have undergone Level 2 validation for temporal consistency may then be evaluated for spatial consistency against data collected at nearby sites, i.e., those in the same airshed, regional network, or monitoring agency, to identify systematic bias. Levels 2 and 3 data validation will be performed when historical data at the site or nearby comparable sites are available. The ability to conduct these validation levels is dependent on the monitoring history (e.g., for PAMS, air toxics programs, criteria pollutant monitoring, etc.) at the site or nearby sites within the airshed. Data validation activities will be documented in sufficient detail such that a QA staff member may recreate the validation as part of the annual ADQ. Data will be validated in portions of time consisting of one to four weeks' worth of data, depending on the volume of data to be validated, so that the dataset is manageable. For example, speciated VOCs data will be validated in one- week portions that include the bracketing weekly precision QC checks. Validating four weeks of speciated VOCs data in one dataset is unwieldy and is more appropriate for carbonyls data. Data validation activities should be completed in sufficient time to allow for potential corrections to data, uploading data to AQS, and confirming data uploads to AQS were successful and accurate. Data validators are encouraged to begin validation on datasets as soon as data verification has been completed on the appropriate size dataset as detailed in Table Dl-2. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 107 of 145 Table Dl-2. Dataset Durations (Sizes) for Validation Parameter Appropriate Duration (Size) of Data Set Speciated VOCs One week's worth - to include bracketing weekly QC checks Carbonyls Two to four weeks' worth - ensure concurrent speciated VOCs data are available for validation True NO2 Two to four weeks' worth - ensure that QC checks bracket the duration undergoing validation Meteorology Two to four weeks' worth - ensure concurrent pollution data to prepare pollution roses D1.4 Reporting of Validated Data to AQS After the data validation has been completed minimally through Level 1, measurement data may be uploaded to AQS. As required in 40 CFR 58.16(d), "the state shall report VOC and if collected, carbonyl, NH3, and HNO3 data from PAMS sites, and chemically speciated PM2.5 mass concentration data to AQS within 6 months following the end of each quarterly reporting period..." Therefore, PAMS VOC and carbonyl data that are collected in June are due to AQS by December 31, and data collected in July and August are due to AQS by March 31. Prior to upload, the data validator will verify flagged data have been qualified appropriately, which may involve performing automated parity checks on the data translated into AQS format and performing spot checks on the transformed data. Chemical measurements for speciated VOCs and carbonyls will include the associated MDL in the AQS coded data. Monitoring agencies are encouraged to have an independent reviewer verify data have been appropriately coded for AQS submission. Such verification checks will be documented. Once reported to AQS, the monitoring agency will query AQS to verify the data were uploaded properly and perform parity checks to verify there are no discrepancies. Such verifications will be documented. Dl.4.1 Reporting Values Below Method Detection Limits (Carbonyls and Speciated VOCs) Instrument sensitivity for carbonyls and speciated VOCs for the PAMS Required Sites is characterized by determining the MDL as described in Section 3.3.5.1 of Revision 3 of the PAMS TAD. The determined MDL for each parameter represents the lowest concentration that can be detected above background with 99% certainty. Concentrations measured at less than the MDL, so long as the qualitative identification criteria have been met (analyte is positively identified), are valid and the measured concentration will be reported to AQS. There will be no substitution of the values (such as Vz MDL) or censoring (reporting as 0) concentrations measured below the MDL. Alarms may be set in the DAS to alert users when low values are recorded; however, the DAS will be configured to permit all data values to be recorded from the instruments and will not censor data. For speciated VOCs and carbonyls measurements for which the target analyte is not qualitatively identified, the concentration will be reported as zero (0) and the QA Qualifier "ND" added when coded for input to AQS. This combination of concentration and qualifier indicates to the data ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 108 of 145 user that the measurement was made but the analyte was not identified and could not be quantitated. D2 Data Verification and Validation Methods The monitoring agency will specify the software and procedures to validate data, where applicable, within this QAPP. The procedures may be abbreviated within this QAPP provided proper detail is included by reference in the supporting SOPs describing data verification and validation. Tools, methods, criteria, and guidance on applying qualifiers to data that are identified as being of inadequate quality are described in Section 10 of Revision 3 of the PAMS TAD. D2.1 Data Verification Methods Instrument operators and technical reviewers will ensure data are complete and correct and comply with this QAPP and supporting SOPs. The end result of the data verification is that all data have been reviewed to ensure that data are traceable - that they were generated with instruments that had been calibrated with certified standards according to an approved standard process, that the instrument calibration and other QC checks were performed at the proper frequency and met criteria, and that all calculations and transformations are correct. Data verification activities are tailored to verify that data are error-free and are flagged (qualified) or invalidated when data integrity is compromised. The routine reviews and technical reviews will include examining data manually and using automated tools to verify the data. Manual methods include, for example, direct examination of chromatography data for auto-GCs, 1-minute data for continuous monitoring methods (meteorology and certain chemical parameters such as true NO2), hand-transcribed data, hand calculation of calibration data, and site and maintenance logs. Automated methods include generation and review of summary reports for auto-GC, DAS summary reports and alarm reports, data completeness reports, and similar reports that provide an aggregation of data to provide efficient confirmation that data meet criteria for bias, precision, completeness, and sensitivity. Data verification activities are tailored to the specific parameter being verified. Specific details for each parameter type are discussed in detail in Section 10 of Revision 3 of the PAMS TAD. Monitoring agencies will describe the data verification activities, procedures, and tools in an SOP or combination of SOPs to ensure that data are correct, complete, and meet technical acceptance criteria, and when data integrity are impacted, the data are invalidated or flagged to indicate the deficient aspects of the applicable data. The processes may be briefly summarized here in this QAPP and will be included by reference (SOP). The monitoring agency will create checklists to ensure that critical data verification elements are reviewed, and their review documented during routine reviews and technical reviews. Checklists will indicate whether each critical element was satisfied. Such checklists will be included in the SOP(s) prescribing data verification and validation as specified in this QAPP. D2.2 Data Validation Methods This section describes general tools for conducting data validation for PAMS Required Site data. These tools are useful in identifying anomalous data and increasing confidence in datasets; ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 109 of 145 however, validators will use a combination of such tools to validate data, and not rely on one specific tool to confirm or nullify data validity. As mentioned previously, each monitoring agency will describe the PAMS Required Site data validation process and tools in an SOP or similar controlled document. D2.2.1 Data Visualization Methods Graphical techniques permit comparison of concentrations of each PAMS parameter to the expected concentrations/measurements and relative concentrations/measurements of other datasets to inspect for values which stand out. These graphical techniques can combine and contrast different parameters temporally and spatially to help accentuate data which may stand out from the dataset and warrant further investigation. Some of the simplest of these graphical tools are available in Data Analysis and Reporting Tool (DART) and in DAS software systems and include the following: • Time series plots • Scatter plots • Fingerprint plots • Stacked bar charts • Pollution roses • Box plots • Diurnal profiles More information on these tools and methods is available in Section 10 of Revision 3 of the PAMS TAD. PAMS monitoring agencies will incorporate these tools and methods, as appropriate, in their data validation procedures and specify the checks and comparisons applicable to the given parameter type(s). The processes will be included here or included by reference (SOP). D2.2.2 Statistical Methods A critical part in validating data within a dataset and against external (historical and spatial) datasets is to generate simple statistics. As with data visualization tools, DART and DAS software packages include automated screening checks and statistical tools that aid in identifying data that exceed user-defined criteria. Screening checks include performing comparisons of related pairs or groups of parameters and identifying situations where criteria such as ratios, sums, and presence or absence of parameters deviate from expected relationships or conditions. D2.2.3 Examination of Supporting Data Comprehensive data validation requires the data validator to examine materials and records that support the reported parameter measurements but are not directly reported data. These supporting data sources are integral in identifying data that may be compromised and require qualification or invalidation. As part of Level 1 validation activities, validators will review these supporting data sources and verify compromised data are appropriately flagged or invalidated, as appropriate. Technical Systems Audit Reports: TSAs may uncover nonconformances that can affect the validity of data. For example, if it is found that a site maintenance worker has stored a gasoline ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 110 of 145 container near the inlet probe, the associated speciated VOCs data impacted during that time period would likely be invalidated. TSA reports and related CAPs will be reviewed during data validation to ensure findings that impact measurement data quality have been addressed through corrective action and data validators will assess the impact of any findings on acquired data undergoing validation. Audits of Data Quality Reports: Findings from ADQs directly impact reported data and indicate errors or problems in data transformations, transcriptions, calculations, or reporting. The findings may result in the need to recalculate or reprocess data, or if the error cannot be corrected, to invalidate the affected data. For example, an ADQ may identify that the nominal concentration was incorrectly input as 3.91 instead of 3.19 ppbC input to generate calibration standards for benzene. Such a situation could probably be corrected and the data reprocessed with an updated calibration curve for the parameters on the higher molecular weight hydrocarbon channel (PDMS column) of the auto-GC. Instrument Performance Audit, Performance Evaluation, and Proficiency Test Results: Deviations from acceptance or advisory limits during IP As, PEs, or PTs indicate bias is present in the measurement system. The validator will review IP A, PE, and PT reports for unacceptable results, will verify that corrective actions have been taken to address the out-of-tolerance condition, and may qualify or invalidate affected data based on the severity and scope of the nonconformance. For example, an IPA identifies a flow rate 15% higher than the flow transfer standard for a carbonyls sampling unit. After further evaluation, if the audit proves to be valid, and the sampler flow rate is beyond the acceptance criterion, the monitoring agency would either estimate the associated results with a QA qualifier or invalidate measurement data back to the most recent passing flow check and invalidate the sample data from that sampling unit when reporting to AQS. Laboratory Analysis Result Reports: ASL results reports may include sample narratives or include QC sample results that provide context for the sample measurements. Data provided by the ASL will be verified with respect to the laboratory processes and method QC acceptance criteria; the ASL will flag data when operational or QC criteria nonconformances occur and notify the site monitoring agency. This will typically involve data flags or comments on electronic data deliverables. It is the responsibility of the site monitoring agency to ensure that subsequent sample measurement data transformations and calculations are appropriate, accurate, and flagged properly. Precision Sample Results: When available, validators will evaluate the precision of duplicate and/or collocated sample results to ensure they meet acceptance criteria. Poor agreement between duplicate or collocated and primary sample pairs is indicative of a problem with the measurement system or data transformation/reduction process, and will be investigated. Results for sample pairs will be minimally qualified when precision acceptance criteria are exceeded, unless a technically justifiable rationale is determined and documented (such as one of the two cartridges became disconnected during the sampling event). If a systemic problem is found to be the root cause, affected data may be qualified or invalidated. For example, if collocated carbonyls samples exceed precision acceptance criteria and corrective action uncovers a leak in the primary sampling unit inlet, the data from the primary samples would be invalidated back to the most recent acceptable precision pair. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page lll of 145 Operator Notes and Site-Specific Information: Data validators will review operator notes recorded in the site logbook, maintenance logs, and on sample collection or COC forms to assess unusual events or instrument problems that may impact measurement result validity or representativeness. Examples include unusual events such as forest fires, temporary violations of siting criteria such as nearby construction, or operational difficulties with the monitoring instrumentation. The monitoring agency will use its best judgment about the impact of site conditions on the acceptability of the data and may consult with the EPA PAMS Regional Representative. Corrective Action Reports: Data validators will review corrective action reports, whether in- process or completed, to investigate corrective actions impacting collected measurements undergoing validation. Conditions deemed to impact sample results may result in corrections to data, qualification, or invalidation, as appropriate. D2.2.4 Treatment of Deviations from Requirements Deviations from procedural or QC criteria call for the monitoring agency to correct the data where possible (e.g., if a wind direction sensor is installed 180 degrees out of phase), take corrective action to limit the impact or recurrence of such deviations, appropriately flag or invalidate affected data when reported to AQS, and notify EPA Regional representatives when a significant amount of data (e.g., 10% of the quarterly values or the potential inability to meet the completeness MQO) are affected. D2.2.4.1 Identifying Compromised Data in AQS If data affected by deviations cannot be appropriately corrected, the monitoring agency will identify compromised data within AQS by addition of a qualifier or combination of qualifiers. Qualifiers associated with PAMS data are indicated in Table D2-1 below. (This list does not include all possible qualifiers, and monitoring agencies are encouraged to use additional qualifiers if the PAMS-associated qualifiers do not accurately capture the event.) Note that at the time this QAPP was published, qualifiers for specific deviations had not been defined and were not available in AQS; however, EPA periodically updates the AQS qualifier list which is published at the following link: https://aas.epa.gov/aasweb/documents/codetables/qualifiers.html Data compromised by QC criteria failures will either be flagged or invalidated in AQS as described below and in Tables B5-1 and B5-5 for carbonyls, Table B5-2 for speciated VOCs, |nd Table B5-3 for true N(J. In situations when no qualifier or combination of qualifiers exists to adequately describe the valid compromised data, the data should be estimated by adding the QA qualifier LJ to the data. When invalidating compromised data and no NULL qualifier exists to describe the rationale for invalidation, the data should be invalidated with the NULL qualifier AM. Flagging Data in AQS: Compromised monitoring data will be flagged in AQS only if the data are considered valid for most purposes and uses. AQS permits users to label each data point with up to ten QA qualifiers and/or informational (INFORM) qualifiers. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 112 of 145 Invalidating Data in AQS: Data of uncertain origin, data with unacceptable levels of uncertainty, or data which are known to not be an ambient measurement will not have an associated measurement value included in AQS. Such data may be the result of instrument failure, known instrument contamination, irrecoverable data, data corruption, or other issues. If reported to AQS, data generated from routine QC checks (except auto-GC system blanks), calibration, determination of MDLs, or instrument troubleshooting for continuous measurement methods will be coded with a Null qualifier to ensure it is not inadvertently reported as ambient data. Invalid data are reported to AQS with a Null (NULL) Code Qualifier which eliminates the associated measurement parameter and indicates the reason for the invalidation. AQS accepts a single NULL qualifier and does not permit addition of other qualifiers (QA or INFORM) to the data point. As discussed further below, data will be qualified and estimated with descriptive QA and INFORM flags where the data are compromised but remain valid. In general, such qualification is preferable to invalidation as there remains a measurement value for the data user to access. The data user can then determine whether to use the data value based on the information indicated by the associated qualifier(s). Invalidation removes the measurement entirely from the data point and is therefore of minimal use to an end data user. Table D2-1. AQS Qualifiers and Null Codes for PAMS Qualifier Code Qualifier Description Qualifier Type Comment 1 Deviation from a CFR/Critical Criteria Requirement QA substitute a more descriptive QA qualifier where possible 2 Operational Deviation QA substitute a more descriptive QA qualifier where possible 3 Field Issue QA substitute a more descriptive QA qualifier where possible 4 Lab Issue QA substitute a more descriptive QA qualifier where possible 5 Outlier QA 7 Below Lowest Calibration Level QA DI Sample was diluted for analysis QA applies to carbonyls only DN DNPH peak less than NATTS TAD requirement, reported value should be considered an estimate QA applies to carbonyls only EH Estimated; Exceeds Upper Range QA FB Field Blank Value Above Acceptable Limit QA HT Sample pick-up hold time exceeded QA applies to carbonyls only LB Lab blank value above acceptable limit QA applies to carbonyls only L.T Identification of Analyte is Acceptable; Reported Value is an Estimate QA most common qualifier when an estimate is needed LK Analyte Identified; Reported Value May Be Biased High QA LL Analyte Identified; Reported Value May Be Biased Low QA MD Value less than MDL QA ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 113 of 145 Qualifier Code Qualifier Description Qualifier Type Comment ND No Value Detected QA NS Influenced by nearby source QA rare - in most situations such data should be invalidated QX Does not meet QC criteria QA SQ Values Between SQL and MDL QA ss Value substituted from secondary monitor QA rare - most sites will not have collocated instruments sx Does Not Meet Siting Criteria QA should require invalidation, but no associated null code exists TB Trip Blank Value Above Acceptable Limit QA applies to carbonyls only IT Transport Temperature is Out of Specs. QA applies to carbonyls only V Validated Value QA VB Value below normal; no reason to invalidate QA AC Construction/Repairs in Area NULL AD Shelter Storm Damage NULL AE Shelter Temperature Outside Limits NULL AF Scheduled but not Collected NULL AG Sample Time out of Limits NULL AH Sample Flow Rate out of Limits NULL AI Insufficient Data (cannot calculate) NULL should be used in situations where the 75% of the hour is not met or the sampling period for VOCs is not 40 minutes AM Miscellaneous Void NULL substitute a more descriptive code where possible AN Machine Malfunction NULL AP Vandalism NULL AQ Collection Error NULL AR Lab Error NULL AS Poor Quality Assurance Results NULL substitute a more descriptive QA qualifier where possible AT Calibration NULL AU Monitoring Waived NULL AV Power Failure NULL AW Wildlife Damage NULL AX Precision Check NULL AY QC Control Points (zero/span) NULL AZ QC Audit NULL used for analysis of the VOCs PT sample & TTP for ozone & NO2 BA Maintenance/Routine Repairs NULL BB Unable to Reach Site NULL BE Building/Site Repair NULL BF Precision/zero/span NULL BH Interference/co- NULL applies to auto-GC parameters only ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 114 of 145 Qualifier Code Qualifier Description Qualifier Type Comment elution/misidentification BI Lost or damaged in transit NULL applies to carbonyls only B.T Operator Error NULL BK Site computer/data logger down NULL DA Aberrant Data (Corrupt Files, Aberrant Chromatography, Spikes, Shifts) NULL DL Detection Limit Aialyses NULL EC Exceeds Critical Criteria NULL use a more descriptive NULL qualifier when possible MC Module End Cap Missing NULL applies to carbonyls only QV Quality Control Multi-Point Verification NULL sc Sampler Contamination NULL TC Component Check & Retention Time Standard NULL TS Holding Time or Transport Temperature Is Out of Specs. NULL recommend use of "HT" QA qualifier instead XX Experimental Data NULL used for troubleshooting, instrument conditioning, MDL determination, etc. IC Chem. Spills & Indust Accidents INFORM rare ID Cleanup After a Major Disaster INFORM rare IE Demolition INFORM rare IH Fireworks INFORM rare II High Pollen Count INFORM rare I.T High Winds INFORM rare, may apply to wind speed and direction data IK Infrequent Large Gatherings INFORM rare IM Prescribed Fire INFORM rare IP Structural Fire INFORM rare IQ Terrorist Act INFORM rare IR Unique Traffic Disruption INFORM rare IS Volcanic Eruptions INFORM rare IT Wildfire-U. S. INFORM rare J Construction INFORM rare D2.2.4.2 Corrective Action Process The monitoring agency's corrective action process will be followed in cases of systematic problems or problems affecting a significant amount of data. This process is described in Section CI.2. D2.2.4.3 Notification of EPA or Other Stakeholders For serious or systematic problems impacting data, individuals within the monitoring agency responsible for determining the impact of the data and determining the validation status of the data will be notified. Stakeholders and users of the data that might be impacted by the validation ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 115 of 145 status will also be notified. Monitoring agencies will contact the EPA PAMS Regional Representative who may themselves notify or may instruct the monitoring agency to notify the PAMS Program and EPA PAMS QA Leads to provide documentation of corrective actions affecting the status of a significant amount of reportable data. Such would be the case if the data impacted represented 10% or more of the season's data or jeopardized the ability to meet the completeness MQO. These stakeholders will also be notified when corrective actions have been completed and return to conformance has been demonstrated. Monitoring agencies will include significant problems in their annual QA reports to management. D3 Reconciliation with User Requirements D3.1 Reconciling Results with DQOs The DQOs and intended uses for the PAMS Required Site Network data are discussed in Section A7.1. The DQO for the PAMS Required Site Network is to provide a database of ozone precursors and associated meteorology data that modelers can use to evaluate ozone prediction models. The MQOs listed in Section A7.3 were established to provide the expected data quality modelers need. As needed, EPA modelers will evaluate the quality and suitability of the data and may request revisions to the MQOs which may involve increasing sensitivity, decreasing bias, or increasing precision, for example. Any such adjustments will be communicated to the PAMS Required Site Network stakeholders. As needed, EPA will perform a DQA to assess and characterize the overall network data quality. EPA will prepare a report aggregating the PAMS QA/QC data for the year which may be combined with EPA modelers' data quality and suitability evaluation. The report will attempt to determine whether the PAMS Required Site DQOs are being achieved and whether revisions to the program and QS are needed. Monitoring agencies will perform a DQA for each of their PAMS sites to evaluate the site's attainment of the specified MQOs. Monitoring agencies will include a description of their DQA and the outcomes in the annual QA report described in Section D2.2.4.3. D3.2 Interim Corrective Actions EPA may review PAMS QA/QC data and collected measurements during the first year of the PAMS Required Site network operation. If such an interim assessment indicates that the stated MQOs need to be adjusted to meet the intended use, EPA may revise the sampling design for the PAMS Required Site Network, which may include revising site selection, sampling frequency, QC measurements frequency and acceptance criteria, and equipment maintenance frequency. Changes in MQOs may result in the need to adjust PAMS monitoring procedures during implementation of the program. ------- ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 117 of 145 REFERENCES 1. Review of the National Ambient Air Quality Standards for Ozone https://www.govinfo.gov/content/pkg/FR-2020-12-31/pdf/2020-28871.pdf 2. Cavender, K.A. U.S. EPA OAQPS, Summary of Final Photochemical Assessment Monitoring Stations (PAMS) Network Design. September 25, 2015. Available at (accessed May 2023): http://www3.epa.gov/ttn/naaqs/standards/ozone/data/20150925cavender.pdf 3. Standard Practice for Characterizing Surface Wind Using a Wind Vane and Rotating Cup Anemometer, ASTM Designation: D 5741-96, Annual Book of ASTM Standards, Section 11, 1996. 4. Holzworth, G.C. Estimates of Mean Maximum Mixing Depths in the Contiguous United States .Monthly Weather Review, 92, 235-242, 1964. 5. Holzworth, G.C. Mixing Heights, Wind Speeds, and Potential for Urban Air Pollution Throughout the Contiguous United States, Publication No. AP-101. Research Triangle Park, NC: U.S. EPA, 1972. 6. Irwin, J.S., and J.O. Paumier. Characterizing the Dispersive State of Convective Boundary Layers for Applied Dispersion Modeling. Boundary-Layer Meteorology, 53, 267-296, 1990. 7. Quality Assurance Handbook for Air Pollution Measurement Systems. Volume IV - Meteorological Measurement, EPA-454/B-08-002, U.S. Environmental Protection Agency, March 2008. Available at (accessed May 2023): https://www.epa. gov/ sites/default/files/2021 - 04/documents/volume iv meteorological measurements.pdf 8. U.S. EPA. Technical Note - Use of Electronic Logbooks for Ambient Air Monitoring 04/20/2016. Available at (accessed May 2023): https://www.epa.gov/sites/production/files/2017- 02/documents/electronic logbook final 4 20 16.pdf 9. Quality Assurance Handbook for Air Pollution Measurement Systems. Volume II - Ambient Air Quality Monitoring Program, EPA-454/B-17-001, U.S. Environmental Protection Agency, January 2017. Available at (accessed May 2023): https://www3.epa.gov/ttn/amtic/files/ambient/pm25/qa/Final%20Handbook%20Documen t%201 17.pdf 10. Center for Environmental Research Information, Office of Research and Development. U.S. Environmental Protection Agency Compendium Method TO-11 A. Determination of Formaldehyde in Ambient Air Using Adsorbent Cartridge Followed by High Performance Liquid Chromatography (HPLC) [Active Sampling Methodology], Available at (accessed May 2023): https://www3.epa.gov/ttnamtil/files/ambient/airtox/to-llar.pdf ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 118 of 145 11. U.S. EPA. EPA Traceability Protocol for Assay and Certification of Gaseous Calibration Standards. EPA/600/R-12/531. May 2012. Available at (accessed May 2023): https://cfpub.epa.gov/si/si public file download.cfm?p download id=522029&Lab=NR MRL 12. U.S. EPA. Transfer Standards for Calibration of Air Monitoring Analyzers for Ozone. Technical Assistance Document. EPA-454/B-13-004, October 2013. Available at (accessed May 2023): https://www.epa.gov/sites/default/files/2020- 09/documents/ozonetransferstandardguidance.pdf 13. U.S. EPA. 2002. EPA QA/G-8, Guidance on Environmental Data Verification and Validation. (EPA/240/R-02/004). Washington, DC. Available at https://www.epa.gov/sites/production/files/2015-06/documents/g8-final.pdf accessed May 2023. 14. U.S. EPA. 2006. EPA QA/G-9R, Data Quality Assessment: A Reviewer's Guide (EPA/240/B-06/002). Washington, DC. Available at https://www.epa.gov/sites/production/files/2015-08/documents/g9r-final.pdf accessed May 2023. 15. U.S. EPA. 2023. Technical Assistance Document for Sampling and Analysis of Ozone Precursors for the Photochemical Assessment Monitoring Stations Program. Revision 3. Available at (accessed May 2023): https://www.epa.gov/amtic/photochemical- assessment-monitoring-stations-pams 16. U.S. Census Bureau. Metropolitan and Micropolitan Statistical Areas Population Totals and Components of Change: 2020-2021. Available at (accessed May 2023): https://www.census.gov/data/tables/time-series/demo/popest/2020s-total-metro-and- micro-statistical-areas.html 17. Code of Federal Regulations, Appendix A to Part 58—Quality Assurance Requirements for Monitors Used in Evaluations of National Ambient Air Quality Standards. Available at (accessed May 2023): https://www.ecfr.gov/current/title-40/chapter-I/subchapter- C/part-58#Appendix-A-to-Part-58 18. U.S. EPA. 2000. EPA Order: Policy and Program Requirements for the Mandatory Agency-Wide Quality System. Available at (accessed May 2023): https://www.epa.gov/sites/default/files/2013-10/documents/2105Q.pdf ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 119 of 145 APPENDIX A SLT MONITORING AGENCY QAPP APPROVAL ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 120 of 145 Approval of PAMS Required Site SLT Monitoring Agency QAPP The SLT Monitoring Agency has added or edited the National PAMS Required Site Quality Assurance Project Plan to specify details specific to the monitoring agency in the following Sections (indicated in yellow in the National QAPP): Section Section Title Section Section Title A3 Distribution List B3 Sample Handling and Custody Requirements A5.1 PAMS Required Site(s) B5.1 Quality Control for Field Activities (QA Sample Collection) A6.2 Personnel and Organization B6.1 Instrument Acquisition A6.3 Schedule for PAMS Required Site Activities B6.4 Instrument Maintenance A7.3.1 Waiver for Speciated VOCs by Auto-GC B7.2 Calibration Support Equipment A8 Special Training Requirements/Certification B8 Inspection/Acceptance Requirements for Supplies and Consumables A9 Documentation and Records BIO Data Management A9.1 Recording of Data C.1.1.1 Instrument Performance Audits A9.4 Records Archival and Retention CI.2 Corrective Actions B1 Sampling Process Design (Waivers) C2 Reports to Management Bl.1.2 Speciated VOCs To Be Measured D1 Data Review, Verification, and Validation Requirements B2 Sampling and Measurement Methods Dl.l Data Verification and Validation Responsibilities B2.1 Chemical Parameters - Inlet Composition D2 Data Verification and Validation Methods By signing below, the signatories indicate that the SLT Monitoring Agency has provided the appropriate details for the Sections listed above and has clearly identified all deviations from the National PAMS QAPP Revision 1.0 and provided documentation that the revisions provide equivalent or higher quality monitoring data. Delegated QAPP Approval Authority The has been delegated full QAPP Approval and signature Agency Name authority by EPA Region . State/Local/Tribal Agency Print Name: Signature: Date: Director Print Name: Signature: Date: Quality Assurance Officer EPA Regional Office Acknowledgment or Approval Print Name: Signature: Date: PAMS Regional Coordinator Print Name: Date: Signature: Quality Assurance Manager ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 121 of 145 APPENDIX B EXAMPLE QUALITY BULLETIN ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 122 of 145 Example Quality Bulletin Number: Date: Page of Supersedes No,:_ Dated: Background Subject: QA Lead Y/N Replace and Discard Original Add Material to Document Retain this bulletin until further notice Discard this bulletin after noting contents This bulletin will be invalid after: Date: This bulletin will be incorporated into quality Procedure No. by Date: ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 123 of 145 APPENDIX C EXAMPLE CHAIN-OF-CUSTODY FORM ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 124 of 145 PAMS REQUIRED SITE NETWORK SAMPLE CHAIN OF CUSTODY FORM Sample ID Presample Storage1 Sample Type2 Sample Start (date & time)3 Sample Stop (date & time)3 Sample Shipment Temperature4 Sample Storage at Laboratory5 1 Media storage location (e.g. refrigerator identifier) and storage temperature range {should be <4°C) 2 Ambient Primary (AP), Ambient Duplicate (AD), Ambient Collocated (AC), Field Blank (FB), Trip Blank (TB), Exposure Blank (EB) 3 Note the sample start and end times were recorded on the sample collection form and are transcribed to this form 4 Sample shipment temperature may indicate "in cooleron ice" and may include thermometer identifier 5 Sample storage location (e.g. refrigerator identifier) and storage temperature range (should be <4°C) These Transfer6*7 Date/Time Transfer7 Date/Time fields are Relinquished by: Received by to be Relinquished by: Received by completed Relinquished by: Received by as Relinquished by: Received by needed: Relinquished by: Received by Relinquished by: Received by 6 Collected samples were handled according to SOP. 7 Document transfer of collected samples to/from a shipper or courier, as appropriate, and record shipper and tracking information page of ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 125 of 145 APPENDIX D EXAMPLE STAFF PROFICIENCY TRAINING FORM ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 126 of 145 EXAMPLE PAMS REQUIRED SITE TRAINING FORM Staff Member The staff member has read the following PAMS Required Site quality system documents: Document Version and Effective Date Date Read/Initials Version and Effective Date Date Read/Initials Version and Effective Date Date Read/Initials Monitoring Agency PAMS Required Site QAPP Determination of Speciated VOCs by Auto-GC Collection of Carbonyls Samples Measurement of True NO2 Measurement of Mixing Layer Height by Ceilometer Measurement of Wind Speed and Wind Direction Measurement of Solar Radiation and UV Radiation Measurement of Precipitation Measurement of Temperature, Relative Humidity, and Barometric Pressure Data Verification and Validation Other SOPs as defined by the monitoring agency ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 127 of 145 INITIAL DEMONSTRATION OF CAPABILITY Staff will read the current version of the SOP governing the procedure(s) and complete an initial demonstration of capability (IDOC) which will include either: a. Observing a trained individual perform the procedure(s), performing the procedure with assistance from a trained individual, and performing the procedure(s) independently under the observation of a trained individual, or b. Performance of the procedure(s) independently under the observation of a QA staff member or supervisor Procedure Date Trainee Observed Trainer Perform Procedure(s) Date Trainee Performed Procedure(s) with Trainer Date Trainee Performed Procedure(s) Independently Under Observation Approval by Director to Perform Procedure Independently Determination of Speciated VOCs by Auto- GC Collection of Carbonyls Samples Measurement of True NO2 Measurement of Mixing Layer Height by Ceilometer Measurement of Wind Speed and Wind Direction Measurement of Solar Radiation and UV Radiation Measurement of Precipitation Measurement of Temperature, Relative Humidity, and Barometric Pressure Other Procedures as necessary ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 128 of 145 CONTINUING DEMONSTRATION OF CAPABILITY Once the IDOC is completed, staff will read the current version of the SOP governing the procedure(s) and complete a continuing demonstration of capability (CDOC) which will include performance of the procedure(s) independently under the observation of a QA staff member, supervisor, or other trained staff member. Procedure Date Trainee Performed Procedure(s) Independently Under Observation Approval by Director to Perform Procedure Independently Determination of Speciated VOCs by Auto-GC Collection of Carbonyls Samples Measurement of True NO2 Measurement of Mixing Layer Height by Ceilometer Measurement of Wind Speed and Wind Direction Measurement of Solar Radiation and UV Radiation Measurement of Precipitation Measurement of Temperature, Relative Humidity, and Barometric Pressure Other Procedures as necessary ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 129 of 145 ADDITIONAL AND SUPPLEMENTAL TRAINING The staff member has received the following additional or supplemental training: (provide documentation examples, such as attendance forms, certificates of course completion, etc.) Training Title Type of Training1 Initials/Date 1 ATS = Attended training sessions, ATW = Attended training webinars, RTV = Reviewed training videos, RTC = Received training certifications - refer to attached certificates ------- ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 131 of 145 APPENDIX E EXAMPLE SITE VISIT CHECKLIST ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 132 of 145 Site operators should complete this checklist with each visit to the PAMS Required Site during PAMS season. Observations recorded in the site log may be referenced as "RSL" (refer to site log). Site ID: Date of Visit and Operator Initials: Check OK? (Y/N) Comments GENERAL Vandalism Operational Hazards (broken decking, stinging insects, snakes, icicles, etc.) Nearby recent construction Landscaping activities (mowing, tree trimming, etc.) Weather damage Shelter environmental conditions within specification MANIFOLD INLET Inlet probe clear (no insect nests, debris, etc.) Bypass fan operating Manifold flow within spec Connections to manifold secure Manifold cleaned within prescribed frequency SITE LOG Visitors or events since last visit? Log updated with this visit? DATA ACQUISITION SYSTEM Verify no DAS error messages/alarms Ensure DAS communication with instruments DAS clock is accurate to ± 1 minute ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 133 of 145 Check OK? (Y/N) Comments TRUE N02 Instrument display is on No error messages/alarms Instrument reading is reasonable for scheduled monitoring (ambient, span, zero) Calibration cylinders > 400 psi Zero air generator cycling properly Calibrator does not show errors/alarms Instrument clock is accurate ± 1 minute CARBONYLS Instrument status correct for sampling program If sampling day, instrument is sampling and flow is correct (1 LPM) If non-sampling day, program displays correct date for next sample Sample cartridges are installed correctly Sampling unit does not show error messages/alarms AUTO-GC No error messages/alarms Correct sequence line is active (should be ambient sample during daytime) Correct part of the measurement cycle is active (sample collection, sample desorption, GC analysis, GC cooling, etc.) Hydrogen generator has sufficient water and does not show error messages/alarms ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 134 of 145 Check OK? (Y/N) Comments Carrier gas, RTS, H2 cylinders have sufficient pressure Instrument clock is accurate ± 1 minute Zero air generators) operating properly Compressor operating properly METEOROLOGY Complete weekly meteorology sensor visual checklist Temperature is reasonable with ambient conditions and recorded in DAS Wind speed and direction operation are reasonable for conditions Shrouds for thermometer and hygrometer are clear of debris Solar and UV data in DAS are reasonable to conditions (sunny, cloudy, etc.) Precipitation gauge is operational and has registered precipitation events in DAS Ceilometer lens is clean Meteorology measurements reasonable compared to nearby NWS sites COMMENTS: ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 135 of 145 APPENDIX F GUIDANCE FOR PAMS MONITORING AGENCIES TO INCORPORATE PAMS REQUIREMENTS INTO ANNUAL MONITORING NETWORK PLANS ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 136 of 145 Guidance for (1) New Photochemical Assessment Monitoring Stations (PAMS) Required Network Implementation Plans (and waivers), and (2) New Enhanced Monitoring Plans (EMPs). Air agencies are required to establish and begin operating additional PAMS networks resulting from a new census (see 40 CFR 58.14(b)). This guidance and the following two attachments represent templates for consideration for implementation plans for the (1) Required Monitoring Network PAMS site (at certain NCore sites) and (2) for the EMPs required for moderate or higher nonattainment areas (NA) and states within the Ozone Transport Region (OTR). These templates should help in the development of implementation plans that should be included in the annual monitoring network plan as required by 40 CFR 58.10. For higher population NCore sites (i.e., those in Core Based Statistical Areas (CBSAs) greater than 1,000,000), the Required Monitoring Network Implementation Plan must include the final site location, the types of instruments to be installed, and frequency of measurements that will be made. The Required Monitoring Network Implementation Plans should state the methods and procedures that will be followed as stipulated in the final PAMS rule, national PAMS Quality Assurance Program Plans (QAPP), and the PAMS Technical Assistance Document (TAD). The expected auto gas chromatograph (GC) monitoring systems will require a level of expertise which may not be currently available to monitoring agencies. Early planning is crucial to meeting deployment and measurement deadlines. The final ozone national ambient air quality standards (NAAQS) rule has waiver provisions which allow monitoring organizations which have low concentrations of ozone (as defined in the rule) to request a waiver from implementing PAMS at an otherwise required NCore site entirely1, or to make PAMS measurements at alternative locations such as existing PAMS sites or existing National Air Toxics Trends Station (NATTS) sites11. In addition, while it is expected that auto GCs will be used for VOC measurements in order to report hourly measurements, there is an opportunity to seek a waiver and instead collect three 8-hour canister samples, once every three days111. In addition, a monitoring organization may request that it utilize data from a nearby meteorological station rather than establish its own™. Monitoring organizations must request a waiver from any deviation described above. The waivers will be in the form of a one- or two- page technical memo that describes the need and rationale for the waiver, and any other requisite supporting information including alternative locations (such as existing PAMS sites), and/or proposed alternative measurement procedures (see end notes to this memo in this regard). The waiver will be submitted to the EPA Regional Administrator for review and approval. Waivers may be submitted with the required Annual Monitoring Network Implementation Plan or as a standalone document, if agreed to by the local EPA Regional Office. • Monitoring organizations should submit the draft Implementation Plan for required PAMS locations and any waivers to EPA Regional Offices by May 1 of the year prior to the start of sampling, along with their draft Annual Monitoring Network Plan (AMNP). This will ensure that a 30-day public notice is provided, and EPA may provide comments during that time. Final Implementation Plans should be submitted by July 1 of the year prior to the start of sampling along with the AMNP. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 137 of 145 • As with all AMNPs, the EPA Regions will have 120 days to review the waivers and the proposed PAMS Implementation Plans, and provide a formal response to the state's plan (and waiver if proposed) no later than October 31 of the year prior to the start of sampling (based on the submission of the final AMNP by July 1). All 03 moderate (and worse) NA areas and states in the OTR must develop and implement EMPs. These EMPs must include the final site location, the types of instruments to be installed, and the frequency of measurements that will be made at the site. They should also identify the rational for proposed measurements, and in the case of EMP sites within the OTR, must take into account interstate and interregional transport of ozone and ozone precursors. • As required in 40 CFR 58.10(a)(l 1), an EMP for ozone shall be submitted to the EPA Regional Administrator no later than two years following the effective date of a designation to a classification of Moderate or above O3 nonattainment. Monitoring organizations should submit the draft EMPs for areas in the OTR and moderate NAs to EPA Regional Offices by May 1, along with their draft AMNP. This will ensure that a 30-day public notice is provided, and the EPA can provide comments during that time. Final EMPs should be submitted by July 1 along with the AMNP. • As with all AMNPs, the EPA Regions will have 120 days to review the proposed EMPs, and provide a formal response to the state's plan, no later than October 31. (Based on the submission of the final AMNP by July 1). While not a comprehensive list, EMP may include additional 03 sites; additional NOx or NOy sites; additional VOC/carbonyl measurements (different time periods, different locations and different precursors); or enhanced upper air measurements. EPA encourages that all EMPs be developed in consideration of and in coordination with other nearby PAMS/ EMPs. In the OTR, EPA intends that this coordination should occur and include all states in the OTR. For the states in the OTR, EPA encourages a comprehensive EMP with well-defined objectives. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 138 of 145 References ' Appendix D of 40 CFR Part 58, 5(f) allows an otherwise required NCore site from implementing PAMS if the ozone design value is less than 85% of the NAAQS, and the area is not considered important regarding upwind or downwind nonattainment areas. States/ locals which have such an area should consult with the local EPA Regional Office. Such an area would need to submit a request to the EPA Regional Administrator and include a discussion of design values in the area, and all areas nearby- including a discussion of the closest ozone nonattainment area(s), and its relationship (or lack thereof) to air quality in the area seeking a waiver. That request should be part of the AMNP described above, and EPA would approve (or disapprove) the request when it acts on the AMNP. Any alternative method of seeking such a waiver should be agreed with the appropriate EPA Regional Office. II Appendix D of 40 CFR Part 58, 5(c) allows for the collection for required PAMS measurements at an alternative location. For areas considering such a request, it must be demonstrated that the alternate location will provide representative and useful data for regional or national tracking of trends in ozone precursors. For example, it may be a nearby location that has measured PAMS compounds in the past, and could be beneficial from a trends perspective. Any request should meet the specific requirements of the rule, be included in the AMNP, and to be acceptable, be approved by the EPA Regional Administrator. III Appendix D of 40 CFR Part 58, 5(d) provides that the EPA Regional Administrator may grant a waiver from continuous VOC measurements to allow for speciated VOC measurement as three 8-hour averages on every third day during the ozone season. EPA will consider waivers where precursor concentrations are low, or for other logistical or programmatic constraints. In considering approval of a waiver, the EPA Regional Administrator will consider the ability to compare and utilize other nearby PAMS (and EMP) locations to ensure the data collected can be used in a useful manner. Any request should meet the specific requirements of the rule, be included in the AMNP, and to be acceptable, be approved by the EPA Regional Administrator. IV Appendix D of 40 CFR Part 58, 5(e) provides that the EPA Regional Administrator may grant a waiver allowing representative meteorological data from nearby monitoring stations to be used to meet the meteorological measurements required. To be acceptable, a request must provide for the location of the alternative measurements, a detailed description of the appropriateness and representativeness of the location relative to PAMS location, assurance that the data will always be available, and ensure that the data meet appropriate EPA quality assurance requirement for those measurements. Any request should meet the specific requirements of the rule, be included in the AMNP, and to be acceptable, be approved by the EPA Regional Administrator. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 139 of 145 PAMS Monitoring Implementation Network Plan Example Monitoring Organizations Required to Operate at NCore Sites (Insert monitoring organization) formerly operated two Photochemical Assessment Monitoring Stations (PAMS) sites in the air monitoring network in 2015, at the (Insert Location) and (Insert Location) sites. However, the recently revised monitoring rule (80 FR 65292; October 26, 2015) requires PAMS measurements June 1 through August 31 at NCore sites that are located in Core-Based Statistical Areas (CBSAs) with populations of 1,000,000 or more. Network Decision ~ The NCore site located at (Insert Location) will serve as the location of the required PAMS site and will measure the following parameters described below. An Inventory of equipment used at the site(s) is provided in attachment 2 ~ We request a waiver from implementing PAMS at an otherwise required NCore site entirely, or to make PAMS measurements at alternative locations such as existing PAMS sites or existing NATTS sites. Rationale for this waiver is provided in Waiver attachment Auto GC Decision Volatile organic compounds (VOCs) - A complete list of the targeted compounds is provided in Table 1. ~ We will measure hourly speciated VOC measurements with an auto-gas chromatograph (GC) using (insert manufacturer). ~ We request a waiver to allow three 8-hour samples every third day as an alternative to daily hourly speciated VOC measurements at locations (insert locations). Rationale for this waiver is provided in Waiver Attachment Meteorology Measurements Decision - Note: EPA is suggesting the use of ceilometers for determining mixing height, however other types of meteorological equipment that provide for an indication of mixing height can be proposed ~ Will measure wind direction, wind speed, temperature, humidity, atmospheric pressure, precipitation, solar radiation, UV radiation, and mixing height. We have elected to use the following instrumentation to measure the parameters described above: (insert equipment models and manufacturer). ~ We request a waiver to allow meteorological measurements to be obtained from other nearby sites. Rationale for this waiver is provided in the Waiver attachment. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 140 of 145 Other Required Measurements Carbonyls - Carbonyls sampling at a frequency of three 8-hour samples on a one-in-three- day basis (-90 samples per PAMS sampling season) using (insert sampler and analytical manufacturer). Sites will be required to measure and report formaldehyde and acetaldehyde and are encouraged to measure and report acetone and benzaldehyde. The TO-11A test method, as used in the National Air Toxics Trends (NATTS) program3 will be used. Nitrogen Oxides - Will monitor for NO and NOy (total oxides of nitrogen) in addition to true NO2. The true NO2 is required to be measured with a direct reading NO2 analyzer, cavity attenuated phase shift (CAPS) spectroscopy or photolytic-converter NOx analyzer. We have elected to use (insert type and manufacturer) for the true NO2 measurement. NO and NOy will be measured using a (insert manufacturer). Table 1 PAMS Target Speciated VOCs List Priority Compounds Optional Compounds 1,2,3- trimethylbenzene a m-ethyltoluene a 1,3,5- trimethylbenzene isopropylbenzene b 1,2,4- trimethylbenzene a n-butane 1-pentene m-diethlybenzene 1-butene n-hexane b 2,2-dimethylbutane methylcyclohexane 2,2,4- trimethylpentane b n-pentane 2,3,4- trimethylpentane methylcyclopentane benzene a b o-ethyltoluene a 2,3-dimethylbutane n-decane cis-2-butene o-xylene a b 2,3- dimethylpentane n-heptane ethane c p-ethyltoluene 2,4- dimethylpentane n-nonane ethylbenzene a b propane 2-methylheptane n-octane ethylene propylene 2-methylhexane n-propylbenzenea isobutane styreneab 2-methylpentane n-undecane isopentane toluene a b 3-methylheptane p-diethylbenzene isoprene trans-2-butene 3-methylhexane trans-2-pentene m&p-xylenes a b total non-methane organic carbon (TNMOC) 3-methylpentane a/p-pinene acetylene 1,3 butadiene b cis-2-pentene carbon tetrachloride b cyclohexane ethanol cyclopentane tetrachloroethylene b Source: Revisions to the Photochemical Assessment Monitoring Stations Compound Target List. U.S. EPA, November 20, 2013 a Important SOAP (Secondary Organic Aerosols Precursor) Compounds b HAP (Hazardous Air Pollutant) Compounds c Non-reactive compounds, not considered to be VOC for regulatory purposes 3 See NATTS Technical Assistance Document for TO-11A method. ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 141 of 145 PAMS Monitoring Implementation Network Plan Example Monitoring Organizations Not Required to Operate at NCore Sites (Insert monitoring organization) formerly operated (x#) Photochemical Assessment Monitoring Stations (PAMS) sites in its air monitoring network in 2015, at the (Insert Location) and (Insert Location) sites. The recently revised ozone NAAQS rule1 requires PAMS measurements at NCore sites that are located in Core-Based Statistical Areas (CBSAs) with populations of 1,000,000 or more. Since (Insert monitoring organization) NCore sites are located in CBSAs with populations less than one million, this requirement does not apply (insert monitoring organization). (In some cases, a state may have an NCore site that requires PAMS measurements, but additional "Enhanced Monitoring" sites are necessary to adequately characterize the problem.) States with moderate or above ozone nonattainment areas and states within the Ozone Transport Region (OTR) are required to develop and implement Enhanced Monitoring Plans (EMPs). These EMPs are intended to provide monitoring organizations with the flexibility to implement additional monitoring to suit the needs of their area such as additional ozone, ozone precursor, and/or meteorological monitoring activities. (For an area in the OTR include the following: In developing this plan, we have coordinated with all other states (and DC) in the OTR and EPA Regions 1, 2, and 3. As a contiguous area of interregional transport, we have agreed to the spatial distribution of these monitoring locations, as well as the type and frequency of the air quality (and other measurements). (Insert monitoring organization) has determined the EMP measurement options will include (but are not limited to) additional ozone air measurement at (insert location), upper air measurements (insert location), measurements of total VOC or enhanced/reduced amount of VOCs/carbonyl species (identify), additional nitrogen dioxide monitoring (insert location), and additional meteorology/boundary layer measurements. This required EMP reflects local needs within the context of interstate, interregional transport of ozone and ozone precursors. 180 FR 65292; October 26, 2015 ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 142 of 145 Attachment 1 Waiver Requests and Rationale Waiver from implementing PAMS at an otherwise required NCore site (waiver could be either in its entirety, or to be at a different location) Rationale for this waiver Auto GC Waiver Request We request a waiver to allow three 8-hour samples every third day as an alternative to daily hourly speciated VOC measurements at locations (insert locations). Rationale for this waiver Meteorological Waiver Request We request a waiver to allow meteorological measurements to be obtained from other nearby sites. Rationale for Waiver ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 143 of 145 Attachment 2 Equipment Inventory (Example) ------- EPA-454/R-23-003 PAMS Required Network QAPP (Rl) May 2023 Page 144 of 145 Region 2 State New York AQSID 36-081-0124 CBSA ew York-Newark-Jersey City, NY-NJ-PA Parameter Category Detail Site Is the AQS site ID listed above the expected PAMS Core site location? No What is the status of the decision for the expected PAMS Core site location (not started, draft, or final)? Not Started Is there an alternate PAMS Core site location selected? Yes Identify type of alternative site (existing PAMS, NATTS, etc) Existing PAMs Alternate site AQS ID (if known) 36-005-0133 Mixing Height Is there an existing functional ceilometer or other similar instrument available for use? No but State Installing Network current location (at future PAMS Core site, at other site, not applicable) instrument type (ceilometer, radar profiler, etc) manufacturer model date purchased comments Mesonetwill include: Auto GC Is there an existing Auto GC available for use? Yes current location (at future PAMS Core site, at other site, not applicable) At Site manufacturer Agilent/Markes model 7890A/Unity Air Server 2 date purchased 04/2016//07/2015 Does it have a service contract? GC under warranty/Working on AC for Markes now comments True N02 Is there an existing true N02 instrument available for use? No current location (at future PAMS Core site, at other site, not applicable) instrument type (photolytic conversion, cavity ringdown, CAPS, etc) manufacturer model date purchased comments NOx analyzer at site Carbonyls Sampling Is there an existing sequential carbonyls sampling unit or similar instrument available for use? Yes current location (at future PAMS Core site, at other site, not applicable) In storage at Rensselaer, Site has two channel unit now. manufacturer Atek model 8000 date purchased 2012 comments Carbonyls Analysis Does the site currently have a support laboratory for carbonylsor plans to use a support laboratory? Yes, in house laboratory name NYSDEC Air Resources Laboratory comments Barometric Pressure instrument type (aneroid barometer, etc) Yes - Electronic manufacturer Vaisala model WT520 date purchased comments UV Radiation instrument type (UV radiometer, etc) No manufacturer model date purchased comments Solar Radiation instrument type (pyranometer, etc) No manufacturer model date purchased comments Precipitation instrument type (tipping bucket, weighing, etc) Electronic Gauge - Weighing manufacturer ETI Instrument Systems model NOAH IV date purchased 2011 comments Data in NADP Database ------- United States Office of Air Quality Planning and Standards Publication No. EPA-454/R-23-003 Environmental Protection Air Quality Assessment Division May 2023 Agency Research Triangle Park, NC ------- |