Standard Operating Procedures for Air Toxics Sampling and Analysis by ERG, Exercises of Meteorology

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Viant Ethylene Oxide Monitoring Version 0.0 10/31/2018 Page 1 Michigan Department of Environmental Quality (DEQ) Air Quality Division Quality Assurance Project Plan (QAPP) Viant Ethylene Oxide Monitoring Grand Rapids, MI October 31, 2018 – Original Version 0.0 Viant Ethylene Oxide Monitoring Version 0.0 10/31/2018 Page 2 QAPP Review and Revision Log Document and Version: Viant Ethylene Oxide 0.0 Reviewed: Initials Date Revised: Initials Date Viant Ethylene Oxide Monitoring Version 0.0 10/31/2018 Page 5 3.0 Distribution List Amy Robinson, MDEQ-AQD; Jason Duncan, MDEQ-AQD; Eric Hansen, MDEQ-AQD; Susan Kilmer MDEQ-AQD; Bob Sills MDEQ-AQD. 4.0 Project/Task Organization Table 1: Roles & Responsibilities Individual(s) Assigned Responsible for: Authorized to: Amy Robinson • Project Manager • QAPP revisions/approval, data analysis, data validation, report • Communicate findings to USEPA • Collect, document, ship/deliver samples • Determine whether DQOs are met • Liaison between ERG and MDEQ Amy Robinson/ Jason Duncan/ Eric Hansen • Field Operations • QC on field sampling • Collect, document, ship/deliver samples Eastern Research Group (ERG) (Julie Swift) • Laboratory Analysis • Laboratory QC • Analyze samples Eric Hansen • Sample Custodian • Ship and receive canisters Bob Sills • Toxicology Review • Report Toxicology Results Susan Kilmer • QA Review • Flag Data for QA reasons Figure 1: Organization Chart Amy Robinson Project Mangager Eric Hansen Senior Auditor Jason Duncan Environmental Tech. Bob Sills Toxicologist Eastern Research Group Laboratory Susan Kilmer QA Reviewer Viant Ethylene Oxide Monitoring Version 0.0 10/31/2018 Page 6 5.0 Problem Definition/Background Healthcare facilities and commercial sterilization facilities often use ethylene oxide (EtO) to sterilize moisture and heat-sensitive medical instruments. In December 2016, USEPA updated EtO from a “probable human carcinogen” to a “human carcinogen” and increased its lifetime inhalation cancer risk estimate about 60 times. This means that EtO is considerably more potent, and more likely to induce cancer in humans than previously thought. The updated EtO cancer potency information supports the need to reduce EtO air emissions where it impacts human health. The 2014 draft National Air Toxics Assessment (NATA) estimates as well as refined AERMOD modeling of reported emissions, elevated cancer risk attributable to EtO in the Grand Rapids, Michigan area which warrants further evaluation. As an initial step to evaluate the exposure concentrations of EtO in the area near Viant (N0795), MDEQ will conduct a limited air monitoring study near the Viant facility in Grand Rapids, Michigan. Figure 2: Modeling Results for Viant and Study Map The objective of the ambient air monitoring activities is to reliably detect and quantify ambient air EtO concentration near the Viant facility with USEPA Method TO-15. The monitoring will be conducted in 3 phases. Phase I is intended to be a screening phase to identify whether EtO persists in the ambient air at detectable levels. A set of 24-hr canisters will be deployed on one sampling day around the facility. This will provide a basis for determining whether additional and more extensive monitoring is necessary to better characterize human exposure to EtO. Viant Ethylene Oxide Monitoring Version 0.0 10/31/2018 Page 7 6.0 Project/Task Description The MDEQ will follow the monitor siting criteria detailed in the Code of Federal Regulations (CFR) Chapter 40 Section 58, Appendix E, where possible, relevant and appropriate for this monitoring study. MDEQ will consider monitor placement guidelines such as the following: • Locating the canister in an area that has an unobstructed air flow, especially in the direction of any recognized sources of target analytes (following MDEQs Sampling Plan for this study and any specific instructions form ERG that accompany the canisters); • Avoiding locations that are directly influenced by nearby adjacent, biasing emission sources to the extent possible; • Avoiding locations where reactive surfaces may cause chemical changes in the air sampled; • Documenting the sampler siting location with information such as digital pictures of the site from the eight cardinal directions, sampler height and GPS coordinates (Using the Sampling Location Identification Table for this study). Phase I Monitoring: One (1) sampling day in November or 2018, with multiple canisters deployed, should provide data regarding the ambient concentrations of EtO in the area. Phase I canister analysis will be conducted by ERG, national contractor for the NATTS program. Measured ambient EtO concentrations above the minimum detection limit (MDL) of 0.0453 ppbv or 0.0819 µg/m3 will trigger a second, more extensive monitoring effort. Each sample will consist of one Summa canister with an accompanying critical orifice to be installed on the canister prior to deployment and according to instructions from ERG. The orifice will restrict the flow so that when the canister (starting under vacuum) is opened it will slowly fill over a 24-hour period of time. A field operator will manually open and close each canister, documenting, among other information, sample location, time the canister is opened, time the canister is closed, and make observations about site conditions and meteorology. Samples will be logged on a chain of custody form, and the form and sample will be sent to ERG once all samples are collected. The samples will be analyzed using method TO-15 for VOCs. Primary and duplicate samples will be clearly labeled. One sampling event will be conducted. The dataset will consist of 3-5 Summa canisters being placed around the fence line. An additional canister will be co-located with one of the canisters to provide duplicate results. Upwind and downwind will be determined using meteorology data from MDEQ’s Grand Rapids Monroe Street (26-081-0020) monitoring site. Phase II Monitoring: The Phase II monitoring effort will be designed based on the results of Phase I with respect to the number and location of the samples. Viant Ethylene Oxide Monitoring Version 0.0 10/31/2018 Page 10 a 24-hour period of time. A field operator will manually open and close each canister, documenting sample location, date and time canister is opened and closed, initial and final gauge vacuum, and local observations. The field operator will follow MDEQ AQD’s Standard Operating Procedure found in the AMU QAPP Volume II, Section 8.17, “VOC Fixed Orifice Sampling”, dated 10/2/2018. Samples will be logged on a chain of custody form, and the form and samples will be sent to ERG during Phase I and Phases II and III, if necessary, within 10 days of collection. The samples will be analyzed using method TO-15 for VOCs. The AQD’s Grand Rapids – Monroe Street (26-081-0020) Monitoring Station will be used meteorological measurements of wind speed/wind direction. That meteorology data will be stored in hourly format on the stations data logger and will be backed up in the Envista ARM database. 12.0 Sampling Handling & Custody Physical air samples for VOCs will be collected in Summa canisters which have been cleaned and evacuated according to strict SOPs. ERG has developed and qualified SOPs and QAPPs (Support for the EPA National Monitoring Programs (UATMP, NATTS, CSATAM, PAMS, and NMOC Support) Contract No. EP-D-14-030 2018 Quality Assurance Project Plan Category 1) for the TO-15 analytical method. Chain of custody forms will accompany the canisters to and from the lab and will be completed by the field staff as the samples are collected. The chain of custody form is included in the Sample Plan for this project. 13.0 Analytical Methods Method TO-15 will be used to analyze the samples. ERG has SOPs in place for this method as well as a QAPP. (UATMP, NATTS, CSATAM, PAMS, and NMOC Support) Contract No. EP-D- 14-030 2018 Quality Assurance Project Plan Category 1). 14.0 Quality Control Analytical precision is calculated by comparing the differences between replicate analysis (two analyses of the same sample) from the arithmetic mean of the two results as shown below. Replicate analysis with low variability have a lower Relative Percent Difference (RPD) (better precision), whereas high variability samples have a higher RPD (poorer precision). = | − | ∗ 100 Where: X1 = Ambient Air concentration of a given compound measured in one sample; X2 = Concentration of the same compound measured during replicate analysis; X = Arithmetic mean of X1 and X2. Viant Ethylene Oxide Monitoring Version 0.0 10/31/2018 Page 11 15.0 Instrument/Equipment Testing, Inspection, and Maintenance ERG will inspect all canisters and orifices prior to sending them to the field; the lab will look for any defects or damage to the equipment and will ensure all components are clean. Field operators will inspect all equipment upon receipt, to initiating the sample, at sample collection, and prior to shipping the sample back to the lab. Operators will want to look for damage that occurred during the shipping of sampling, and also to look for cleanliness of the equipment, especially the inlets of the orifices. Field operators should also take care that the orifices are not cross-threaded when attaching the summa canister. The operators will also want to ensure that the connection is tight. Any problems with the orifices or canisters should be documented and communicated to the lab and the principal investigator. 16.0 Instrument/Equipment Calibration and Frequency The Summa canisters and sampling orifices calibration method and frequency are documented in the ERG QAPPs and SOPs. (UATMP, NATTS, CSATAM, PAMS, and NMOC Support) Contract No. EP-D-14-030 2018 Quality Assurance Project Plan Category 1). 17.0 Inspection/Acceptance of Supplies & Consumables Upon receipt of the Summa canisters ERG will visually inspect the canisters to look for any damage that may have occurred during shipping, per ERG QAPPs and SOPs. (UATMP, NATTS, CSATAM, PAMS, and NMOC Support) Contract No. EP-D-14-030 2018 Quality Assurance Project Plan Category 1). 18.0 Non-direct Measurements The placement of the Summa canisters is, in part, being guided by AQD inspection reports written by AQD inspection staff and updated modeling, using verified company data. During inspections, AQD inspectors determined fugitive emission points and collected data from EtO monitors inside the facility, so that new AERMOD modeling could conducted that accounted for fugitive emissions. 19.0 Data Management Record keeping begins when the samples leave the lab and go to the field collectors. Field staff will record information about the samples (dates, time, etc.) and continue filling in the chain of custody. The samples and information will go back to the lab, and the samples will be analyzed. The QA Manager will then quality assure the data, ensuring that the data is valid, and then pass the data on to the project manager. The project manager will then consolidate the results into a database for analysis. This data, and the analysis, will be included in the final report. ERG’s QAPP Viant Ethylene Oxide Monitoring Version 0.0 10/31/2018 Page 12 also addresses data management with respect to the canister preparation and analysis and is addressed in ERG’s QAPP in section 15.0. Meteorological data from the Grand Rapids Monroe Street (26-081-0020) will be used for this project. This data and the analysis will be included in the final report and maintained in a database on the MDEQ Share Drive (S: drive). In addition to the data files that will be kept for this project, records that will be kept will include the following: 1. Field Study Logbook – used to record field activity, including but not limited to sample collection (canister/orifice numbers, start/stop dates and times, gauge vacuum, sampling location, local observations, etc.) 2. QAPP and SAP – a copy of this QAPP and the Project Sampling Plan will be available at all times on MDEQ Share Drive (S: drive) 3. Laboratory analysis results and any related data analysis 4. Final Report Individuals identified in section 4.0 will have access to the project’s share drive and will be notified as necessary and appropriate, via email when the QAPP or other relevant documents are revised. 20.0 Assessments and Response Actions An assessment is defined as an evaluation process used to measure the performance or effectiveness of the quality system or the establishment of the monitoring network and sites and various measurement phases of the data operation. The results of quality assurance assessments indicate whether the control efforts are adequate or need to be improved. Documentation of all quality assurance and quality control efforts implemented during the data collection, analysis, and reporting phases is important to data users, who can then consider the impact of these control efforts on the data quality. ERG already performs a number of quality assurance/quality control exercised in order to ensure and document the integrity of the data analyses. Since there is no network, per se, for this project, a network siting review may not be appropriate. However, location of canister sampling will be documented along with meteorological conditions and will be available for any QA manager/staff to review. 21.0 Reports to Management The project manager will summarize data results after all sampling events are completed and analysis results are received from ERG. The report could address performance evaluation and audits, as well as include a data quality assessment. The final report will consolidate any QA findings and address the primary study questions. The project managers will provide a final report to management within the MDEQ. 22.0 Data Review, Verification and Validation Prior to performing any statistical calculations, the reported data from the chain of custody forms will be checked to ensure accurate transcription. ERG will also perform data review, verification, Vol. II QA Manual Section: 8.17 Revision: 0.0 Date: 10/2/2018 Page: 2 Revision/Change History The table below identifies changes to this controlled document and the respective effective date(s) over time. Revision Number History/Change Description Document Author/Owner Management Approver Effective Date 0 Original Document Amy Robinson Susan Kilmer 10/2/2018 Vol. II QA Manual Section: 8.17 Revision: 0.0 Date: 10/2/2018 Page: 3 1.0 Purpose This standard operating procedure describes steps for collection of ambient air samples in the field for later analysis at Easter Research Group (ERG) Laboratory. This SOP is intended for use by field technicians, so samples are collected consistently and documented properly. 2.0 Applicability/Scope This document applies to the collection of air samples in the field. Field Technicians should follow this SOP to ensure samples are collected properly and consistently, and that all documentation is completed. The official signed copy of this SOP will be stored on the AQD Shared Drive under the folder SOPs&QAPPs/SOPs/AMU’s SOPs and will be available to all field sampling staff. The SOP should be reviewed annually. This document outlines obtaining the sampling vessels (i.e. bottles or canisters) from ERG, collecting and documenting the sample in the field, completing the chain-of-custody, and returning the samples to ERG. This SOP is written to provide general instruction for collecting samples; individual projects will have specific needs and processes. Refer to the project specific Quality Assurance Project Plan (QAPP) or sampling plan for details. 3.0 Definitions COC Chain of Custody ERG Eastern Research Group PID Photo Ionization Detector QAPP Quality Assurance Project Plan VOC Volatile Organic Compounds TO-15 Toxic Organic Method 15 4.0 Summary of Method/Procedure Field staff will use containers supplied by ERG to collect air samples by opening the valve on the canister, allowing the sample to enter the canister or bottle then closing the valve. Samples may be grab samples, or composite samples collected over a period of time. Staff will document relevant information on the sample labels (supplied by ERG), Canister Sampling Field Test Data Sheet (from Compendium Method TO-15) and chain of custody form (supplied by ERG). Labelled samples, Field Test Data Sheet and the COC form(s) are then returned to AQD’s sample custodian. The sample custodian will then ship the canister back to ERG for analysis, with the original COC. A copy of the COC form(s) and the original Field Test Data Sheet is retained by the AQD sample custodian. Results will be reported by ERG at a future date. In addition to obtaining canisters from ERG, bottle vac can be obtained from the MDEQ lab for grab samples. The MDEQ COC form is filled out with each sample and a copy is made and retained before dropping the sample off at the MDEQ lab. Vol. II QA Manual Section: 8.17 Revision: 0.0 Date: 10/2/2018 Page: 4 5.0 Personnel Qualification/Responsibilities Personnel involved in the collection of samples must meet the minimum training requirements for safety and technical expertise. Minimum training will include a background in air programs and hands on training with air monitoring personnel. The field staff is also responsible for reviewing this SOP prior to conducting sampling using passive canisters. Approved copied of this SOP and the project-specific air monitoring QAPP will be available to field staff throughout the duration of sampling activities. 6.0 Equipment and Supplies Equipment used for the collection of VOC samples will vary depending on the objective of the project and the compounds of interest. Metal canisters or glass bottles could be used to hold the sample, and different volumes of containers are available. Both factors are dictated by the compounds of interest, project goals, and resource availability. Regulators/orifices (obtained from ERG and provided with the vessels) may be attached to the vessels to restrict the flow, allowing for a long and or specific sampling time. Sample labels and COC forms will be supplied by ERG to document sample information. 7.0 Reagents and Standards No reagents or standards are used during sample collection. All reagents and standards used as part of the laboratory analysis can be found the ERG SOPs. 8.0 Health and Safety Considerations Field staff must complete the minimum safety training as required by the MDEQ AQD. Minimum safety trainings include AQD safety training class. Any necessary health and safety equipment need for specific projects must be made in coordination with the AQD safety coordinator. 9.0 Interferences The possibility of contamination of canister samples exists due to the improper handling and wear of canister valves. Additional possibilities of laboratory and storage contamination and preventative procedures would be documented in the ERG or MDEQ laboratory SOPs. Vol. II QA Manual Section: 8.17 Revision: 0.0 Date: 10/2/2018 Page: 7 a) PROJECT NAME = Project name should be a unique name for you to identify this group of samples. b) SAMPLER NAME = Write the sampler’s name and signature. c) STA. NO. = Station Number. For the first canister write “1” for the second canister write “2”, etc. d) DATE = write the date. e) TIME = write the time the sample was taken. This should be filled out last since it will take some time to complete all paperwork before the sampler is actually taken. f) COMP/GRAB = “Composite or Grab Sample”. Check the box under Grab sample. g) STATION LOCATION = write the GPS coordinates of where the sample was taken. h) NO. OF CONTAINERS = “1” 4) Remove the ¼ inch cap from the inlet of the canister. 5) Install the sample inlet assembly and tighten snugly with a 9/16” wrench. 6) Place the canister in the desired sampling position and secure it with a lock and chain, if needed. 7) Record the following information on the Canister Sampling Field Test Data Sheet, attached. Note that not all information requested on the general TO-15 form is needed. a) Site Location b) Sampling Date c) Canister Serial Number d) Operator e) Temperature Start Ambient f) Canister Pressure Start g) Local Time Start h) Leave all of Section C blank 8) Open the canister valve (righty-tighty, lefty loosey). 9) The canister is now filling. It is a good idea to return to the station in a few hours to observe the pressure. It is imperative that the canister still be under slight vacuum at the conclusion of the sampling time. 10) At the conclusion of the sampling time, close the valve tightly, remove the sample inlet assembly and replace the ¼” cap and tighten. 11) Record the following information on the Canister Sampling Field Test Data Sheet, attached. Note that not all information requested on the general TO-15 form is needed. a) Temperature Stop Ambient b) Canister Pressure End c) Local Time Stop d) Leave all of Section C blank 12) Place the canister back in the box and store it in a safe spot under lock and key. Sample should be delivered to the lab as soon as possible. Ensure that the sampler signs and dates the COC under “relinquished by” and that the sample custodian signs and dates the COC under “received by”. A copy of the COC should be given to the sampler. Section C of the Canister Sample Field Test Data Sheet should be filled out before the sample is shipped to the lab. Fill in Laboratory Name, Date Shipped, Who Shipped, How Shipped, and Type of Analysis Requested. Vol. II QA Manual Section: 8.17 Revision: 0.0 Date: 10/2/2018 Page: 8 13) Additional notes may be helpful such as other meteorological conditions and distinct odors. Sampling Handling and Preservation: • Samples should be handled gently and packed to prevent breakage. Ensure all information has been recorded on the sample labels. • Immediately transport samples back to the shipping or lab location with completed Canister Sampling Field Test Data Sheet and COC. Sample Preparation and Analysis Samples will not be prepared or analyzed in the field. Samples will be prepared and analyzed by the lab following their procedures in the laboratory. Troubleshooting • Field Technicians should inspect sample vessels before collecting a sample to be sure the vessel hasn’t been compromised prior to use. Do not use any vessel suspected of having a leak prior to sample collection. • Technicians may hear a hiss or pop as air rushes into a vessel (especially for a grab sample). No sound may indicate the vessel leaked prior to use. • Record all information onto the sample label at the time of collection. Data Acquisition, Calculations and Data Reduction N/A 11.0 Waste Management N/A 12.0 Data and Records Management All COC forms and other field notes will be submitted to the project manager and will be stored with other data associated with the project. The lab will complete analysis of the canisters or bottles as soon as possible after sampling. The lab will submit valid data to the project manager. 13.0 Quality Control & Quality Assurance The field staff must note any deviations from the sample plan or procedure on the sample label and field notes. Also note anything unusual or unexpected that may influence the sample results (i.e. markers, vehicle fuels, newly paved roads, nearby non-target activities, etc.). Vol. II QA Manual Section: 8.17 Revision: 0.0 Date: 10/2/2018 Page: 9 14.0 References USEPA SOP for collection of VOC samples, Document Number R5-ARD-0003-r2, Effective date 9/29/2017. 15.0 Attachments ERG COC MDEQ COC Compendium Method TO-15 Canister Sampling Field Test Data Sheet ERG QAPP A. General Information Site Location: Site Address: Sampling Date: Type of Sample: B. Sampling Information Pressure Interior Ambient Maximum Minimum Start Start Stop Stop Local Time Manifold Flow Rate Canister Flow Rate Flow Controller Readout Start Start Stop Stop C. Laboratory Information Laboratory Name: Date Shipped: Who Shipped: How Shipped: Type of Analysis Requested: Date Results Received: Data Validated: Date Yes No Valid: NULL Code: I, hearby sign, data has been reviewed and validated: Signature/Title Canister Pressure Flow RateSampling Times Elapsed Time Meter Reading Shipped Date: Canister Serial No.: Sampler ID: Operator: Canister Leak Check Date: Compendium Method TO-15 Canister Sampling Field Test Data Sheet Temperautre SUPPORT FOR THE EPA NATIONAL MONITORING PROGRAMS (UATMP, NATTS, CSATAM, PAMS, and NMOC Support) Contract No. EP-D-14-030 2018 Quality Assurance Project Plan Category 1 Eastern Research Group, Inc. 601 Keystone Park Drive, Suite 700 Morrisville, NC 27560 ERG-QAPP-0344-4 Project No. Element No. Revision No. Date Page 0344.00 A2 4 March 2018 ii of xvi 2018 Quality Assurance Project Plan, Category 1 UATMP, NATTS, CSATAM, PAMS, and NMOC Support (Contract No. EP-D-14-030) Approved by: U.S. EPA Project Officer: U.S. EPA QA Manager: U.S. EPA Delivery Order Manager: ERG Program Manager: __ Q __v-£,=---u..-----'(_._&_~----+-, __ Date: =+ ·( 21-( t'6· ERG Deputy Program Manager: { Ja;it 8u.1 l.ic Date: f /.:, 7 /2 ?f tJ I I ERG Program QA Officer: __ Du_v_~ _ f_~------ Date: 7/zr/1~ ERG Deputy Program QA Officer: DISCLAIMER This Category 1 Quality Assurance Project Plan has been prepared specifically to address the operation and management of the U.S. EPA National Monitoring Programs (UATMP, NATTS, CSATAM, PAMS and NMOC). The contents have been prepared in accordance with Level I Specifications of the EPA Requirements for Quality Assurance Project Plans, EPA QA/R-5 and the EPA Guidance for Quality Assurance Project Plans, EPA QA/G-5. Project No. 0344.00 Element No. A2 Revision No. 4 Date March 2018 Page v of xvi TABLE OF CONTENTS (Continued) Section 13 Instrument Calibration and Frequency .................................................................... 1 of 7 13.1 SNMOC Calibration .................................................................................... 1 of 7 13.2 VOC Calibration ......................................................................................... 2 of 7 13.3 Carbonyl Calibration ................................................................................... 4 of 7 13.4 HAPs Calibration ........................................................................................ 5 of 7 13.5 Laboratory Support Equipment Calibration ................................................ 6 of 7 14 Inspection/Acceptance for Supplies and Consumables ........................................... 1 of 5 14.1 Purpose ........................................................................................................ 1 of 5 14.2 Critical Supplies and Consumables ............................................................. 1 of 5 14.3 Acceptance Criteria ..................................................................................... 1 of 5 15 Data Management ................................................................................................... 1 of 7 15.1 Data Recording ............................................................................................ 1 of 7 15.2 Data Validation ........................................................................................... 3 of 7 15.3 Data Reduction and Transformation ........................................................... 3 of 7 15.4 Data Transmittal .......................................................................................... 4 of 7 15.5 Data Summary ............................................................................................. 5 of 7 15.6 Data Tracking .............................................................................................. 6 of 7 15.7 Data Storage and Retrieval .......................................................................... 7 of 7 ASSESSMENT/OVERSIGHT 16 Assessments and Response Actions ........................................................................ 1 of 7 16.1 Assessment Activities and Project Planning ............................................... 1 of 7 16.1.1 External Technical Systems and Data Quality Audits .................... 1 of 7 16.1.2 Internal Technical Systems Audits .................................................. 2 of 7 16.1.3 Proficiency Testing ......................................................................... 3 of 7 16.1.4 Data Assessment for Final Report ................................................... 4 of 7 16.2 Documentation of Assessments .................................................................. 4 of 7 16.2.1 TSA, Data Quality Audit, and PT Documentation .......................... 4 of 7 16.2.2 Internal Data Review Documentation ............................................. 4 of 7 16.3 Corrective Action Reports ............................................................................... 5 of 7 17 Reports to Management .......................................................................................... 1 of 2 17.1 Frequency, Content, and Distribution of Reports ....................................... 1 of 2 17.1.1 Monthly and Annual Reports .......................................................... 1 of 2 17.1.2 Internal Technical System Audit Reports ....................................... 2 of 2 DATA VALIDATION AND USABILITY 18 Data Review and Verification ............................................................................... 1 of 11 18.1 Data Review Design .................................................................................. 1 of 11 18.2 Data Verification ....................................................................................... 2 of 11 18.3 Data Review .............................................................................................. 2 of 11 18.4 Data Reduction and Reporting .................................................................. 3 of 11 18.5 Data Validation ......................................................................................... 4 or 11 Project No. 0344.00 Element No. A2 Revision No. 4 Date March 2018 Page vi of xvi 18.6 Air Quality System .................................................................................... 5 of 11 18.6.1 AQS Flagging and Reporting ........................................................ 6 of 11 19 Data Validation, Verification and Analysis ............................................................ 1 of 2 19.1 Process for Validating and Verifying Data ................................................. 1 of 2 19.1.1 Verification of Data ......................................................................... 1 of 2 19.1.2 Validation of Data ........................................................................... 1 of 2 19.2 Data Analysis .............................................................................................. 2 of 2 20 Reconciliation with Data Quality Objectives .......................................................... 1 of 1 20.1 Conduct Preliminary Data Review .............................................................. 1 of 1 20.2 Draw Conclusions from the Data ................................................................ 1 of 1 21 References ............................................................................................................... 1 of 2 APPENDICES A Exemptions Table B 2018 Sampling Schedule C ERG Standard Operating Procedures ERG-MOR-003B Field Procedure for Collecting Ambient Air Toxics and Carbonyl Compounds Samples Using the ERG:AT/C Sampling System (with O3 Denuder Scrubber) ERG-MOR-003C Field Procedure for Collecting Ambient Air Toxics and Carbonyl Compounds Samples Using the ERG(C):AT/C Sampling System (with O3 Denuder Scrubber) ERG-MOR-003D Field Procedure for Collecting Ambient Air Toxics and Carbonyl Compounds Samples Using the ERG:AT/C Sampling System (with O3 Denuder Scrubber and Mass Flow Meter) ERG-MOR-005 Standard Operating Procedure for the Concurrent GC/FID/MS Analysis of Canister Air Toxic Samples using EPA Compendium Method TO-15 and EPA Ozone Precursor Method ERG-MOR-013 Field Procedure for Collecting Ambient Air Hexavalent Chromium Samples Using the ERG:CR6 Sampling System ERG-MOR-017 Standard Operating Procedure for Developing, Documenting, and Evaluating the Accuracy of Spreadsheet Data ERG-MOR-022 Standard Operating Procedure for the Preparation of Standards in the ERG Laboratory ERG-MOR-024 Standard Operating Procedure for Preparing, Extracting, and Analyzing DNPH Carbonyl Cartridges by Method TO-11A Project No. 0344.00 Element No. A2 Revision No. 4 Date March 2018 Page vii of xvi ERG-MOR-030 Standard Operating Procedure for Canister Sampling System Certification Procedures ERG-MOR-033 Standard Operating Procedure for Hazardous Waste ERG-MOR-039 Standard Operating Procedure for Maintaining Laboratory Notebooks ERG-MOR-044* Standard Operating Procedure for Method 8270C – GC/MS Analysis of Semivolatile Organics ERG-MOR-045 Standard Operating Procedure for Sample Receipt at the ERG Chemistry Laboratory ERG-MOR-046* Field Procedure for Collecting Speciated and/or Total Nonmethane Organic Compounds Ambient Air Samples Using the ERG:S/NMOC Sampling System ERG-MOR-047B Field Procedure for Collecting Ambient Carbonyl Compounds Samples Using the ERG:C Sampling System ERG-MOR-047C Field Procedure for Collecting Ambient Carbonyl Compounds Samples Using the ERG:C Sampling System (new timer) ERG-MOR-049 Standard Operating Procedure for analysis of Semivolatile Organic Compounds (Polynuclear Aromatic Hydrocarbons) Using EPA Compendium Method TO-13A & ASTM D 6209-13 ERG-MOR-057 Standard Operating Procedure for Project Peer Review ERG-MOR-060 Standard Operating Procedure for PDFID Sample Analysis by Method TO-12 ERG-MOR-061 Standard Operating Procedure for Standard Preparation Using Dynamic Flow Dilution System ERG-MOR-062 Standard Operating Procedure for Sample Canister Cleaning Project No. 0344.00 Element No. A2 Revision No. 4 Date March 2018 Page x of xvi LIST OF TABLES (Continued) Table 18-1 Qualifier Codes ................................................................................................................... 7 of 11 18-2 Null Codes .......................................................................................................................... 9 of 11 18-3 Summary of Quantitation and Detection Limit Flags and Applications .......................... 11 of 11 ---- Project No. 0344.00 Element No. A2 Revision No. 4 Date March 2018 Page xi of xvi LIST OF FIGURES Figure 1-1 National Monitoring Programs Organizational Chart ......................................................... 6 of 8 3-1 Duplicate/Collocate and Replicate Analysis Schematic ..................................................... 4 of 4 7-1 NMOC, SNMOC, and 3-Hour Air Toxics Sampling System Components ...................... 2 of 10 7-2 VOC/Carbonyl Sampler Training Form ............................................................................ 3 of 10 7-3 24-Hour Integrated Air Toxics Sampling System Components ........................................ 6 of 10 7-4 Carbonyl Sampling System Components .......................................................................... 7 of 10 7-5 Hexavalent Chromium Sampling System Components .................................................... 9 of 10 9-1 Example NMOC COC ...................................................................................................... 2 of 16 9-2 Example Air Toxics COC ................................................................................................. 3 of 16 9-3 Example ERG LIMS Login Page ...................................................................................... 5 of 16 9-4 Canister Tag ...................................................................................................................... 5 of 16 9-5 Canister Cleanup Log for the ERG Heated Cleaning System ........................................... 7 of 16 9-6 Canister Cleanup Log for the ERG Unheated Cleanup System ........................................ 8 of 16 9-7 Example Carbonyl Compounds COC ............................................................................. 10 of 16 9-8 Example SVOC Sample COC ......................................................................................... 12 of 16 9-9 Example Ambient Hexavalent Chromium COC ............................................................. 13 of 16 9-10 Example Metals COC ...................................................................................................... 14 of 16 9-11 ERG Blank COC Record ................................................................................................. 15 of 16 10-1 Heated Canister Cleanup System Schematic .................................................................... 3 of 13 10-2 Unheated Canister Cleanup System Schematic ................................................................ 5 of 13 10-3 Gas Chromatograph/Mass Spectrometer/FID System ...................................................... 9 of 13 10-4 HPLC System .................................................................................................................. 11 of 13 13-1 Dynamic Flow Dilution Apparatus ............................................................................................. 4 of 7 15-1 Data Management and Sample Flow Diagram ................................................................... 2 of 7 16-1 ERG Response/Corrective Action Report Form ................................................................. 7 of 7 Project No. 0344.00 Element No. A2 Revision No. 4 Date March 2018 Page xii of xvi SYMBOLS AND ABBREVIATIONS AAC Atmospheric Analysis and Consulting AMTIC Ambient Air Monitoring Technical Information Center AQS Air Quality Subsystem ASTM American Society for Testing and Materials BFB 4-Bromofluorobenzene BLK Blank BS/BSD Blank Spike/Blank Spike Duplicate CAA Clean Air Act CAR Corrective Action Report CCB Continuing calibration blank CCV Continuing calibration verification CFR Code of Federal Regulations COC Chain of Custody CSATAM Community Scale Air Toxics Ambient Monitoring CV Coefficient of Variation DFTPP Decafluorotriphenylphosphine DNPH 2,4-Dinitrophenylhydrazine DPR Daily Performance Check DQOs Data Quality Objectives DUP Duplicate DVD Digital Versatile Disk EPA U.S. Environmental Protection Agency ERG Eastern Research Group, Inc. FACA Federal Advisory Committee Act FB Field Blank FC-43 perfluorotributylamine FEM Federal Equivalency Method FID Flame Ionization Detector GC Gas Chromatograph GPRA Government Performance and Results Act HAPs Hazardous Air Pollutant(s) He Helium H2 Hydrogen Project No. 0344.00 Element No. A2 Revision No. 4 Date March 2018 Page xv of xvi SYMBOLS AND ABBREVIATIONS (Continued) QC Quality Control QL Quantitation Limit RE Relative Error RF Response Factor RPD Relative Percent Difference RRF Relative Response Factor RRTs Relative Retention Times RSD Relative Standard Deviation RT Retention Time RTP Research Triangle Park SB Solvent Blank SIM Selected Ion Monitoring SIP State Implementation Plan SNMOC Speciated Nonmethane Organic Compounds SOPs Standard Operating Procedure(s) SQL Sample Quantitation Limit SRD Serial dilution SRM Standard Reference Material SSQC Second Source Quality Control STI Sonoma Technology, Inc. SVOC Semivolatile Organic Compounds TAD Technical Assistance Document. TSAs Technical System Audits TSP Total Suspended Particulate UAM Urban Airshed Model UATMP Urban Air Toxics Monitoring Program UPS United Parcel Service of America UV Ultraviolet VOCs Volatile Organic Compound Project No. 0344.00 Element No. A2 Revision No. 4 Date March 2018 Page xvi of xvi DISTRIBUTION LIST Copies of this plan and all revisions will be provided to: • Jeff Yane, Work Assignment Manager, U.S. EPA, C404-02, RTP, NC • Dave Shelow, Delivery Order Manager, U.S. EPA, C339-02, RTP, NC • Greg Noah, AT QA Coordinator, U.S. EPA, C304-06, RTP, NC U.S. EPA Regional contacts may obtain a copy of the QAPP by contacting the ERG Program Manager. It is the responsibility of each Regional contact to make copies of the plan for appropriate State personnel or to refer them to ERG Program Manager. The ERG staff working on this contract will receive a copy of this QAPP and all revisions. Project No. 0344.00 Element No. Section 1 - A4 Revision No. 4 Date March 2018 Page 1 of 8 PROJECT MANAGEMENT SECTION 1 PROJECT/TASK ORGANIZATION 1.1 Assignment of Program Personnel Table 1-1 presents the program organization listing the program assignment and responsible person for each aspect of the Environmental Protection Agency (EPA) National Monitoring Programs (NMP). The program organizational chart is presented in Figure 1-1. All Eastern Research Group, Inc. (ERG) staff working on this contract are provided access to a current electronic copy of this signed, EPA approved Quality Assurance Project Plan (QAPP). ERG’s primary support on this contract includes Nonmethane Organic Compounds (NMOC), Speciated Nonmethane Organic Compounds (SNMOC), Volatile Organic Compounds (VOCs), Polycyclic Aromatic Hydrocarbons (PAHs), Metals, Hexavalent Chromium, and other Hazardous Air Pollutants (HAPs). Subcontracting services are extended by ChromIan for onsite technical assistance for Photochemical Assessment Monitoring Stations (PAMS) analysis, Sonoma Technology, Inc. (STI) for data validation, Atmospheric Analysis and Consulting, Inc. (AAC) Lab for VOCs by Method TO-17, pesticides/Polychlorinated biphenyls (PCBs), anions, diisocyanates, and 4,4’-methylenedianiline, and RTI International for metals analysis, in the event of a large workload. ERG is responsible to the client for the work of the subcontractor and choosing subcontractors that meet the applicable requirements for the methods and contracts. The subcontractor should meet the Data Quality Objectives (DQOs) requirements for the appropriate method. ERG shall maintain a record of subcontractor compliance, including documentation of subcontractor’s Method Detection Limits (MDLs), QAPPs, etc. Sample analysis will not begin with the subcontractor until MDLs, QAPPs, etc., have been approved by EPA and ERG. Before sample analysis, the subcontractor may perform Proficiency Testing (PT) samples and/or Technical System Audits (TSAs) if they are available through Office of Air Quality Planning and Standards (OAQPS). If such measures are not Project No. 0344.00 Element No. Section 1 - A4 Revision No. 4 Date March 2018 Page 4 of 8 1.1.6 Task Leaders ERG Task Leaders are responsible for meeting the project objectives, meeting report schedules, and directing the technical staff in execution of the technical effort for their respective task(s). The Task Leaders will review 100 percent of all sample analyses. The Program QA Coordinator will request 10 percent of that data for review prior to data reporting by the Program Manager. The Task Leaders manage the day-to-day technical activities on delivery orders for this program. They assess and report on the project’s progress and results (e.g., recordkeeping, data validation procedures, sample turnaround time) and ensure timely, high-quality services that meet the requirements in this QAPP. Project No. 0344.00 Element No. Section 1 - A4 Revision No. 4 Date March 2018 Page 5 of 8 Table 1-1 Program Organization Program Assignment Program Personnel Assigned Phone Number Email Address Program Manager Julie Swift (919) 468-7924 julie.swift@erg.com Deputy Program Manager Laura Van Enwyck (919) 468-7930 laura.vanenwyck@erg.com Task Leader - Network Site Coordination Randy Bower (919) 468-7928 randy.bower@erg.com Task Leader - Shipping and Receiving Randy Bower (919) 468-7928 randy.bower@erg.com Task Leader - Air Toxics Randy Bower (919) 468-7928 randy.bower@erg.com Task Leader - Carbonyl Analysis Laura Van Enwyck (919) 468-7930 laura.vanenwyck@erg.com Task Leader – Hexavalent Chromium Glenn Isom (919) 468-7940 glenn.isom@erg.com Task Leader – Metals Randy Mercurio (919) 468-7922 randy.mercurio@erg.com Task Leader - NMOC Analysis Mitchell Howell (919) 468-7915 mitch.howell@erg.com Task Leader - Semivolatiles Scott Sholar (919) 468-7951 scott.sholar@erg.com Task Leader - SNMOC Analysis Mitchell Howell (919) 468-7915 mitch.howell@erg.com Task Leader - PAMS Support * Julie Swift (919) 468-7924 julie.swift@erg.com Task Leader - HAPs Support ** Laura Van Enwyck (919) 468-7930 laura.vanenwyck@erg.com Task Leader - Data Characterization Regi Oommen (919) 468-7829 regi.oommen@erg.com Task Leader - Annual Report/AQS Entry Jaime Hauser (919) 468-7813 jaime.hauser@erg.com Program Technical Adviser Dave Dayton (919) 468-7883 dave.dayton@erg.com Program QA Coordinator Donna Tedder (919) 468-7921 donna.tedder@erg.com Deputy QA Coordinator Jennifer Nash (919) 468-7881 jennifer.nash@erg.com Project Administrator Kerry Fountain (919) 468-7962 kerry.fountain@erg.com *Subcontracting support when requested from Chromian and Sonoma Technology, Inc. **Subcontracting support when requested from AAC and RTI International (miscellaneous HAPs). Project No. 0344.00 Element No. Section 1 - A4 Revision No. 4 Date March 2018 Page 6 of 8 Figure 1-1. National Monitoring Programs Organizational Chart Program Technical Advisor ~ Dave Dayton I Program QA Coordinator Donna Tedder -Deputy QA Coordinator Jennifer Nash I carbonyl Analysis Hexavalent Task Lead Chromium Analysis Laura Van Enwyck Task Lead Glenn Isom Metals Analysis SNMOC Data Analysis Task Lead Task Lead Randy Mercurio Mitchell Howell Semivolatile (PAH) Analysis Task Lead Scott Sholar I EPA Project Officer Jeff Vane EPA Delivery Order Manager DaveShelow Program Manager Julie Swift I Deputy Program Manager Laura Van Enwyck I I Air Toxics Analysis Task Lead Randy Bower Subcontracted HAPs Task Lead Laura Van Enwyck NMOCAnalysis Task lead Mitchell Howell Subcontractors AACLab RTI International EPA QA Officer Greg Noah Contracts Manager Serena Vetere I Project Administrator I Kerry Fountain QA Audit & PAMS Support Task Lead Julie Swift - Subcontractors Chramian Sonoma Technologies, Inc. Data Characterization - Task Lead - RegiOommen I Network Site Coordination Task Lead Randy Bower Shipping & Receiving Task Lead Randy Bower Annual Reports/ AQS Entry Task Lead Jaime Hauser Project No. 0344.00 Element No. Section 2 - A5 Revision No. 4 Date March 2018 Page 1 of 3 SECTION 2 PROBLEM DEFINITION/BACKGROUND The Clean Air Act (CAA) Amendments of 1990 required EPA OAQPS to set National Ambient Air Quality Standard (NAAQS) for the “criteria” pollutant ozone (O3). In areas of the country where the NAAQS for O3 was being exceeded, additional measurements of the ambient NMOC were needed to assist the affected States in developing/revising O3 control strategies. Measurements of ambient NMOC are important to the control of VOCs that are precursors to atmospheric O3. Due to previous difficulty in obtaining accurate NMOC concentration measurements, EPA started a monitoring and analytical program in 1984 to provide support to the States. ERG has continuously supported EPA for the NMOC programs since 1984. In 1987, EPA developed the Urban Air Toxics Monitoring Program (UATMP) to help State, Local and Tribal air monitoring agencies characterize the nature and extent of potentially toxic air pollution in urban areas. Since 1987, several State and local agencies have participated in the UATMP by implementing ambient air monitoring programs. These efforts have helped to identify the toxic compounds most prevalent in the ambient air and indicate emissions sources that are likely to be contributing to elevated concentrations. Studies indicate that a potential for elevated cancer risk is associated with certain toxic compounds often found in ambient urban air(1). As a screening program, the UATMP also provides data input for models used by EPA, State, local and risk assessment personnel to assess risks posed by the presence of toxic compounds in urban areas. The UATMP program is a year-round sampling program, collecting 24-hour integrated ambient air samples at urban sites in the contiguous United States every 6 or 12 days. The SNMOC program was initiated in 1991 in response to requests by State agencies for more detailed speciated hydrocarbon data for use in O3 control strategies and Urban Airshed Model (UAM) input. Project No. 0344.00 Element No. Section 2 - A5 Revision No. 4 Date March 2018 Page 2 of 3 Title I, Section 182 of the CAA Amendments of 1990 requires States to establish PAMS as part of their State Implementation Plan (SIP) for O3 nonattainment areas. The rule revises the ambient air quality surveillance regulations to include enhanced monitoring of O3 and its precursors. The regulations promulgated in 1993 require monitoring of O3, oxides of nitrogen (NOx), selected carbonyl compounds, and VOCs. The required monitoring is complex and requires considerable lead time for the agencies to acquire the equipment and expertise to implement their PAMS network. Under the PAMS program, each site may require a different level of support with respect to sampling frequency, sampling equipment, analyses, and report preparation. Presampling, sampling, and analytical activities are performed according to the guidance provided in the Technical Assistance Document (TAD)(2), for Sampling and Analysis of Ozone Precursors, 1998 revision. The program objective of PAMS is to provide data that are consistent with the proposed rule for ambient air quality surveillance regulations in accordance with Code of Federal Regulations Title 40, Part 58 (40 CFR Part 58). The ERG team offers site support to any State that needs to set up a PAMS site and/or provide technical help. The specific analytical methodology applicable to the PAMS program will be discussed in this QAPP. In 1999, EPA expanded this program to provide measurements of additional CAA HAPs to support the Government Performance and Results Act (GPRA). As required under the GPRA, EPA developed a Strategic Plan that includes a goal for Clean Air. Under this goal, there is an objective to improve air quality and reduce air toxics emissions to levels 75 percent below 1993 levels by 2010 in order to reduce the risk to Americans of cancer and other serious adverse health effects caused by airborne toxics. In 2001, EPA designed a national network for monitoring air toxics compounds present in ambient air entitled the National Ambient Toxics Trends Station (NATTS). The primary purpose of the NATTS network is tracking trends in ambient air toxics levels to facilitate measuring progress toward emission and risk reduction goals. The monitoring network is intended for long term operation for the principle purpose of discerning national trends in air toxics ambient concentrations. Project No. 0344.00 Element No. Section 2 - A5 Revision No. 4 Date March 2018 Page 3 of 3 Beginning in 2003/2004, EPA conducted periodic Community Scale Air Toxics Ambient Monitoring (CSATAM) grant competitions. The resultant 1- to 2-year grants are designed to help State, Local, and Tribal communities identify and profile air toxics sources, characterize the degree and extent of local air toxics problems, and track progress of air toxics reduction activities. Grants have been awarded across the United States, in large, medium, and small communities. The ERG team can offer site support and analysis to any agency for the UATMP, NATTS and CSATAM programs. The data obtained by following this QAPP will be used by EPA, State, Local, Tribal and risk assessment personnel to determine prevalent O3 precursors and air toxics in the urban air. The data collected from the continuous yearly sites gives the data analyst consistent high quality analytical results. Sampling and analytical uncertainties are determined through this program by performing 10 percent sampling duplicate (or collocated) and analytical replicate samples for each of the ambient air sites. This QAPP defines the preparation, sampling, laboratory analyses and QA/QC procedures conducted by ERG for EPA’s NMP to deliver data of sufficient quality to meet the programs’ objectives. Many of these procedures described in this QAPP are based on experiences obtained during previous National Program Studies. Project No. 0344.00 Element No. Section 3 - A6 Revision 4 Date March 2018 Page 3 of 4 Table 3-1 List of Analytical and Support Services Analysis Based on Method SOP (ERG-MOR- XXX) Analysis Total NMOC TO-12(3) -060 Speciated NMOC/PAMS Hydrocarbons via GC/FID TAD for Ozone Precursors(2) -005 VOCs via GC/MS TO-15(4) -005 * Concurrent SNMOC and VOC via GC/MS/FID TAD for Ozone Precursors(2)/TO-15(4) -005 Carbonyls via HPLC TO-11A(5) -024 PM10 HAP Metals via ICP-MS IO-3.5(6)/EQL-0512-201(7)/ EQL-0512-202(8) -095 TSP Hexavalent Chromium via IC ASTM D7614(9) -063 SVOC analysis via GC/MS (SCAN) TO-13A(10) / Method 8270D(11) -044*** * PAH analysis via GC/MS (SIM) TO-13A(10) / ASTM D6209-13(12) -049 PCB/Pesticides via GC * TO-4A(13) * Anions via IC * NIOSH 7903(14) ** * VOCs via GC/MS (from cartridge) * TO-17(15) * Diisocyanates * OSHA Method 42(16) * 4,4’-Methylenedianiline * NIOSH Method 5029(17) * Site Support NMOC/SNMOC TAD for Ozone Precursors(2) -046*** VOC TO-15(4) -003 or -021 Carbonyls TO-11A(5) -003 or -047 Hexavalent Chromium ASTM D7614-12(9) -013 PAMS Technical NA NA PAMS QA NA NA Other Services Performance Samples for VOC TO-15(4) -061 Performance Samples for Carbonyls TO-11A(5) -024 Performance Samples for PAH TO-13A(10) / ASTM D6209-13(12) -049 Performance Samples for PM10 HAP Metals IO-3.5(6)/EQL-0512-201(7)/ EQL-0512-202(8) -095 Performance Samples for TSP Hexavalent Chromium ASTM D7614-12(9) -063 Sampler Certification for Carbonyls TO-11A(5) -100 Sampler Certification for VOC TO-15(4) -030 Uniform Calibration Standards TO-15(4) -061 AQS Data Entry (per pollutant group) NA -098 Report Development/Data Characterization NA NA *Will be supplied by subcontractor when analysis is requested. **NIOSH Method 7903 was replaced with 7906, 7907 and 7908. ***SOP is currently archived but will be updated if needed for sample analysis. Project No. 0344.00 Element No. Section 3 - A6 Revision 4 Date March 2018 Page 4 of 4 ERG can provide sampler, sampler training, and any technical assistance needed throughout the monitoring program. Canister and/or carbonyl samples are collected by State/Local/or Tribal agency personnel every 6 or 12-days at each of the designated sites. At least one week before each sample collection episode, ERG ships the necessary clean, certified canisters and/or carbonyl cartridges to the site along with the field COC forms. The time- integrated ambient samples are then collected and shipped to ERG for analysis. ERG then prepares the program data for a final annual report describing sampling and analysis procedures, results, discussion of results, compilation of statistics, and recommendations. To determine the overall precision of analysis for the programs, replicate analyses (10 percent of the total number of samples) are used following the schematic shown in Figure 3-1. After the final data report receives approval by the EPA Project Officer and Delivery Order Manager, ERG distributes the final report to designated recipients. ERG provides the final data summaries to the associated agencies electronically in Excel® and Adobe® formats. ERG staff finalizes and uploads the data into the Air Quality Subsystem (AQS) database. Figure 3-1. Duplicate/Collocate and Replicate Analysis Schematic Primary Sample (Designated D1 or C1) Duplicate or Collocate Sample (Designated D2 or C2) Replicate Analysis of Primary Sample (R1) Replicate Analysis of Duplicate or Collocate Sample (R2) / Project No.: 0344.00 Element No.: Section 4 - A7 Revision No.: 4 Date: March 2018 Page: 1 of 5 SECTION 4 DATA QUALITY OBJECTIVES AND CRITERIA FOR MEASUREMENT DATA As ERG performs measurement services only, DQOs for defining a toxics network program are not identified in this QAPP. A well-prepared description of the Measurements Quality Objectives (MQOs) can be found in the TAD for the NATTS Program prepared for EPA in October 2016(18). This section will discuss the MQOs of the ERG laboratory analyses, emphasizing the levels of uncertainty the decision maker is willing to allow/accept from the analytical results. The DQOs for the four programs – NMOC, UATMP, PAMS, and CSATAM – are similar but are not identical. Therefore, the programs are discussed separately. The NATTS TAD presents the requirements for collecting and reporting data for the NATTS network. Eighteen compounds have been identified as major risk drivers based on a relative ranking performed by EPA and have been designated as NATTS Core or “Tier I” compounds. All other reported compounds, for any NMP, are considered compounds of interest, but do not necessitate the NATTS MQOs. The Tier I compounds are acknowledged throughout this document. ERG exemptions from the NATTS TAD are listed in Appendix A. Once a DQO is established, the quality of the data must be evaluated and controlled to ensure that data quality is maintained within the established acceptance criteria. MQOs are designed to evaluate and control various phases (sampling, preparation, analysis) of the measurement process to ensure that the total measurement uncertainty is within the range prescribed by the DQOs. MQOs can be defined in terms of the following data quality indicators: Precision - a measure of mutual agreement between individual measurements performed according to identical protocols and procedures. This is the random component of error. Bias - the systematic or persistent distortion of a measurement process that causes error in one direction. Bias is determined by estimating the positive and negative deviation from the true value as a percentage of the true value. Project No.: 0344.00 Element No.: Section 4 - A7 Revision No.: 4 Date: March 2018 Page: 4 of 5 Table 4-1 Measurement Quality Objectives for the National Program (UATMP, NATTS, CSATAM, PAMS, NMOC) Program Reporting Units Precision from analysis of Replicate Samples (RPD) Precision (CV) from collection of Duplicate/Colloca te Samples Representativeness Comparability/ Based on Method Bias Completeness Minimum Detection Limits* NMOC ppmC ≤ 10% ≤ 20% Neighborhood GC-PDFID EPA Compendium Method TO-12(3) ± 25% >85% To be determined upon need SNMOC ppbC ≤ 25% ≥ 5x MDL ≤ 25% ≥ 5x MDL Neighborhood GC-FID TAD for O3 Precursors (2) ± 25% >85% See Table 11-12 VOC ppbv ≤ 25% ≥ 5x MDL For NATTS Tier I compounds, ≤15%, others ≤ 25% ≥ 5x MDL Neighborhood GC-FID/MS EPA Compendium Method TO-15(4) ± 25% >85% For NATTS Tier I, see NATTS TAD Table 4.1-1 Others, see Table 11-13 Carbonyls ppbv ≤ 10% ≥ 0.5 µg/cartridge For NATTS Tier I compounds, ≤15%, others ≤ 20% ≥ 0.5 µg/cartridge Neighborhood HPLC EPA Compendium Method TO-11A(5) ± 25% >85% For NATTS Tier I, see NATTS TAD Table 4.1-1 Others, see Table 11-14 Metals ng/ per cubic meter (ng/m3) ≤ 20% ≥ 5x MDL For NATTS Tier I compounds, ≤15%, others ≤ 20% ≥ 5x MDL Neighborhood ICPMS IO-3.5(6)/EQL-0512- 201(7)/ EQL-0512-202(8) ± 25% >85% For NATTS Tier I, see NATTS TAD Table 4.1-1 Others, see Table 11-16 Hexavalent Chromium ng/m3 ≤ 20% for conc. > 5x MDL ≤ 20% Neighborhood IC-UV Detector ASTM D7614-12(9) ± 25% >85% 0.0038 ng/m3 *For NATTS Tier 1 compounds, minimum detection limits are listed in the NATTS TAD. Project No.: 0344.00 Element No.: Section 4 - A7 Revision No.: 4 Date: March 2018 Page: 5 of 5 Table 4-1 Measurement Quality Objectives for the National Program (UATMP, NATTS, CSATAM, PAMS, NMOC) (Continued) Program Reporting Units Precision from analysis of Replicate Samples (RPD) Precision (CV) from collection of Duplicate/Colloca te Samples Representativeness Comparability/ Based on Method Bias Completeness Minimum Detection Limits Semivolatiles micro- gram/m3 (μg/m3) ≤ 10% for conc. ≥ 0.5 µg/mL For NATTS Tier I compounds, ≤15%, others ≤ 20% for conc. ≥ 0.5 µg/mL Neighborhood GC/MS EPA Compendium Method TO-13A(10) and ASTM D6209- 13(12), (or SW-846 Method 8270D(11)) ± 25% >85% For NATTS Tier I, see NATTS TAD Table 4.1-1 Others, see Table 11-15 PCB/ Pesticides ng/m3 ≤ 15% ≤ 15% Neighborhood GC EPA Compendium Method TO-4A(13) ± 25% >85% To be determined upon need Anions ppbv ≤ 15% ≤ 15% Neighborhood IC NIOSH Method 7903(14) ± 25% >85% To be determined upon need VOCs via cartridge ppbv ≤ 15% ≤ 15% Neighborhood GC/MS EPA Compendium Method TO-17(15) ± 25% >85% To be determined upon need Diisocyanates µg/m3 ≤ 15% ≤ 15% Neighborhood HPLC OSHA Method 42(16) ± 25% >85% To be determined upon need 4,4’- Methylene- dianiline µg/m3 ≤ 15% ≤ 15% Neighborhood HPLC NIOSH Method 5029(17) ± 25% >85% To be determined upon need *For NATTS Tier 1 compounds, minimum detection limits are listed in the NATTS TAD. Project No. 0344.00 Element No. Section 5 - A8 Revision No. 4 Date March 2018 Page 1 of 2 SECTION 5 SPECIAL TRAINING REQUIREMENTS/CERTIFICATION The activities of EPA’s NMP are performed using accepted EPA, National Institute for Occupational Safety and Health (NIOSH), and Occupational Safety and Health Administration (OSHA) sampling and analytical protocols for the field sampling training personnel and analytical laboratory staff. 5.1 Field Activities Training Personnel Field activities training personnel involved in this project have over 30 years of experience in the duties they will be performing in the field. The training of ERG field activities personnel is recorded in the ERG Training Records files. Special certification is not needed for an operator to set up the sampling systems. Each State should document and record the training of their personnel on the field testing procedures provided by ERG. The States’ field testing staff will be subject to on-site surveillance by EPA. ERG’s Task Leader will provide appropriate corrective action enforcement, if necessary, for the ERG personnel setting up the sampling equipment and the field testing staff. ERG provides on-the-job training in the field on sampler use and maintenance, for supervisors and field site operators. The appropriate SOPs used during training are presented in Appendix C. ERG does not provide SOPs for sampling systems that are not maintained by ERG. Sampling System Training forms used during operator training in the field is presented in Figure 7.2 for VOC/Carbonyl and Carbonyl samplers. The forms will only be provided when new site personnel are trained on the sampling systems. After training is completed and signed in the field, the yellow copy is retained for site records. The original copy is scanned in the laboratory and stored by the QA coordinator. The sampling equipment for monitoring sites may be inside a sampling building or outside. There are no hazards inherent to the samplers and no special safety training or equipment will be required. Site hazards should be addressed on a site-by-site basis by the site Project No. 0344.00 Element No. Section 6 - A9 Revision No. 4 Date March 2018 Page 2 of 6 6.3 Quarterly QA Report A QA report for each type of data analysis is sent to EPA and appropriate State/Local/Tribal agencies on a quarterly basis in the form of control charts including initial calibration verifications, continuing calibration verifications, method blanks, initial calibration blanks, continuing calibration blanks, and blank spikes. 6.4 Annual Summary Reports Submitted to EPA Hard copies of the final report are presented to EPA contacts at the end of the sampling period. State/Local/Tribal agencies receive electronic copies (i.e., PDF). The final report is submitted for the data collected from January 1 to December 31 of the previous year. The report can contain the following information: • Names of participating sites and corresponding metadata information, including city name, location and the AQS codes; • Description of the sampling and analytical methodologies used by the laboratory; • Completeness of the monitoring effort for each site; • Background information on the methodology used to present and analyze the data; • General combined and individual site summary of the year’s results; • Discussion of different trends for the select HAPs chosen for analysis; • Risk screening evaluations using toxicity factors (e.g., UREs or RfCs); • Variability analysis (intra-site and seasonal comparisons); • Pollution roses to determine predominant direction for select compounds; • Discussion of precision and accuracy and other prevalent QC concerns; and • Yearly discussions of conclusions and recommendations. Project No. 0344.00 Element No. Section 6 - A9 Revision No. 4 Date March 2018 Page 3 of 6 If corrections are needed after the final report is presented to EPA, the report is easily retrieved, and corrections are sent to all relevant personnel. 6.5 Records and Supporting Data All raw data required for the calculation of air toxics concentrations, submission to the EPA/AQS database, and QA/QC data are collected electronically or on data forms that are included in the field and analytical methods sections. All hardcopy information is filled out in indelible ink. Corrections are made by inserting one line through the incorrect entry, initialing the correction (ERG maintains a signature log), and placing the correct entry alongside the incorrect entry, if this can be accomplished legibly, or by providing the information on a new line. Table 6-1 presents the location of the data records for field and laboratory operations stored at the ERG laboratory. Table 6-1. Data Documentation and Records Item Record Short Term Location Storage Long Term Location Storage Field Operations Sampling System Training Sampling System Training Form ERG Copy scanned and hardcopy stored by ERG COC ERG COCs Field gets “pink” copy, ERG gets “yellow” and “white” copy Copy scanned and stored on ERG LIMS QC Sample Records (field blanks, duplicate/ collocated, sample integrity, etc.) COC Field Copy scanned and stored on ERG LIMS General Field Procedures COC Field Copy scanned and stored on ERG LIMS Laboratory Records Sample Prep Data Bench sheets Hardcopy filed, LIMS, shared network drive Hardcopy archived, LIMS, shared network drive Project No. 0344.00 Element No. Section 6 - A9 Revision No. 4 Date March 2018 Page 4 of 6 Table 6-1. Data Documentation and Records, Continued Item Record Short Term Location Storage Long Term Location Storage Laboratory Operations Sample Management Records (sample receipt, handling, storage, etc.) COCs LIMS, with sample analytical data LIMS, with sample analytical data Test Methods SOPs Hardcopy filed, shared network drive Shared network drive QA/QC Reports (General QC records, MDL information, calibration, etc.) Individual records for each analysis Hardcopy filed, shared network drive Hardcopy archived, shared network drive Corrective Action Reports Individual records for each analysis Hardcopy filed, a copy in data package if appropriate All copies archived Data Reduction, Verification, and Validation Electronic Data (used for reporting and AQS) Excel® and Access® Shared network drive Shared network drive 6.5.1 Notebooks ERG issues laboratory notebooks upon request. These notebooks are uniquely numbered and associated with the laboratory personnel. Notebooks are archived upon completion for at least 5 years from the end of a project. Although LIMS data entry forms are associated with all routine environmental data operations, the notebooks can be used to record additional information about these operations. The procedures for maintaining notebooks are presented in SOP for Maintaining Laboratory Notebooks (ERG-MOR-039) in Appendix C. Field Notebooks - Field notebooks are the responsibility of EPA, States, Local or Tribal agencies as ERG is not responsible for the collection of samples. Laboratory Notebooks - Notebooks are associated with general procedures such as calibration of analytical balances, standard preparation logs, etc., used in this program. Project No. 0344.00 Element No. Section 7 - B1 Revision No. 4 Date March 2018 Page 1 of 10 MEASUREMENT DATA ACQUISITION SECTION 7 SAMPLING PROCESS DESIGN Sampling procedures for the NMOC, SNMOC, UATMP, NATTS, and CSATAM programs are discussed in this section. ERG provides site-specific support for the PAMS and HAPs sampling. All parameters listed in this section are necessary for the sampling systems listed below. ERG is not responsible for the collection of samples nor the design of these programs. 7.1 NMOC and SNMOC Canister Samplers Sampling for NMOC and SNMOC takes place each workday from the beginning of June to the end of September at designated NMOC and SNMOC sites from 6:00 a.m. to 9:00 a.m. local time. Sampling procedures have been discussed in detail in other documents. (1, 2) Figure 7-1 is a diagram of the ERG sampling system used for collecting the ambient air samples. Clean, evacuated passivated stainless-steel canisters are shipped daily from ERG's Research Triangle Park (RTP) Laboratory to the NMOC and SNMOC sites. Canisters are connected to the sampling system by local operators. The digital timer automatically activates the pump and solenoid valve to start and stop sample collection. The pump pressurizes air samples during the sampling period to about 15 pounds per square inch gauge (psig), and the flow control valve (variable orifice) ensures a constant sampling rate over the 3-hour period. A 2-micron stainless steel filter is installed in the sampling line to remove particulate from the ambient air that may damage or plug the variable orifice. The sample probe inlet is positioned from 2 to 10 meters (m) above ground level. ERG installs the sampling systems at the site location and trains associated local operators on site. Operator training is documented on the Sampler Training Form (Figure 7-2). It is the responsibility of the local operators to operate the sampling apparatus and complete the field sample COC form that ERG supplies with each canister. ERG staff maintain telephone Project No. 0344.00 Element No. Section 7 - B1 Revision No. 4 Date March 2018 Page 2 of 10 Figure 7-1. NMOC, SNMOC, and 3-Hour Air Toxics Sampling System Components Bellows Valve Duplicate Sample Canister Primary Sample Canister Bellows Valve Pressure Gauge Receptacle Outlet • (Optional Use) 11 Inlet to Sample Manifold or Direct to Atmosphere 2-Way Fluxtron Flow Control Valve Valve Digital Timer Sample Line Sample Rotameter Elapsed Channel2 Channel l ,__ _____ _, IIlllllll Timer 2-Micron Filter Project No. 0344.00 Element No. Section 7 - B1 Revision No. 4 Date March 2018 Page 3 of 10 Figure 7-2. VOC/Carbonyl Sampler Training Form VOC/Carbonyl Sampling System Training 3-2018 Installation Date: Site ID: Installed Sampler ID #: Time Set: Timer Set: Trainee: NOTES : Signature: Trainer: Copy of SOP on Site : """(Y_/N)----'------­ Replaced Sampler ID #: Carb Line Replaced: ~(Y_/N) _______ _ VOC Line Replaced: ~(Y_/N)----'------- Date: ERG assumes no personal and/or property liability realized by the user from the use of ERG provided equipment. The user, by virtue of accepting the ERG equipment for use, undertakes any/all personal and/or property liabilities that could be associated with its use (including operational, housing, and/or safety). Project No. 0344.00 Element No. Section 7 - B1 Revision No. 4 Date March 2018 Page 6 of 10 Figure 7-3. 24-Hour Integrated Air Toxics Sampling System Components Key In let to Sample Manifold or Direct to Atmosphere Plumbing Connections Electrical Connections Primary DupHcate Pressure Gauge 2-Micron Filter Mass Flow Controller (0-20 sccm) COM No No By-Pass Ca pillary Re lief r------------ ' ' ' 3-w a Ca pilla-y : Fluxtron: '-----' : Solenoid: : ·------------------------------------~ ' ' Orifice/liter Assembly Relief Capillay ' @ ' : --- - - - - - - - - - - - - - - - - - - Rotameter Tube Rotameter Elapsed Timer Orifice/liter Assembly :--------------[I] Thermocouple ~-----'-, Mass f low Digital Timer ' ,.. - - - - - - - - - - - - - -- Temperature Controller Control L - - - ....... -1----~-------l ._D_i_s_Jll_av_ 0 , _ _ _ _ _ _ _ _ Channel 11 Channel 2 ' ' ' ------------------ 0 \1/; ~ - ' -- ----------~ Receptacle Outlet '---=---...r Project No. 0344.00 Element No. Section 7 - B1 Revision No. 4 Date March 2018 Page 7 of 10 Figure 7- 4. Carbonyl Sampling System Components Inlet to Sample Manifold or Direct to Atmosphere Key Sample AirSou,re Primary Plum bing Connections - - - - - - - - - - - - · Electrical Connections DNPH Cartridge ~ Vacuum Source Orifice/filer Assembly igh acuum ,------------ Pump -----.i Relief Capillay :--------------------@ ' Digital Timer , ,--------------- ' Denuder Ozone rubber Rotameter Tube Rotameter Elapsed Timer Duplicate Orifice/filer Assembly :--------------, ~ I Thermocouple Temperature Controller Channel 11 Channel 2 , _ - - - - - - _( .__ ____ .., __ ______ • ___ ~ Receptacle Outlet Project No. 0344.00 Element No. Section 7 - B1 Revision No. 4 Date March 2018 Page 8 of 10 Compendium Method TO-11A(5) to verify that the system meets the required cleanliness criteria and can produce non-biased samples as required by the NATTS TAD(18). These results are documented in a permanent file specific to each sampler by system identification number. The certification procedure is presented in the SOP for Carbonyl Sampling System Certification (ERG-MOR-100) in Appendix C. A total of 31 sampling cartridges for a 12-day sampling schedule and 61 sampling cartridges for a 6-day sampling schedule will be collected and analyzed per site. Duplicate (or collocated) samples and field blanks will be collected monthly and are designated in the 2018 Sampling calendar presented in Appendix B. 7.4 Hexavalent Chromium Samplers Sodium bicarbonate-impregnated cellulose filters are connected to the Hexavalent Chromium sampler as shown in Figure 7-5 and ambient air is drawn through the filters through a glass sampling probe using Teflon sampling lines. Prepared filters are shipped to each site for the hexavalent chromium sampling. ERG ships the bicarbonate-impregnated sodium cellulose filters to each site in coolers (chilled with blue ice packs). The samples are collected for a 24-hour period. Disposable polyethylene gloves are used by the field operators when handling the filters to reduce background contamination. After sampling, the filters are removed from the sampling apparatus, sealed, and returned to the ERG laboratory in the coolers and ice packs in which they were received. Additional qualifying information for the hexavalent chromium sampling and analysis techniques is presented in the American Society for Testing and Materials (ASTM) D7614-12(9) method and specific details are provided in ERG’s SOP for the Preparation and Analysis of Ambient Air for Hexavalent Chromium by Ion Chromatography (ERG-MOR-063) presented in Appendix C. Project No. 0344.00 Element No. Section 8 - B2 Revision No. 4 Date March 2018 Page 1 of 1 SECTION 8 SAMPLING METHOD REQUIREMENTS The sampling methods that are used in this program are described in this Section. Since there are four separate sampling systems and subsequently four separate analytical techniques, each of the sampling methods is different. The SOPs for each method are reviewed annually and updated as necessary. The QA Coordinator, Program Manager and Writer/Editor will review, sign and date SOPs before distributing to the laboratories satellite file areas. The previous copies will be replaced with the revised edition. The appropriate users are notified of the updated procedure. The original, and all previously revised edits, are stored in an archive file maintained by ERG’s Project Administrator. As ERG is not responsible for actual execution of the field sampling in this program, the ERG SOPs list general sampling guidelines needed for the NMOC, UATMP, Carbonyl, and Hexavalent Chromium sampling. Table 8-1 identifies the different methods and SOP numbers for operation of each type of sampler ERG provides. Some HAPs sampling is not addressed in the NMP Support contract (Metals, PAHs, etc.), and are not discussed in this QAPP. Table 8-1 EPA Methods and ERG SOPs for each Sampling System Sampling System Based on Applicable Method ERG SOP Number NMOC EPA Compendium Method TO-12(3) ERG-MOR-046 VOC EPA Compendium Method TO-15(4) ERG-MOR-003 Carbonyl EPA Compendium Method TO-11A(5) ERG-MOR-047 Hexavalent Chromium ASTM D7614-12 Method(9) ERG-MOR-013 Project No. 0344.00 Element No. Section 9 - B3 Revision No. 4 Date March 2018 Page 1 of 16 SECTION 9 SAMPLE HANDLING AND CUSTODY REQUIREMENTS Similar sample custody procedures are followed for all monitoring programs. However, program-specific differences exist because the analytical requirements for the programs vary. As these activities are conducted under one EPA contract, United Parcel Service of America (UPS) with Overnight Delivery will handle all shipping to and from the sites. Unless specified below, samples taken in the field should not require any extra special precautions for shipping. The Shipping and Receiving Task Leader will ensure that sample media that leaves and field samples that are received in the laboratory follow all procedures listed in this QAPP and the individual SOPs. The Task Leader will also advise the Project Manager of any issues or obstacles regarding sample shipping, receipt, login and storage. The sample custodian working under the Shipping and Receiving Task Leader will ship sample media to the field and receive custody of samples, complete COC receipt information, document sample receipt, and enter COC information into LIMS to create a work order. 9.1 Canister Sample Custody 9.1.1 Canister Custody A color-coded, three-copy canister sample COC form (Figures 9-1 and 9-2) is shipped with each 6-liter canister for the NMOC, SNMOC, UATMP, NATTS, CSATAM, or PAMS sites. If duplicate or collocated samples are to be taken, two canisters and two COC forms are sent in the shipping container(s) to the site. When a sample is collected, the site operator fills out the form per the instructions in the on-site notebook. The site operator detaches the pink copy to be retained on-site and sends the remaining copies with the canister in the shipping container to ERG’s laboratory. Project No. 0344.00 Element No. Section 9 - B3 Revision No. 4 Date March 2018 Page 2 of 16 Figure 9-1. Example NMOC COC !. 1--~ IERG Lab ID# ~01 Keys1one Park Drive, Sute 700, Morrisville, NC 27560 NMOC SAMPLE CHAIN OF CUSTODY Site Code: Canister Number: City/State : Lab Initial Can. Press . ("Hg) : t:I) AQS Code: Date Can . Cleaned: ·= Q. Collection Date: Cleaning Batch # : .a E ta ta Options ...I 1/) I! NMOC (Y/N) : CL SNMOC (Y/N): Duplicate Event (Y/N): TOXICS (Y/N): Duplicate Can# : ~------------------------------------------------------------- ,:, C. Operator: ______ Sys.#: ____ Rotameter Setting: - :::, a, -·- a, Setup Date: _____________ Elapsed Timer Reset (Y/N): u. 1/) Field Initial Can. Press. ("Hg) : Canister Valve Opened (Y/N): ____ _ ~-------------------------------------------------------------~ Recovery Date: ____________ Sample Duration (3 or 24 hr) : ____ _ ~ ~ Field Final Can. Press. (psig): _______ Elapsed Time: U:: ~ Canister Valve Closed (Y/N): cc ~-------------------------------------------------------------i;' Received by: ______ Date:____ Lab Final Can . Press . (psig) : ';l j; Status: Valid Void (Circle one) ....1 ~ If void , why: ------------------------------- ~-------------------------------------------------------------Analyst: ____________ Database entry by: ____ Date: ____ _ Date: ____________ Batch ID ______________ _ (.) 0 :I!: z NMOC Instrument: --------- 1 n j. 1 (AC) : (ppmC): (ppmC): lnj . 2 (AC): lnj . 3 (AC): _____ (ppmC): ___ _ Average AC: Standard Dev. (AC): _______ _ Average Cone. (ppmC): Standard Dev. (ppmC): ~------------------------------------------------------------- g 5 Analyst : :I!::;:; t)'i & Batch ID Date: ------- ~------------------------------------------------------------- fj 5 Analyst : ·>< a {=. 0 Batch ID Comments: Date: ------- ------------------------------------- White Sample Traveler Canary: Lab Copy Pink Field Copy Project No. 0344.00 Element No. Section 9 - B3 Revision No. 4 Date March 2018 Page 5 of 16 identification (ID) number and tagged (see Figure 9-4), noting the site location and the sample collection date. Figure 9-3. Example ERG LIMS Login Page Figure 9-4. Canister Tag The LIMS ID number is recorded on the canister tag and on all ERG copies of the COC. The remaining copies of the canister sample COC are separated. The white copy is scanned (the Analysis: _________________________ Sample ID: _______________________ Laboratory ID: ________________________ Date Sampled: ____________________ Canister #: ______ Press/Vac: _______ Site: ___________ Dup/Rep: ________ Comment: ________________________ ~ Samples - 6012904 [U.S. Environmental Protection Agency, Region 9 - PXSS] 3341 items 1<12 Months Work Order 16012904 Samoles 1:,:1 "IM!II 6012904-02 6012904-03 Sample Information ) Containers ) Qualifiers ) Name IPXSS Alias I Regulatory ID I Comments I P' History P' Schedule r Transfer r QC Source Cross-Table I ~ Work Analyses Modify ) Analyses included for this sample r Field Data T Field Info T Field Info T Memos Sample T Details T Location T Well Data Lab Matrix Sampled [Eastern) IAir iJ 101125116 2359 i.l~ Report Matrix IAir Sampled Begin iJ 101125/16 0000 i.l Sample Type Sampled By IField Sample ..:.JI ..:.J Metals Analysis· 47mm ~ Analysis I Subanalysis I Comments I TAT I Due I Hold I Subcontract SNMOC 20l 6 .....lo... 1-T0- --15_2_0_16-----~--~--~----~4-5-~0-3/-13-/-16_1_2-:0-0-~30--~----r T0-1 lA 2016 .....,,,.,- T0-13A 2016 • I < I > Add Edit Copy Delete Group Edit Field Data <<Work Orders e:J j __ D_on_e _ _. 0 Project No. 0344.00 Element No. Section 9 - B3 Revision No. 4 Date March 2018 Page 6 of 16 PDF is stored in the LIMS system) and is kept with the canister sample until analysis is complete. After sample analysis, the white copy goes into the data package with the sample data. The yellow copy is stored chronologically in a designated file cabinet for one year. The file cabinet is in Room 102 in the Laboratory building. 9.1.2 Canister Analytical Routing Schedule Each canister has a unique canister identification number inscribed on the canister. This number is used during can cleaning, field collection, laboratory receipt, and laboratory sample analysis and is included on the individual Toxics/SNMOC COCs and entered into the LIMS. The canister sample analysis hold time is 30 days from the sampling date. The samples are sent to the ERG Air Toxics Laboratory for VOC and SNMOC/PAMS GC/Flame Ionization Detector/Mass Spectrometer (FID/MS) analysis. The canister sample is analyzed and kept in the laboratory until after the analyst reviews the relevant analytical data. 9.1.3 Canister Cleanup All canisters are cleaned prior to reuse following SOP ERG-MOR-105 (SOP for Sample Canister Cleaning using Wasson TO-Clean Automated System) as shown in Appendix C. The canisters are cleaned using the procedure described in Section 10.1.1. The unheated system (following SOP ERG-MOR-062, SOP for Sample Canister Cleaning) is maintained as a backup, if needed, and is described in Section 10.1.2. The canisters are cleaned to <3x MDL or 0.2 parts per billion by volume (ppbV), whichever is lower, and 20 parts per billion as Carbon (ppbC) for Total SNMOC. If the canister fails the Blank criteria, it is returned to the cleaning system bank with the other canisters that were cleaned along with it and all canisters are put through an additional Vacuum and Pressure cycle. The same canister is analyzed again. All canisters, whether used for NMOC, SNMOC, UATMP, NATTS, CSATAM, or PAMS, are cleaned by the same procedure and are entered into the canister cleanup log, shown in Figure 9-5 for the heated systems and in Figure 9-6 for the unheated systems. Project N o. 0344.00 Elem ent N o. Section 9 - B 3 R evision N o. 4 D ate M arch 2018 Page 7 of 16 Figure 9-5. C anister C leanup L og for the E R G H eated C leaning System Upper Rear Front Lower r- Rear Front Upper Rear Front Lower r- Rear Front Heated Canister Cleaning Systems Logbook 2016-2 Heated System 1 Batch ID Cleaning Date ------- Initials Pass Fail Extra Cycle Date Program _______ I I Oven Temperature (°C) Final Evac Date ------- Leak Check Heated System 2 Pass Fail Batch ID Cleaning Date ------- Initials Extra Cycle Date Program ------- Oven Temperature (0 C) Final Evac Date ------- Leak Check Review Initials & Date L:\Forms\Canister clean ing\Wasson Can Cleaning system log v2.x lsx Project No. 0344.00 Element No. Section 9 - B3 Revision No. 4 Date March 2018 Page 10 of 16 Figure 9-7. Example Carbonyl Compounds COC ;,ERG f .. , ..... , ... ,,.,_ IERG lab lD# I 601 ic.--P.ii~.S.- 700, lrilonilwAa. NC 21S&O CARBONYL COMPOUNDS CHAIN OF CUSTODY c1 Site Code: Colection Date: ... ~ Cit)t'S1ate: Cartridge l ot•: ~ 'Z AOSCode: Duplicate E\/9nt (Y/N): a: Relinquished by: Date: ------ --------------------------------------------------------Rooailed by: Date: :!! a. ti SeWpDate: Operalor: Sys. #: Pre-Samplilg Rolameter Rea<ing (cc/min): Elapsed rmer Rosel (Y/l',I) : ------ --------------------------------------------------------Recovery Date: Sample Duration (3 or 24 hr) : ~ Operator: Elapsed rme: :!! I Posl Sampling Rolameler Reading (cc/mil): Slatus: VALID VOID (Ci'cle one) .. .. I Cartridges Capped (Y /l',I) : Relinquished by: Date: ------ --------------------------------------------------------Rooailed by: Date: ... i S1alus: VALID VOID (Ci'cle one) UnCOO'ected Temperature: ~ § II void, why: Corrected Temperature: a:: Sample Voltme (Iola! Uers) : IRGun: 1 2 (Ci'cle one) Samol•• 1torwJ in Rofda.,.or 11 11 Sample Samplo Sample Cartridgo "-Dote Tino Du- Volume Lot • Sa....,_ID LablD .. =I Q, Comments: --------------------------------- While: Sample Traveler Cana,y: Lab Copy Pink: Fielc:I CQA' Project No. 0344.00 Element No. Section 9 - B3 Revision No. 4 Date March 2018 Page 11 of 16 9.3 HAPs Sample Custody Samples collected on prepared sample media (i.e., XAD-2®, Polyurethane Foam (PUF), hexavalent chromium filters, etc.) use supplied three-copy COC forms to document sample collection. Field testing personnel will record applicable collection data (such as time, date, location, meteorological parameters) on the appropriate COC forms (Figures 9-8, 9-9 and 9-10) and keep the pink copies for site records. The COCs are then shipped to ERG with the prepared sample media. Because the sites supply the filters used for metal analysis, COC forms are normally supplied by the State, Local or Tribal agency for these samples. If needed, however, COC forms can be supplied by ERG electronically inputting multiple filters for metal analysis (Figure 9-11). Samples are received at ERG’s laboratory as presented in the SOP for Sample Receipt at ERG Chemistry Laboratory, ERG-MOR-045. All HAPs samples received at the ERG laboratory will be logged into the LIMS as described in the SOP for Sample Login to the Laboratory Information Management System, ERG-MOR-079. 9.4 Invalid Samples The sample COC form may indicate that the sample sent from a site is invalid. The sample can be determined invalid at the site or in the laboratory. SOP ERG-MOR-045 describes the sample receiving procedure and sample acceptance. Individual sites will be contacted if there are any questions about the samples upon receipt. When a sample is designated as invalid, the assigned LIMS ID number is notated as a void and is invalidated on the individual respective COC form. Another sample media will be sent to the site with the COC designated to make up on non-standard sampling days. If the site has repeated invalid samples, normally three voids in a row, the ERG site coordinator Task Leader will work with the site personnel to diagnose and correct the problem. The sites will also be notified in the monthly analytical reports of any invalid samples. Project No. 0344.00 Element No. Section 9 - B3 Revision No. 4 Date March 2018 Page 12 of 16 Figure 9-8. Example SVOC Sample COC .,ERG j' ......... ' .. IERG Lab ID# I 1iD1~PWaDnw.a.7m......._NC27SIO SVOC SAMPLE CHAIN OF CUSTODY Site Code: Container #: I Ciy/Slate: Collection Date: lL AOSCode: Collocated Eveni (Y/N): !! SUR IO: Cartridge Certification Date: XADLat E PUFLot Relinquished by: Date: Ater lot ----~-------------------------------------------------------· i Received by. Date: Site Operator: System#: ... .. Set-Up Date: Bapsed Timer Reset (Y/N): ii: ----~-------------------------------------------------------· Recovery Date: Collection SV<lltem Information: Barometric ....... 1 lbgnehelc -Ea-...t Tne T_,.,., ("H,O) 1 m•-1 ~ Start • ~ End i ll .. ... Total Collection Tme (M'nutes) Total Collection Volume (std. m3) Status: Valid Void (Circle one) Site Operator: Relinquished by: Date: ----~------------------------·---------------------------·--· Received by: Date: Container #: !I Status: Valid Void (Circle one) Uno01Tecied Temper-ah.re: If void, why: ColTected Temperaitre.: Thennometer: IR1 IR2 (Ci-one) 5 ... _..--... 6tored in R~tor# 7 Cornmenm:~-------------------------------- WNte: Sample T ravele< Cana,y: Lab Copy Pink: Field Copy Project No. 0344.00 Element No. Section 9 - B3 Revision No. 4 Date March 2018 Page 15 of 16 Figure 9-11. ERG Blank COC Record Chain of Custody Record "" Pairt....,._s- - ..,,.,,.., PROJECT ANALYSES STORAGE LOCATION SITE OOLLECTEO BY fSlgnat.R) .. Iii • ~ ~ EiRG U MS ID FIB.O SAMPLE l.D~ Sl'.-..E-TRJX ~TE/TIM E g REMARKS Fu la> use onl'll RE-.RKS: RECEIVED BY: I O.TE Tit.E IR.EUNQI.ASHED BY:: I DATE I TWE RECEJVED BY: =re I TIME IREUNQUtSHED BY: DATE I TIME RECEIVED FOR LA80RATORY BY: TIME AIRBLLNO. PEO BY: TIME TE.MP "'C CONDITION REMARKS: Project No. 0344.00 Element No. Section 9 - B3 Revision No. 4 Date March 2018 Page 16 of 16 9.5 Analytical Data After analysis, the laboratory will provide narratives describing any anomalies and modifications to analytical procedures, data and sample handling records, and laboratory notes for inclusion in the final report. All laboratory electronic records will be stored for archive on Digital Versatile Disk (DVD), or shared network drive. DVDs are stored in Room 102 in the Laboratory building and the shared network has limited access. Raw data will be stored on the shared network for at least 5 years after the end of the closed contract. All records generated by measurement activities are signed or initialed by the person performing the work and reviewed by an appropriate Task Leader. Measurement results become part of a project report, of which 10 percent is requested by the QA Coordinator (or a reviewer designated by the QA Coordinator) for review. 9.6 Sampling Monitoring Data All COC forms from the monitoring sites will be stored with the analytical results. The forms are also scanned and stored in the LIMS as described in the SOP for Sample Login to the Laboratory Information Management System, SOP ERG-MOR-079. The COC forms will be reviewed by the sample custodian(s), Task Leaders and Program Manager. The laboratory will contact the individual site if necessary information is not completed on the COC forms. The original field data will remain in ERG custody and will eventually be stored on file with the final report until 5 years after the end of the closed contract. Project No. 0344.00 Element No. Section 10 - B4 Revision No. 4 Date March 2018 Page 1 of 13 SECTION 10 ANALYTICAL METHODS REQUIREMENTS Analytical procedures are program-specific because the instrumentation and the target compounds of the four programs differ. The primary analytical instrument is GC/FID/MS for SNMOC, VOCs and PAMS hydrocarbons; High Performance Liquid Chromatography (HPLC) for carbonyls; GC/MS for Semivolatiles (SVOC); Inductively Coupled Plasma/Mass Spectrometer (ICP-MS) for Metals; and Ion Chromatography (IC) for Hexavalent Chromium. All samples taken for SNMOC, VOCs, or PAMS hydrocarbons can be evaluated by GC/FID/MS because the instrumentation is collecting all of the data at the same time. Corrective action for analytical system failures realized at time of analyses is initiated by the Analyst and supported by the Task Leader for that method. All analytical method SOPs are provided in Appendix C. The methods used for NMOC and other individual HAPs analysis not currently discussed will be added to this QAPP when the individual States request the analyses. Samples will not be analyzed until ERG receives approval from EPA. The SOPs for each method are reviewed annually and updated as necessary. The QA Coordinator, Program Manager and Writer/Editor will review, sign and date SOPs before distributing to the laboratories satellite file areas. The previous copies will be replaced with the revised edition. The original, and all previously revised edits, are stored in a historical file maintained by ERG’s Project Administrator. 10.1 Canister Cleanup System The canisters are cleaned using a Wasson TO-Clean Model TO 0108 heated canister cleaning system and is explained in Section 10.1.1. The unheated system is used as backup and is described in Section 10.1.2. A bulk liquid N2 dewar is located external to the ERG laboratory facility. This dewar continuously produces a volume of ultrapure gaseous N2 in its headspace area (~100 psig) that is more than adequate to accommodate all in-lab gaseous N2 applications. Ultrapure gaseous N2 is extracted from the dewar headspace and delivered to the cleaning