### RTI/0212053/01QA May 11, 2012



# Quality Assurance Project Plan Chemical Speciation of PM 2.5 

# Filter Samples

Prepared for:

U.S. Environmental Protection Agency Office of Air Quality Planning and Standards Research Triangle Park, NC 27711

EPA Contract No. EP-D-09-010

Prepared by:

RTI International*

P.O. Box 12194 3040 Cornwallis Road Research Triangle Park, NC 27709

∗ RTI International is a trade name of Research Triangle Institute.QAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 3 of 95



## A.2 Table of Contents

Section Page

A.1 QA Project Plan Identif ication and Approval ................................................................................... ............... 2

A.2 Table of Co ntents ............................................................................................................. ............................... 3

A.3 Distribu tion .................................................................................................................. ................................... 7

A.4 Project/Task Or ganiza tion ..................................................................................................... .......................... 7 A.4.1 Key Pers onnel ................................................................................................................. ............... 9 A.4.1.1 Program Manager and Administra tive Program Coordinator .................................. 9 A.4.1.2 QA Manager ........................................................................................................... 10 A.4.2 Analytical S ubcontractors ..................................................................................................... ...... 10 A.4.2.1 CHESTER LabNet ................................................................................................. 11 A.4.2.2 Desert Research Institu te ....................................................................................... 11

A.5 Problem Definiti on/Background ................................................................................................. .................. 13

A.6 Project/Task De scrip tion

...................................................................................................... ......................... 14 A.6.1 Schedule ...................................................................................................................... ................ 14 A.6.2 Sample Types and Quan tities ................................................................................................... ... 14

A.7 Quality Objectives and Crite ria for Measur ement Data .......................................................................... ...... 15 A.7.1 Data Quality Obj ectives Pr ocess ............................................................................................... .. 15 A.7.2 Quality Objectives for To tal Measuremen t Error ........................................................................ 16 A.7.3 Measurement Quality Objectives ................................................................................................ 18 A.7.4 References .................................................................................................................... ............... 19

A.8 Special Training Requ irements/Cer tification .................................................................................. ............. 20 A.8.1 Current Personnel ............................................................................................................ ........... 21 A.8.2 Summary of Experien ce and Tr aining ......................................................................................... 24 A.8.3 New Personnel ................................................................................................................ ............ 25

A.9 Documentation and Records .................................................................................................... .................... 26 A.9.1 QA/QC Records ................................................................................................................ ......... 27 A.9.2 SHAL Records ................................................................................................................. .......... 27 A.9.3 Analytical Labora tories’ Records ............................................................................................. .. 28 A.9.4 Gravimetric Mass La boratory R ecords ....................................................................................... 29 A.9.5 XRF Laborator y Reco rds ....................................................................................................... .... 30 A.9.6 IC Laborato ry Records ........................................................................................................ ....... 30 A.9.7 OC/EC Laborato ry Reco rds...................................................................................................... .. 31 A.9.8 Denuder Refurbishment Laboratory Re cords .............................................................................. 31

B.1 Sampling Process Design (Experimenta l Design) ................................................................................. ........ 33

B.2 Sampling Methods Requirements ................................................................................................. ................. 33

B.3 Sample Handling and Custody Requi rements ...................................................................................... ......... 33 B.3.1 Sample Handling Deliver y Order Process ................................................................................... 33 B.3.2 Chain of Custody .............................................................................................................. ........... 35 B.3.3 Processing System for PM Ch emical Speciatio n Modules .......................................................... 35 B.3.3.1 Assembly of Samp ling Modules ............................................................................ 39 B.3.3.2 Shipping to and fr om the Field ............................................................................... 39 B.3.3.3 Disassembly of Sa mpling Modules ........................................................................ 41 B.3.3.4 Internal Tracking of Analytical Samples ............................................................... 41 B.3.3.5 Archiving of Filte rs and Extracts .......................................................................... 41 B.3.3.6 Denuder Preparation .............................................................................................. 43QAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 4 of 95

B.4 Analytical Method s Requirem ents ............................................................................................... ................. 44 B.4.1 Gravimetric Mass Determination ................................................................................................ 44 B.4.2 EDXRF Analysis for Elements ................................................................................................... . 44 B.4.3 Extraction and Analysis of Anions and Cations .......................................................................... 45 B.4.4 Carbon An alysis

............................................................................................................... ........... 45 B.4.5 Semivolatile Orga nic Compounds ............................................................................................... 46 B.4.6 Characterization of Particles by El ectron and Optical Microscopy ............................................. 46 B.4.6.1 Scanning Electro n Microscopy .................................................................................................. .. 46 B.4.6.2 Optical Micr oscopy ............................................................................................................ ......... 47

B.5 Quality Control Requirements .................................................................................................. ..................... 48 B.5.1 Quality Criteria for Grav imetric Anal yses .................................................................................. 48 B.5.1.1 Gravimetric Disaster Recovery Plan ........................................................................................... 49 B.5.2 Quality Criteria fo r Ion Anal ysis ............................................................................................. .... 49 B.5.2.1 Ion Disaster Recovery Plan for Data ........................................................................................... 50 B.5.3 Quality Criteri a for ED XRF .................................................................................................... .... 50 B.5.3.1 RTI ......................................................................................................................... 5 0 B.5.3.2 CHESTER LabNet ................................................................................................................ ...... 51 B.5.4 Quality Criteria for RT I OC/EC Anal ysis ................................................................................... 52 B.5.4.1 RTI OC/EC Lab Disaster Rec overy Plan for Data ...................................................................... 55 B.5.5 Quality Criteria for Denu der Refurbishments ............................................................................. 55 B.5.6 Uncertainty De termina tion ..................................................................................................... ..... 56 B.5.7 Method Detec tion Limits ....................................................................................................... ...... 57

B.6 Instrument/Equipment Testing, Inspectio n, and Maintenance Requirements ............................................... 57 B.6.1 Gravimetric Mass Laboratory ................................................................................................... ... 57 B.6.2 Ion Chromatographi c Laboratory ................................................................................................ 58 B.6.3 EDXRF Laboratory .............................................................................................................. ....... 59 B.6.3.1 RTI ......................................................................................................................... 5 9 B.6.3.2 CHESTER LabNet ................................................................................................. 60 B.6.4 ICP/MS Labo ratory ............................................................................................................. ........ 60 B.6.5 Organic/Elemental Carbon (OC/EC) Laboratory ........................................................................ 62 B.6.5.1 RTI OC/EC Labo ratory .......................................................................................... 62 B.6.5.2 DRI OC/EC Labo ratory ......................................................................................... 62

B.7 Instrument Calibratio n and Frequency .......................................................................................... ................ 63 B.7.1 Gravimetric Mass Laboratory ................................................................................................... ... 63 B.7.2 Ion Chromatography Laboratory ................................................................................................. 63 B.7.3 EDXRF Laboratory .............................................................................................................. ....... 63 B.7.3.1 RTI ......................................................................................................................... 6 4 B.7.3.2 CHESTER LabNet ................................................................................................. 65 B.7.4 OC/EC Labor atories ............................................................................................................ ........ 65 B.7.4.1 RTI OC/EC Labo ratory .......................................................................................... 65 B.7.4.2 DRI OC/EC Labo ratory ......................................................................................... 66

B.8 Inspection/Acceptance Requirements for Supplies and Consumables .......................................................... 67 B.8.1 Filters ....................................................................................................................... .................... 67 B.8.1.1 Teflon F ilters .......................................................................................................... 68 B.8.1.2 Nylon Filte rs .......................................................................................................... 68 B.8.1.3 Quartz Filters ......................................................................................................... 68 B.8.2 Criteria for Othe r Materials .................................................................................................. ....... 69

B.9 Data Acquisition Requirements (Non-direct M easuremen ts) ....................................................................... . 69

B.10 Data Management ............................................................................................................... .......................... 69 B.10.1 Overview ...................................................................................................................... ............... 70 B.10.2 DMS Design Features ........................................................................................................... ....... 70 B.10.2.1 Sample Identifiers .................................................................................................. 70QAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 5 of 95

B.10.2.2 Barcode Scanners ................................................................................................... 71 B.10.2.3 Relational In tegrity ................................................................................................ 71 B.10.2.4 Double Entry of Field Data .................................................................................... 71 B.10.2.5 Direct Transfer of Laboratory Data ........................................................................ 71 B.10.2.6 Training and Develo pment Databases .................................................................... 72 B.10.2.7 Database Backup and Recovery ............................................................................. 72 B.10.3 Automated and Semi-Automated QC Li mit Checks for Outlie r Detection ................................. 72 B.10.4 Report Preparation an d QA Screening ........................................................................................ 74 B.10.4.1 Data Set Completene ss and Integrity ..................................................................... 74 B.10.4.2 Entry and Verification of Data Changes from the States ....................................... 75 B.10.5 AQS Data Entry ................................................................................................................ ........... 75 B.10.6 Data Management in the Laboratories ......................................................................................... 8 0 B.10.7 Management and Reporting of Field Aud it Data ......................................................................... 80 C.1 Assessments and Re sponse Actions .............................................................................................. ................ 81 C.1.1 External Quality Assu rance Assessments .................................................................................... 81 C.2 Reports to Management.................................................................................................... ............................. 83

D.1 Data Review, Validation, an d Verification Requirements ........................................................................ .... 85

D.2 Validation and Verification ................................................................................................... ........................ 85 D.2.1 Level 0 Va lidatio n ............................................................................................................ ........... 85 D.2.2 Level 1 Va lidatio n ............................................................................................................ ........... 86 D.2.3 Screening of Subcontractor Data ............................................................................................... .. 86 D.2.4 Data Corr ections .............................................................................................................. ............ 87

D.3 Reconciliation With User REquirements .................................................................................... .................. 85



### List of Tables Table Page
A.3.1. QAPP Di stribution List ................................................................................................ ...................................... 7 A.4.1. Personnel Responsibilitie s and Lines of Communica tion ................................................................. ................. 9 A.6.1. Families of SVOCs to be Quantitated by GC/M S Methodologies ............................................................ ....... 12 A.6.2. Sample Quantities for Base Period January 26, 2009 throug h January 25, 201 2 ........................................... .. 14 A.7.3. Recommended MQOs fo r Total Measur ement Error .......................................................................... ............. 16 A.7.4. Laboratory MQOs ....................................................................................................... ..................................... 18 A.9.1. Management Records .................................................................................................... .................................. 26 A.9.2. QA/QC Records ......................................................................................................... ...................................... 27 A.9.3. SHAL’s Records ........................................................................................................ ...................................... 27 A.9.4. Analytical La boratories’ Records ...................................................................................... .............................. 28 A.9.5. Gravimetric Ma ss Laboratory Records ................................................................................... ......................... 29 A.9.6. XRF Labo ratory Records ................................................................................................ ................................. 30 A.9.7. IC Laboratory Records ................................................................................................. .................................... 31 A.9.8. OC/EC Laboratory Records .............................................................................................. ............................... 31 A.9.9. Denuder Refurbishm ent Laboratory Records .............................................................................. .................... 32 B.3.1. Sampler Component and Labora tory Speciation An alysis Matrix ........................................................... ........ 40 B.4.1. Carbon Fr actions Re ported ............................................................................................. ................................. 47 B.5.1. QC Criteria for Ion Chro matography (Anions and Cations) ............................................................... ............. 50 B.5.2. RTI QC Procedures to Analyze EDXR F Elements ........................................................................... ............... 51 B.5.3. CHESTER LabNet’s QC Procedures Used to Analyze EDXRF Elements ...................................................... 51 B.5.4a. QC Criteria for OC/EC Analysis by CS N/TOT and IMPROVE_A/TOR-TOT Methods in RTI’s OC/EC Labor atory .............................................................................................................. ............ 52 B.5.4b. QC Criteria for OC/EC Analysis by IMPROVE_A/TOR-TOT Methods in DRI’s OC/EC Laboratory .................................................................................................................... ................... 54 B.5.5. QC Criteria for Denuder Refurb ishments ................................................................................ ........................ 56QAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 6 of 95

B.6.1. Inspection Criteria for Gravimetric Mass Laborato ry ................................................................... ................... 57 B.6.2. Gravimetric Mass Laboratory Ma intenance Schedule and Respon sibility ................................................... .... 58 B.6.3. Inspection Criteria fo r Ion Analysis Laborato ry ....................................................................... ....................... 58 B.6.4. Ion Analysis Laboratory Ma intenance Schedule and Respons ibility ....................................................... ........ 59 B.6.5. Inspection Criteria for RTI EDXRF Laboratory .......................................................................... .................... 59 B.6.6. RTI EDXRF Laboratory Mainte nance Schedule an d Responsibility .......................................................... ..... 60 B.6.7. Inspection Criteria for CH ESTER LabNet EDXR F Laboratory ............................................................... ....... 60 B.6.8. CHESTER LabNet XRF Laboratory Ma intenance Schedule and Responsibility ............................................ 60 B.6.9. Elements to be Analyzed by ICP/MS ..................................................................................... .......................... 61 B.6.10. Quality Contro l Activities for ICP/MS Analysis Se quences ............................................................. ............. 62 B.6.11. OC/EC Laboratory Mainte nance Schedule an d Respons ibility ............................................................. ........ 62 B.6.12. OC/EC Laboratory Mainte nance Schedule an d Respons ibility ............................................................. ........ 63 B.7.1. Elements Present on Micromatter, Co. Standard ......................................................................... .................... 64 B.7.2. Certified Values of Elements Present on NIST Standard Refere nce Material No. 1832 ................................ 65 B.7.3. RTI OC/EC Instrument Calibration an d Freque ncy ........................................................................ ................. 66 B.7.4. DRI OC/EC Instrument Calibration an d Freque ncy ........................................................................ ................ 67 B.10.1. Label Identifiers for Tr acking CSN Records and Equipment ............................................................. ........... 71 B.10.2. Statistical Validatio n Limits for Ro utine Data ....................................................................... ........................ 73 B.10.3. Statistical Valida tion Limits fo r Blanks ............................................................................. ............................ 73 B.10.4. Mapping of Outlier Flags onto AQS Codes .............................................................................. ..................... 74 B.10.5. Automated Checks Based on Fixed Criteria ............................................................................. ..................... 74 B.10.6. Analytes and AQS Parameter Codes (PM 2.5 Only) ........................................................................................ 76 B.10.7. Field Data an d AQS Parameter Codes ................................................................................... ........................ 78 B.10.8. AQS Validity Status Codes ............................................................................................ ................................ 78 B.10.9. AQS Null Value Codes ................................................................................................. ................................. 79



### List of Figures Figure Page
A.4.1. Schematic of RTI’s team members and organization for the chemical speciation of PM 2.5 filter samples. ...................................................................................................................... ....................... 8 B.3.1. Overview of sample handling and custody system. ....................................................................... .................. 34 B.3.2. Diagram of RTI filter processing and analys is activities by filter type (arrangement may vary by sampler model). ............................................................................................................... ................ 37 B.3.3. Movement of filters and extracts th rough RTI and subcontr actor labora tories

. .......................................... ..... 38 B.3.4. RTI Laboratory COC form used in tracking. ............................................................................. ...................... 42QAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 7 of 95



## A.3 Distribution
Upon finalization, controlled copies of this Quality Assurance Project Plan (QAPP) will be distributed in hard copy to the individuals listed in Table A.3.1. The latest version of each Standard Operating Procedure (SOP) will also be available at the laboratory where it is used. The Quality Assurance (QA) Manager will oversee control and update of the QAPP and SOPs.

Table A.3.1. QAPP Distribution List

Copy Number Recipient Name Position Organization 1 M. Dougherty Project Officer U.S. EPA/OAQPS 2 D. Shelow Technical Project Manager U.S. EPA/OAQPS 3 D. Crumpler Quality Assurance Officer U.S. EPA/OAQPS 4 P. Schraufnagel Delivery Order Project Officer U.S. EPA 5 J. Delwiche Delivery Order Project Officer U.S. EPA 6 L. Hyden Delivery Order Project Officer U.S. EPA 7 J. Elkins EPA Quality Assuranc e Laboratory Director U.S. EPA 8 R.K.M. Jayanty Program Manager RTI/EISD

9 D.M. Haas Administrative Coordinator RTI/EISD 10 J.B. Flanagan Quality A ssurance Manager RTI/EISD

11 J.A. O’Rourke* SHAL Tec hnical Area Supervisor RTI/EISD

13 P. Pressler Jur* Gravimetric Ma ss Technical Area Supervisor RTI/EISD 14 E.D. Hardison* Ions Analysis Technical Area Supervisor RTI/EISD 15 E.E. Rickman* Data Management Technical Area Supervisor RTI/EISD 16 A.C. McWilliams* Elemental Analysis Technical Area Supervisor RTI/EISD 17 P. Doraiswamy* Carbon Analysis Technical Area Supervisor RTI/EISD 18 F.X. Weber* ICP-MS Technical Area Supervisor RTI/EISD 19 R. Tropp* DRI Quality Assurance Manager DRI 20 P. Duda* CHESTER LabNet Quality Assurance Manager CHESTER LabNet * Individuals responsible for maintaining current SOPs at laboratory stations wher e procedures are performed.



## A.4 Project/Task Organization
This QAPP describes quality planning for contract numbe r EP-D-09-010 with the U.S. Environmental Protection Agency (EPA) Offi ce of Air Quality Planning and Standards (OAQPS). Work on this contract in support of the PM Chemical Speciation Network (CSN) program is performed by staff from RTI Intern ational’s Environmental and Industrial Sciences Division (EISD), which is a component of the Discovery and Analytical Sciences. CHESTER LabNet, a subcontractor to RTI, and RTI will pe rform x-ray fluorescence (XRF) analysis. Desert Research Institute (DRI), another subcontractor to RTI, will perform organic/elemental carbon (OC/EC) analysis using the same method that is used in the Interagency Monitoring of Protected Visual Environments (IMPROVE) program: a nd semivolatile organic compounds (SVOC), andQAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 8 of 95


### optical density (OD) analysis on selected filters. Sound management requires a clear understanding of the roles, functions, and a ssignments of each position within the project
structure. Figure A.4.1 shows RTI’s team members. Table A.4.1 shows the responsibilities and lines of communication for each of the positions on this program.

Figure A.4.1. Schematic of RTI’s team members and organization for the chemical speciation of PM 2.5 filter samples.QAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 9 of 95

Table A.4.1. Personnel Responsibilities and Lines of Communication

Position Responsibilities Lines of Communication Program Manage r R. K. M. Jayanty Accountable to corporate management for successful accomplishment of the project objectives. Supervises project. Coordinates project activities with client and subcontractors. Reports Director Bruce Harvey.

QA Manage r James B. Flanagan Responsible for monitoring all aspects of QA/QC. Reports to Program Manager. Works closely with technical area supervisors and staff. Performs peer-to-peer coordination with subcontractor QA staff. Technical Area Supervisors Owen Crankshaw Paige Presler-Jur Eva Hardison Andrea McWilliams James O’Rourke Prakash Doraiswamy Edward Rickman Frank Weber Responsible for maintaining technical quality, data handling and transfer, and identifying and resolving technical problems. Responsible for staff training and assessment. Reports to Program Manager. Works closely with technical staff and QA Manager.

Technical Staf f Performs technical ta sks. Interacts with other team members. Reports to Technical Area Supervisors.

CHESTER LabNet Paul Duda, Project Manager Rick Sarver Lisa Ball Emmely Briley Jess Mace Responsible for receiving samples from RTI, performing XRF analyses, maintaining technical quality, data handling and transfer, and identifying and resolving technical problems for staff training and assessment. Reports to RTI Program Manager.

DRI Judy Chow, Project Manager Barbara Zielinska, SVOC Dana Trimble, OC/EC R. J. Tropp J. G. Watson Responsible for receiving samples from RTI, performing OC/EC by IMPROVE method and SVOC analysis on selected filters, maintaining technical quality, data handling and transfer, and identifying and resolving technical problems for staff training and assessment. Reports to RTI Program Manager.



### RTI coordinates its laboratory support activ ities with EPA/OAQPS and with the State, Local, and Tribal (SLT) agencies. Lab QA aud iting and technical assistance are provided by EPA/ORIA as described in the Field QAPP (Qua lity Assurance Project Plan: PM2.5 Chemical Speciation Sampling at Trends, NCore, SLAMS, and Tribal Sites, USEPA/OAQPS, October 2011), Sections 4.0 and 4.3.2, and Figure 4-1.

A.4.1 Key Personnel A.4.1.1 Program Manager and Admi nistrative Program Coordinator The CSN program is led by Dr. R. K. M. Jayanty, who provides overall supervision to ensure that the technical program is being pe rformed in accordance with the EPA statement of work and according to this QAPP.
The RTI Program Manager’s responsibilities include:QAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 10 of 95


### 1. Maintaining cooperative working relationships with the EPA Project Manager, Delivery Order Project Offi cer (DOPO), and QA Manager in the following ways: Conference calls to be held biweekly in itially, or as frequently as needed Meetings with EPA staff in RTP on an as-needed basis Written communications and e-mails to document planning and decisions 2. Facilitating interaction among team personnel 3. Ensuring that proper technique s and procedures are followed 4. Ensuring that reporting re quirements are satisfied 5. Maintaining cost and schedule control 6. Adjusting schedules to meet the needs of the client 7. Reviewing and approving deliverables submitted to the client.

Ms. Diane M. Haas is the Administrative Program Coordinator fo r the CSN program and is responsible for financial and other pr oject coordination activ ities within RTI.
A.4.1.2 QA Manager Dr. James B. Flanagan is the RTI QA Manage r for this project. As a member of the Quality Systems Program (QSP) Department, he is administratively independent from the staff performing the project work and data generation. Fo r the purposes of this project, he will report to Mr. Bruce Harvey, EISD Division Director, an d to Dr. Jayanty, the Program Manager. Dr. Flanagan will monitor quality assurance/quality c ontrol (QA/QC) for the project. Dr. Flanagan selected staff members will investigate prob lems and recommend corrective actions, perform periodic in-lab and data review audits, host external auditors during anticipated visits, and distribute EPA-provided Performa nce Evaluation (PE) samples and summarize the results of analysis of PEs.

A.4.2 Analytical Subcontractors RTI has engaged CHESTER LabNet as a subcontractor to provide limited energy dispersive x-ray fluorescence spectroscopy (EDXRF) services for this program. RTI has also engaged DRI as a subcontractor for OC/EC analysis by the IMPROVE_A method, and SVOC analysis, and determination of OD on selected filters.

All subcontractor laboratorie s providing analytical servi ces for this program have contributed to this project-sp ecific QAPP and must provide th eir SOPs for EPA approval. If requested by EPA, subcontractors will undergo technical systems a udits of their facilities and will analyze EPA-provided PE samples. RT I will maintain standards and document comparability of laboratories performing the same analyses through an intercomparison program for each type of analysis. Calibration check samples from the same source will be analyzed by both laboratories. The RTI XRF laboratory coordi nates a filter reanalys is program in which selected filters are reanalyzed by the particip ating XRF laboratories (currently just RTI and Chester Labnet). Intercomparison results ar e summarized in annual qua lity assurance data reports. Subcontractors are also required to provide input for th e quarterly metadata reports and the annual quality assurance data report.QAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 11 of 95


### The capabilities of each subcontractor are br iefly outlined in the following subsections.

A.4.2.1 CHESTER LabNet RTI will send XRF samples to CHESTER LabNet as long as CHESTER LabNet demonstrates that it can meet the quality, samp le turnaround, and cost requirements for this program. The initial throughput capacity usi ng the CHESTER LabNet Kevex 770 XRF for Protocol #6 was 25 samples per day. To boos t productivity, CHESTER LabNet purchased a second Kevex XRF, numbered 771. Samples we re analyzed on both the 770 XRF and the 771 XRF to test for equivalency, and a report titled “Tests of Equivalency for Two XRF Instruments Operated by CHESTER LabNet,” which showed acceptable equivalency of the two XRFs, was submitted to EPA and approved. With these two approved instruments, CHESTER LabNet has a total capacity of approximately 50 samples pe r day. CHESTER LabNet has purchased a third Kevex XRF for serving its other clie nts, but this instrument is not used for CSN analyses because no equivalency study has been performed.

RTI and Chester obtain their calibration stan dards from the same supplier (Micromatter Co). Both labs analyze a multi-element standard that is prepared by Micromatter, containing Si, Ti, Fe, Se, Cd, and Pb at levels of 5-10 μ g/cm 2 

### . The multi-element standard is analyzed with each tray of samples.

A.4.2.2 Desert Resear ch Institute The Desert Research Institute is the nonprof it research campus of the University and Community College System of Nevada (UCCSN). The main campuses are located in Las Vegas, NV (Southern Nevada Science Park) and Reno, NV (D andini Research Park), with subsidiary campuses in Boulder City, NV, and Steamboat Springs, CO. DRI’s environmental research programs are directed from three core divisions (Atmospheric Sciences, Earth and Ecosystem Sciences, and Hydrologic Sciences) and two interdisciplinary centers (the Center for Arid Lands Environmental Management and th e Center for Watersheds and E nvironmental Sustainability). DRI's analytical capabilities on this program are described below.

IMPROVE_A OC/EC Analysis for URG 3000N Filter Samples 

### RTI has subcontracted with DRI to provide OC/EC analysis for filter samples obtained using the URG 3000N sampler following the same method as currently employed by the IMPROVE program. This analyt ical protocol, known as IM PROVE_A, was developed by DRI using the DRI Model 2001 Thermal/Optical Ca rbon Analyzer (manufactured by Atmoslytic, Calabasas, CA) and was placed in service on the IMPROVE program beginning January 1, 2005. The method is based on the tech nical requirements given in DRI’s SOP. RTI and DRI have defined data transfer formats and procedures and have developed an SOP for IMPROVE OC/EC analysis.
The DRI Model 2001 analyzer used by DRI cons ists of essentially the same components as the Sunset Laboratory instru ment used by RTI, although the c onfiguration is quite different. The basic components of the system include a sa mple oven fitted with a laser-photodiode sensor, an oxidizer oven, a methanator, a flame ionizati on detector (FID), other components used to control oven temperature and gas composition a nd flows, and a computer workstation running software through which analysis parameters ar e controlled and data from the FID, photodiodeQAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 12 of 95


### sensor, and oven thermocouples are collected. All carbon volatilized from the filter is converted to CO 2 

### in the oxidizer, and the CO 2 

### is converted to methane (CH 4 

### ) in the methanator before passing into the FID, where it is measured. The lase r is used to track and correct for the pyrolysis of OC that occurs during the iner t combustion phase. laser shines on the quartz filter section in the oven, and some of the light is reflected or scattered back onto a photodiode located on the same side of the filter and some of the lig ht is transmitted through the filter. The laserphotodiode sensors are used to mon itor reflectance and transmittance of laser light from the filter section during analysis.
Data generated by the IMPROVE_A method is reported using both the Thermal Optical Transmittance (TOT) and Thermal Optical Refl ectance (TOR) methods. TOT and TOR results for certain OC fractions differ, so both will be reported to EPA’s Air Quality System (AQS) database under separate parameter codes.

Semivolatile Organics Compound Analysis 

### RTI has subcontracted with DRI to provide S VOC analysis on selected filter samples.DRI will analyze selected quartz fiber or Teflon filters and back-up sorbent traps for semivolatile organic aerosol compounds using an extraction procedure that can accommodate multiple filters. DRI will extr act semivolatile organic aerosol compounds from the filters and back up sorbent traps. The families of semi-volatile organic compounds (target analytes) to be quantitated for routine analysis are given in Table A.6.1. When requested, seve ral filters may be combined for extraction to yield a more concentr ated extract solution. Ex tracts will be analyzed for semi-volatile organic aer osol compounds using gas chro matography/mass spectroscopy (GC/MS) methodology. All anal ytical runs will be supported by QC analyses including replicate analyses. Sample extracts will be stored at DRI for at least 6 months and up to the life of the
contract as re quested by EPA.

Table A.6.1. Families of SVOCs to be Quantitated by GC/MS Methodologies

Family Examples
n-alkanes n-tricosane, n- tetracosane, n-pentacosane

iso-alkanes Iso-hentrac ontane, iso-dotracontane

anteiso-alkanes anteiso-triac ontane, anteiso-hentriacontane

alkenoic acids Cis-9-n-octadecenoic acid

aldehydes nonanaldehydes levoglucosan levoglucosan Polycyclic aromatic hydrocarbons numerous hopanes and steranes numerous



### Optical Density 

### RTI has subcontracted with DRI to provide OD (also known as “black carbon”) analysis on selected filter samples. DRI will analyze selected Teflon filters for OD as described by Watson and Chow (1988). The densitometer used for the analysis is similar to the integrating plate method used by photographers to evaluate black-and-white negatives. Transmittance is measured before and after filter exposure, and th e difference in the logarithms of the transmittedQAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 13 of 95


### light is proportional to the absorption of the pa rticle deposit. Transmittance is standardized using photographers’ neutral-density filters that are commonly used for light attenuation in camera lenses and photographic enlargers. A high corr elation between OD and IMPROVE EC has been found.


## A.5 Problem Definition/Background
In 1997, the EPA promulgated the new Na tional Ambient Air Quality Standards (NAAQS) for particulate matter (PM). The regu lations (given in 40 CFR Parts 50, 53, and 58) apply to the mass concentrations ( : g/cubic meter of air) of partic les with aerodynamic diameters less than 10 micrometers (the PM 10 

### standard) and to particles with aerodynamic diameters less than 2.5 micrometers (the PM 2.5 

### standard). To support these standards, a 1500-site mass measurements network and a smaller PM 2.5 

### Chemical Speciation Network (CSN) were established. Gravimetric mass and chemical speci ation analyses will also be performed for PM 10 

### and coarse PM as part of the NCore program and for research studies as part of the CSN contract. Coarse PM, both total mass and individual chemical species, will be determined either as PM 10 

### minus PM 2.5 

### ( PM 10-2.5 

### ) based on separate PM 10 

### and PM 2.5 

### filter samples, or as coarse PM obtained by dichotomous sampling.

The ambient air data from the network, whic h measures solely the mass of particulate matter, are used for NAAQS comparison purposes in identifying areas that meet or do not meet the NAAQS criteria and in supporti ng designation of an area as attainment or non-attainment. The CSN consists of a set of core sites and addi tional non-core sites. Chem ically speciated data are used to serve needs associated with devel opment of emission mitigation approaches to reduce ambient PM concentration levels. Such needs include emission inventory establishment, air quality model evaluations, and source attribution analysis. Other uses of the data sets will be regional haze assessments, estimating personal e xposure to PM and its components, evaluating potential linkages to health effects, and support for setting a secondary NAAQS for PM.
RTI supports the CSN by shipping ready-to-use filter packs and denuders to the field sites and by conducting gravimetric and chemical analyses of the several types of filters used in the samplers. This QAPP focuses on the QA activities a ssociated with RTI’s role in filter scheduling and distribution, performing the filter analys es, and validating a nd reporting the data.
Prior to operation of the core and additional sites, EPA ran a prototype network, informally known as the “mini-trends” network, in early 2000. This network was comprised of 13 monitoring stations in th e continental U.S. Each site had two or more PM 2.5 

### chemical speciation monitors to enable various sampler intercomparisons . The mini-trends network ran from February 2000 to August 2000. RTI is curr ently supporting approximately 180 sites.
Beginning in May 2007, the CSN began operation of 57 URG 3000N samplers, which are used to obtain samples on quartz filters that are comparable to those being sampled by the IMPROVE network. The filter samples obtained us ing the 3000N sampler are analyzed by the IMPROVE_A method by subcontractor DRI. Outf itting the remaining sites in the CSN with URG 3000N samplers was complete in FY10. Sa mpling of quartz filters on the MetOne SASS sampler and analysis by the CSN method con tinued past the end of FY10 to support an intercomparison special study being conducted by EP A. Legacy CSN sampling and analysis also continued into 2011 at a small number of s ites at the request of the air agencies.QAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 14 of 95


### Beginning with the laboratory contract that began in 2009, gravimetric and chemically speciated measurements were added for PM 10 

### and coarse PM filters. The XRF method was modified to omit 15 rarely seen elements, and several new measurements were incorporated, including, for selected filters, inductively coupled plasma/ma ss spectrometry (ICP/MS), SVOC analysis, and optical density (OD); as well as de termination of gas phase ammonia, nitric acid, and SO 2 

### using denuder technology.


## A.6 Project/Task Description
The CSN laboratory contract involves four broad areas: 1. Supplying each site or monitoring agency with sample collection media (loaded filter packs and, when ordered, denuders) and field data documentation forms. RTI will ship the collection media to the sites or other designated locations specified by the monitoring agencies on a sche dule specified by the DOPO.

2. Receiving the samples from the field site s and analyzing the sample media for mass and for an array of chemical constituents including elements (by EDXRF), soluble anions and cations, and carbonaceous speci es. Analysis of SVOCs, OD, gas-phase ammonia, ICP/MS, and examination of par ticles by electron or optical microscopy will be provided for selected samples.

3. Assembling validated sets of data from th e analyses, preparing data reports for EPA management and the states, and entering da ta into the AQS data bank 60 days after initial data reports are first submitted to the DOPO and the states.

4. Establishing and applying a compre hensive QA/QC system. RTI’s Quality Management Plan, this QAPP, and associ ated SOPs provide the documentation for RTI’s quality system.

RTI will provide all the staff, facilities, analytical instru mentation, computer hardware and software, and consumable supplies necessary to carry out tasks from these work areas and will ensure that all contract ual specifications are met.

A.6.1 Schedule The present contract pe riod extends from January 26, 2009 to January 25, 2014.
A.6.2 Sample Types and Quantities

Table A.6.2 shows the number of samples for th e base period (January 26, 2009 through January 25, 2010) that were specified in RTI's contract with EPA/OAQPS. Similar quantities have been received in subsequent co ntract years, and this level of activity is expected to continue for the remainder of the contract unless program funding is reduced.QAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 15 of 95

Table A.6.2. Sample Quantities for Base Period January 8, 2009 through January 7, 2010

Line Item Description Each No. Samples

0001 PM 2.5 Gravimetric Mass Each 100 0002 Elemental Analysis by EDXRF Each 100 0003 Sulfate, Nitrate, Ammonium, Water-Soluble Sodium and Potassium Each 100

0004 Magnesium Oxide/SC Denuder Each 60 0005a Organic, Elemental, and Total Carbon (CSN) Each 5,850 0005b Organic, Elemental, and Tota l Carbon (IMPROVE) Each 13,650
0006 Suite 1-3 Each 19,500 0007 Ammonia Analysis and Denuder Refurbishment Each 250 0008 Nitric Acid and SO2 analysis and Denuder Refurbishment Each 100 0009 Semivolatile Organic Aerosol Analysis Each 10 0010 Electron Microscopy Analysis Each 50 0011 Optical Density Analysis Each 10 0012 Organic Denuder Refurbishment Each 50 0013 Elemental Analysis by ICP/MS Each 100



## A.7 Quality Objectives and Criteria for Measurement Data A.7.1 Data Quality Objectives Process The data quality objectives (DQO) process is a strategic planning approach used to prepare for a data collection activ ity in order to achieve data of adequate quality to support decision making. The DQO process helps to ensure that the type, quantity, and quality of environmental monitoring data will be su fficient for the data’s intended use, while simultaneously ensuring that resources are no t wasted collecting unnecessary, redundant, or overly precise data. The formal DQO process consis ts of seven steps that allow an experimental design to be developed to meet decision criteria specified by st akeholders in the decision, as described in EPA QA/G-4, Guidance for the Data Quality Objectives Process (EPA, 1994).
A Chemical Speciation DQO Workgroup was established to develop and document DQOs for the PM 2.5 

### CSN. The primary DQO, detection of tr ends in the chemical speciation data, was defined as follows by participants in the EPA workgroup, who acted as stakeholders for the program, see: http://www.epa.gov/ttn/ amtic/files/ambient/pm25/spec/dqo3.pdf .

“to be able to detect a 3%–5% annual tr end in the concentrations of selected chemical species with 3–5 years of data on a site-by-site basis after adjusting for seasonality, with power of 0.80.” (EPA, 1999a)
Several secondary objectives for data collect ed at the CSN sites and other chemical speciation sites were identified, but these were not evaluated quantitatively by the workgroup. Five important secondar y data uses are as follows:

 

### Model evaluation, verification, and/or validation

 

### Emission inventoryQAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 16 of 95

 

### Source attribution

 

### Spatial and seasonal characteriza tion of aerosol distributions

 

### State Implementation Plan (SIP) a ttainment and strategy development

The desirable data quality characteristics for these secondary objectiv es are significantly different from those applicable to trend assessment.
A.7.2 Quality Objectives fo r Total Measurement Error The DQO study also concluded that with samp ling every third day for 5 years, trends greater than 5% (or less than –5 %) per year can be detected for sulfate, calcium, and total carbon on a single-site basis. For nitrate, however, th e annual trend must exceed ±6.3% to be detected with a power of 80%. The workgroup members conc luded that this was not sufficiently different from the 5% goal to require adjustment to th e sampling design. Sampling daily instead of every third day provides little improvement in the abil ity to detect trends; however, the model showed that cutting the sampling rate to every sixth day begins to impair the ability to detect concentration trends within 5 years.
The Speciation Strategic Plan (U.S. EPA 1999b) quotes Measurement Quality Objectives (MQOs) for the overall measurement process that must be achieved in order to meet the DQO for trend detection. These MQOs, which should be inte rpreted as the total co efficient of variation (CV) attributable to sampling and analysis, are summarized in Table A.7.3. Analysis of the IMPROVE data and the model indi cated that reduction of measurement errors below levels shown in this table is unlikely to result in any significant improvement in the ability to detect a trend within the parameters specified in the DQO statement. Note that th ere is no MQO-specified bias. In terms of completeness, the trend dete ction model was found to be relatively insensitive to sampling interval as long as approximately 1- in-3-day sampling is achieved. Thus, 1-in-3-day sampling was implemented at the original trends sites.

Table A.7.3. Recommended MQOs for Total Measurement Error

Analysis MQO for Total Measurement Error (expressed as % CV) Ions (anions and cations) by IC 10% Total Carbon by TOR 15% Elements by EDXRF 20%

Source: U.S. EPA 1999bQAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 17 of 95


### Total measurement error corresponding to the values given in Table A.7.3 may be estimated by combining individual components of random error using QC data collected by the laboratories and in the field. However, the best way to determine total error of measurement for comparison with the target MQOs given in Table A.7.3 is by statistical an alysis of data from sites that operate collocated monitors. Estim ates based on results from six CSN sites where collocated samplers are operated are include d in the Annual Data Summary Reports.
Work during the first two CSN contracts (2000–2008) has helped to identify some additional quality issues that we re incorporated into the program as they were recognized:

 Shipping/handling components of uncertainty – The laboratory component of random error is typically much smaller than the to tal random error observed with paired field samples. Thus, improving the precision of laboratory measurements beyond a certain point (e.g., better than + 5% for most species) does not appreciably help overall uncertainty. This is reflected in Tabl e A.7.4, which reports the MQOs for total
measurement error.

 Sensitivity issues – The majority of the PM 2.5 

### sampling for the CSN is being performed using the MetOne SASS sampler, wh ich operates at a flow rate of 6.7 liters per minute and uses 46.2 mm filters. Comp ared with the IMPROVE program, this relatively low flow rate and large filter size results in a sensitivity deficit of up to 11- fold. This sensitivity difference is imma terial for gravimetric mass and species present in large amounts, such as sulfat e, nitrate, and OC. Many trace elements analyzed by XRF that are usually detectible at high levels include iron, sulfur, and silicon. Inclusion of ICP/MS, a much more sensitive method than XRF, will help identify some of the trace elements but, b ecause of cost, ICP/MS cannot be performed on the majority of CSN filters.

 OC artifact – The OC artifact is thought to be the result of adsorbed SVOCs from the gas phase and represents a non-particulate source of carbon. With the MetOne sampler, the OC artifact can amount to 2 μ g/m 3 

### or more, which can bias the results by 20%–30% on a typical sample. Methods for co rrecting for the artifact are available but can never be perfect. Because of the relatively higher flow and smaller surface area, the OC artifact for samples ta ken with the URG 3000N or the IMPROVE samplers are much smaller than for thos e taken with the MetOne SASS. Samples taken with higher flow samplers, such as the PM 2.5 

### FRM sampler, will have intermediate magnitude of OC artifact.

 Uncertainty definitions – Work with receptor modelers during the first two CSN contracts has highlighted the importance of c onsistent definitions of uncertainty to be reported to the AQS database. The original formulation of uncertainty was based on the IMPROVE program’s propagation of erro rs approach and relied on uncertainty values provided by the analytical instru ments software (for XRF and OC/EC). To meet the needs of receptor modeling, it was important that the uncertainties be calculated in a consistent way across all anal yzers. RTI, working with experts in the field of XRF analysis at EPA, UC Davis, and the XRF instrument vendors, developed an approach for harmonizing the uncert ainties reported between different XRFQAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 18 of 95


### instruments. In the process, we also ensured that the total uncertainties for the other CSN analytical techniques (gravime try, ion chromatography, OC/EC) were comparable with those for XRF and were re alistic, based on the collocation results.

DQOs and MQOs for Speciated PM 10 

### and PM coarse 

### PM coarse 

### involves subtraction of results from tw o different filters. A straightforward approach to calculating precision would be to combine the indivi dual uncertainties reported for the PM 2.5 

### and the PM 10 

### filter, assuming additivity of varian ce. This may turn out to be a valid approach for simple species such as gravimet ric mass; however, this approach is likely to significantly underestimate the random variability for other ch emical species for a variety of reasons. Research necessary to develop e xpressions for accuracy and precision and the corresponding DQOs and MQOs applicable to PM coarse 

### is currently being conducted under contract EP-D-08-047, work assignment 4-07.
A.7.3 Measurement Quality Objectives There are several components of total data variability included in the model used in the original DQO study. Of these, laboratory measur ement error is the component that can be controlled and/or quantified most readily th rough the QA/QC program, even though it is significantly smaller than either the day-to-day va riability in environmenta l pollutant levels (U.S. EPA, 1998) or the errors asso ciated with sampling and hand ling (Flanagan et al., 2006).
The original set of MQOs for laboratory an alyses were developed by considering the MQOs for total error shown in Table A.7.4 and the known capabilities of the analytical methods to be used. In this table, systematic bias and random errors are aggregated into a single figure that was called “measurement error” in the DQO study.

Table A.7.4. Laboratory MQOs

Measurement Measurement Erro r a Completeness Goal b

Cations and Anions ± 10% if C > 10 H MDL c

or
± MDL if < 10 H MDL 90%

Carbon Species ± 20% if C > 10 H MDL 90% Filter Weight ± 10% if Wt > 6 μg/m 3 90% Elements (EDXRF) ± 20% if C > 10 H MDL 90%

SVOCs d ± 10% if C > 10 H MDL

or
± MDL if < 10 H MDL 90%

SEM and Optical Microscopic Examination d N/A 90% Denuder Analysis for Ions TBD e 90% Optical Density TBD e 90% Elements (ICP/MS) TBD e 90%QAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 19 of 95

a Measurement error is an aggregate figure that combines systematic bias and random error as described above. b Completeness is based on the number of filters successf ully exposed and returned to RTI for the specified

analysis. Historically, the CSN laboratories have ac hieved completeness well in excess of 95% completeness on a continuing basis.

c MDL = Method detection limit. Typically determined as three times the standard deviation of seven or more replicate measurements of a reagent blank, matrix blank, or low-level ca libration standard; however, other methods for determining the MDL may be used, depending on the analysis. d SVOC and microscopic measurements were not made during the mini-trends portions of the project.

e TBD = To be determined as data are gathered under the proposed effort.



### One justification for combining bias and rando m errors into a single figure is that, over the long time frame of the trends detection study (5 years), bias determinations will tend to fluctuate randomly, so it is appropriate to aggr egate them with measurements of random error, particularly when multiple analyzers are used to perform the same analysis, as is done in the OC/EC, XRF, and ion chromatography laboratories.
Completeness is defined as the percentage of samples successfully analyzed divided by the number successfully sampled and returned to RTI. The DQO study found that 1-in-3-day sampling was adequate to meet the objective of trend detection after 5 years. Other sites not included in the trends portion of the network operate d on either 1-in-3-d ay or 1-in-6-day sampling schedules.

A.7.4 References Flanagan, J.B., R.K.M. Jayanty, E.E. Rickman, Jr., and M.R. Peterson. (2006). PM 2.5 

### Speciation trends network: eval uation of whole-system uncerta inties using data from sites with collocated samplers. Journal of the Air and Wast e Management Association 56 :492– 499. April

. U.S. EPA (1999a). Particulate Matter (PM 2.5 

### ) Speciation Guidance Document (Third Draft)
, U.S. EPA, Research Triangle Park, NC. January 5, 1999.

U.S. EPA (1999b). Strategic Plan: Devel opment of the Particulate Matter (PM 2.5 

### ) Quality System for the Chemical Speciation Monito ring Trend Sites, U.S. EPA, Research Triangle Park, NC, April 16, 1999.

U.S. EPA (1998). Data Quality Objectives for the Trends Component of the PM 2.5 

### Speciation Network , U.S. EPA, Research Triangle Park, NC, 1999. Available on AMTIC at http://www.epa.gov/ttn/amtic/f iles/ambient/pm25/spec/dqo3.pdf . (Accessed 08/09/2011)

U.S. EPA (1994). Guidance for the Data Quality Ob jectives Process: EPA QA/G-4 , Report No. EPA/600/R-96/055, U.S. EPA, Washington, DC.

Watson, J.G, and J.C. Chow (November 8, 1988). The 1987–1988 Metro Denver Brown Cloud Study, Vol. II: Measurements. DRI Document No. 8810 1F2. Final Report.QAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 20 of 95 

## A.8 Special Training Re quirements/Certification
It is important that the analytical re sults produced by each analyst meet MQOs. Attainment of MQOs will be measured by attainme nt of acceptable recovery and precision from analysis of identified reference samples, “blind” test samples, and previously analyzed field samples.
Analysts new to the CSN program will be re quired to be experienced with the basic measurement techniques relevant to the analyses that they are to perform. These techniques include the operation of an an alytical microbalance, XRF, ion chromatography, GC/MS, and electron and optical microscopy. Determination of OC/EC requires an analyst who has been trained to use the apparatus and to practice good laboratory techniques to avoid contamination of filters and standards.
With experience in the basic methodology, the anal yst to be trained (her eafter referred to in Section A.8 as “the analyst”) will read and understand the appropr iate SOP. Under the direction of an analyst experienced in the me thod, the analyst will follow the SOP and use the method to analyze reference samples and, if av ailable, samples that have been analyzed previously by an experienced analyst. These samples might include split filters, filter extracts, and whole filters for XRF and elec tron microscopy. This effort will be continued until the analyst achieves MQOs for recovery (or bias) and precisi on. The Technical Area Supervisor or mentor will also audit the performance of the analyst, checking such operations as calibration, data treatment, system maintenance, and record keep ing. With both acceptable analytical results and a successful systems audit, the analyst will be considered ready to perform program sample analysis. Even then, the analyst will work unde r the direction of a mentor until the mentor believes the analyst is considered ready to work independently. Ongoing performance will be monitored by the program QA Manager through revi ew of analytical data , which are identified by the analyst.
RTI will require gravimetric analysts to pa ss a test similar to the certification test administered to analysts working on the EPA’s PM 2.5 

### Federal Reference Method Performance Evaluation Program (FRM PEP), which RTI he lped to develop under another contract.
Permanent RTI employees, including hi gh-level personnel and Technical Area Supervisor, are eligible to atte nd training courses releva nt to the project areas. Both in-house and extramural training opportunities are provided to RTI’s employ ees at its expense. Most employees attend one or more such courses each year. Project staff will be encouraged to attend courses such as manufacturers’ training sessions or method-specific courses that are relevant to this program.
The training and acceptable performance will be documented in the analysts’ training folder. This will include a record of readi ng and utilizing the SOP and verification by the Technical Area Supervisor and/or mentor th at acceptable method performance has been demonstrated. These folders will include records of all performance standard analyses, formal training, and in-house tr aining and testing.QAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 21 of 95



### A.8.1 Current Personnel RTI believes that no further training is required for current personnel who have performed the chemical and gravimetric analyses in the past. Analysts and other personnel will receive copies of the QAPP and the relevant SO Ps necessary to perform their duties. These documents will contain the requirements applicable to the performance of each analyst’s job.
Relevant experience of current analytical staff are as follows:

Gravimetric Mass Determination 

### Paige Presler-Jur – 11 years of laboratory experien ce, including currently managing RTI’s PM Gravimetry Laboratory ensuring th at proper techniques and procedures are followed in the determination of gravimetric mass, maintaining adequate internal documentation, adjusting schedules to meet the needs of the project, and reviewing and approving deliverables submitted to the client.

Stacy Doorn – Over 15 years of relevant experien ce, including extensive experience in the preparation and analysis of samples by electron microscopy and over 10 years in the determination of gravimetric mass.

Maurice Gerald – Over 16 years of relevant expe rience, including 9 years in the determination of gravimetric mass and 8 months’ prior experience working in the Sample Handling and Archiving Laboratory.

Okisha Hammond – Over 9 years of relevant laborat ory experience, including 4 years in the determination of gravimetric mass.

Karen McCombs – 22 years of laboratory experience, including 9 years in the determination of gravimetric mass.

Ion Analysis



### Eva Hardison – 33 years of relevant experience in the technical and fiscal management of ion chromatographic analysis, including 14 years of filter analysis experience for the National Park Service. Also, extensive experience in sample handling, data reduction/analysis, and report preparation.

David Hardison – 32 years of relevant analytical experience, including 9 years in performing ion analysis of filter extracts fo r the National Park Service, the American Lung Association, the EPA, and the California Air Resources Board.

Christine Van Hise – 15 years of relevant expe rience in sample handling and preparation, including over 3 years of experience in air filter extraction.

Dorrie Pickett – Over 20 years of relevant e xperience in sample handling and preparation, including over 4 years of experience in air filter extraction.QAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 22 of 95



### Metal Analysis



### Andrea McWilliams – 10 years of relevant experien ce, including 8 years of experience operating, maintaining, and troubleshooti ng the ThermoNoran QuanX (EDXRF).

Paul Duda – (CHESTER LabNet) 20 y ears of relevant experien ce including 9 years of experience in air filter analysis by EDXR F and 9 years of experience as a LIMS administrator.

Richard Sarver – (CHESTER LabNet) 23 years of relevant analytical experience, including 17 years of experi ence in environmental air qual ity analysis, specializing in analysis of air particulates by EDXRF.

Organic/Elemental Carbon 

### Prakash Doraiswamy – More than 6 years of relevant experience, including OC/EC analysis by the IMPROVE_A method at Desert Research Institute and at RTI. Recent experience with the current EPA adaptation of NIOSH Method 5040 at RTI. Significant experience in data analysis and interpretation of OC/EC by the IMPROVE_A and CSN protocol s, and their differences.

Melville Richards – More than 25 years of relevant experience, including experience in ion chromatography and carbon analysis. Al so, 6 years of experience in OC/EC analysis by the current EPA adaptation of NIOSH Method 5040.

OC/EC by IMPROVE Method 

### Judy Chow – (DRI) More than 30 years of experi ence in conducting air quality studies and performing statistical da ta analysis. Directs DRI’s Environmental Analysis Facility (EAF). Supervises filter processing and chemical operations and develops cost-effective, yet accurate, methods for aerosol sampling and analysis. Prepared and revised sections of the U.S. EPA’s air qual ity criteria document that pertained to chemical analysis and source emissions. Co -principal investigat or on evaluation of aerosol measurement methods, sampling strate gies, and databases for the U.S. EPA’s guidance document on network design, c ontinuous particulate monitoring, and aerosol measurement methods.

D. L. Trimble – (DRI) More than 16 years of experience in ambient air quality measurements and quality assurance. Serv es as Laboratory Manager for DRI’s EAF Carbon Analysis Laboratory, including data validation, reporting, and analysis of OC/EC measurements.

Steven Kohl – (DRI) More than 10 years of expe rience with scheduling and coordination of laboratory work. Responsibilities include the quality assurance and reporting of data generated by the inorganic analytical laboratory, as well as performing chemical analysis of aerosol samples by x-ray fl uorescence. Also manages field studies, maintains a vast array of field sampling e quipment, and supervises three laboratory technicians. Before coming to DRI, Mr. Kohl developed immunochemical pesticideQAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 23 of 95


### assays for use in fiber optic biosensors fo r environmental monitoring applications for EPA. Mr. Kohl will serve as DRI’s EAF Laboratory Coordinator.

Richard Tropp – (DRI) More than 30 years of expe rience conducting air quality studies, statistical data analysis, and quality assurance. Project Manager for PM 2.5 

### FRM laboratory support to the states of Texas and Oklahoma. Provides coordination among laboratory groups, field personne l, contractors, and subcont ractors. Provided technical support to EPA in preparing PM 2.5 

### regulatory proposal and promulgation packages. Outside reviewer of Section 2.12 of EPA’s QA Handbook.

John Watson – (DRI) More than 30 years in e nvironmental sciences, including the planning and conducting of ma jor air pollution studies. Serves as QA Manager and senior technical advisor for the EAF. Has undertaken review s of visibility science and regulation and is currently investigating the comparability of existing methods for carbon analysis and ways to obtain better, more useful information.

Microscopy



### Owen Crankshaw – 21 years of relevant experien ce with scanning electron microscopy (SEM) and transmission electron microscopy. Sp ecifically experienced in analysis of PM 10 

### and PM 2.5 

### samples, including the analysis of Teflon, polycarbonate, and fibrous glass/quartz filters.

Semivolatile Organic Compound Analysis



### Barbara Zielinska – (DRI) More than 30 years of experience in the development, enhancement, and application of coll ection and analysis methods for trace atmospheric organic species present in bot h gaseous and particulate phases. Work includes the development of analytical methods for measuring biologically active compounds in primary and secondary part iculate organic matter; atmospheric transformations of organic compounds; ozone precursors; and part icle-associated and VOC emissions from various sources, including diesel- and gasoline-powered vehicles, wood combustion, and meat cooking. Currently a member of EPA’s Clean Air Scientific Advisory Committee (CAS AC) and a regular reviewer for the professional journals Environmental Science & Technology and Atmospheric Environment

. Sample Handling



### James O’Rourke – 20 years of relevant experience in sample handling and preparation and denuder refurbishment. Specifically trained in handling and shipping of hazardous materials. Experience in logistic s of shipping and receiving large numbers of samples through EPA radon proficiency te sting program and American Industrial Hygiene Association Environm ental Lead Proficiency An alytical Testing program.

Jessie Deal – 9 years of relevant experience supporting the PM 2.5 

### chemical speciation project, which includes handling, packagi ng, and maintaining records for different types of air filters used for air sampling studi es. Serves as assistant supervisor of the sample handling laboratory and oversees ope rations in Mr. O’Rourke’s absence.QAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 24 of 95


### Database Development/Management



### Edward Rickman – More than 20 years of rele vant experience in design and implementation of environmental and QA data bases, including a database for EPA’s OAQPS PM 2.5 

### Performance Evaluation Program and preparation of programs and queries to combine information from EPA’s Envirofacts Oracle Data server with additional information from other (off-line) sources. Also experienced in statistical evaluation of test data and analytical methods.

Linda Andrews – 12 years of relevant experience in data management and database design. Participated in various database development efforts, which included designing a relational database ; creating necessary data entry forms, queries, reports, and functions; providing technical support or management of data; and creating relationship diagrams and data dictiona ries for database documentation. Also responsible for final flagging and uploadi ng CSN data to AQS after review by the SLT air agencies.

Quality Assurance 

### James Flanagan – More than 20 years of relevant e xperience in data reduction/analysis and QA/QC, including over 12 years with the CSN program. Performed numerous QA plan reviews as well as audits of fi eld measurements and laboratory operations. Provided support for a major QA contract for EPA’s Air Pollution Protection and Control Division (APPCD).

Denuder Refurbishment



### James O’Rourke – Over 20 years of relevant experience in supervision, filter sample preparation and analytical chemistry. Expe rience with the design and operation of PM samplers employed in the CSN and related speciation programs. Experience with the analysis of silica samples for the Am erican Industrial H ygiene Association Environmental Lead Proficiency Analytical Testing program. Over a 25 year career at RTI, has supported a number of EPA sponsored projects including indoor radon, aldehydes and ketones in indoor air, a nd Method 29 multi metals analysis.
A.8.2 Summary of Experience and Training The qualifications of each analyst are maintained in training folders, along with a record of courses taken, special in-house traini ng, and results of performance audits.
Highlights of the present status of experien ce and training of RTI personnel include the following:

 

### Gravimetric mass laboratory staff have given instructional workshops and prepared SOPs to train analysts for the PM 2.5 

### Performance Evaluation Program.

 

### The RTI ion chromatographic team has performe d air filter analysis for the National Park Service for the IMPROVE program. PM 2.5 

### ion analysis has been performed in support of EPA evaluation of PM 2.5 

### samplers, for the California Air Resources Board, and for a variety of other clients.QAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 25 of 95

 

### Three staff members have trained other pe rsonnel in the use of single channel PM 2.5 

### samplers and in the handling and shipment of filters for the FRM PEP.

 

### Several members of the RTI staff have been actively involved in evaluating commercially available speciation samplers and have partic ipated in operating them at sites across the country.

 

### At least three members of the staff have serv ed as sample custodians or sample managers to send and receive filters, prepare denuder surfaces, and send and retrieve COC forms and field data sheets for each of the available speciation samplers.

 

### RTI XRF operator Andrea McWilliams has su ccessfully completed training courses in the operation and application of the Ther moNoran EDXRF unit and understands the problems associated with the analysis.

 

### CHESTER LabNet personnel have successfu lly completed training courses in the operation of XRF units, has participated in numerous audits, and understands the problems associated with the analysis.

 

### RTI operators of the thermo-optical analys is method for carbon species have shown good agreement with other laborator ies through sample analysis in tercomparisons and analysis of certified standards.

A.8.3 New Personnel RTI will hire new personnel as necessary to meet the needs of this program. These personnel will typically be involved with routine, but important, activities such as assembling sample packages in the Sample Handling and Ar chiving Laboratory (SHAL), receiving exposed samples, and data entry. It is critical that errors in these areas be held to an absolute minimum; therefore, an in-house training pr ogram has been implemented to ensure that new personnel or personnel learning a different function are fully proficient in their responsibilities.
RTI’s approach to assessing and training new hires (and cross-training of existing employees) is as follows:

 

### New personnel are interviewed and their creden tials carefully assessed with regard to prior experience and aptitude for the assi gned task. Candidates ar e interviewed by the Technical Area Supervisor and by at least one other senior-level project participant, such as the Program Manager, QA Manager, or a Te chnical Area Supervisor in another area.

 

### RTI regular and temporary personnel to be hire d for sample shipping and receiving in the SHAL must have excellent work habits and mu st be particularly car eful and attentive to detail. These individuals must also be comfortable with working under tight deadlines imposed by contractual turnaround times. References will be contacted to verify that the applicant meets these particular qualifi cations with regard to work habits.

 

### New hires in the analytical labo ratories must have experience or aptitude equivalent to 2 years of experience, but individuals are asse ssed on a case-by-case basis by the TechnicalQAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 26 of 95


### Area Supervisor. References are contacted to verify that the applicant has the required laboratory skills and aptitude.

 

### For individuals hired as permanent RTI employ ees, a probationary period of 6 months is provided, at which time the employee may be te rminated for failing to meet required job standards; temporary employees may be dismi ssed at any time. The majority of training is on-the-job and is provided by the Technica l Area Supervisor or by a staffer who has already mastered the task area. The specific SOPs are the main training material used.

 

### All SOPs will be written in sufficient detail to allow a new staff member with the requisite training and experien ce to perform the task. Any de partures from the written SOPs will require consultation with the Technical Area Supervisor for that area. Departures from SOPs necessitated by system atic or recurring pr oblems should result in corrective actions, which may in clude revision of the SOP.

 

### All new hires will work under close supervis ion of the Technical Area Supervisor. The individual may work unsupervised only afte r the Technical Area S upervisor provides a memo to the individual’s training file. An alysts must demonstrate proficiency with analyzing standards and duplicates of previously analyzed samples. These results will be included in the training file.



## A.9 Documentation and Records

Table A.9.1 provides a summary of the documentation and records that will be maintained in each functional area for this program. Management records will include monthly data reports, correspondence with the EPA Project Officer, and correspondence and orders from the DOPOs. Consolidated requests from the DOPOs will be received and examined by the Program Manager and will be circulated to all of the laboratories for advanced planning and materials procurement.

Table A.9.1. Management Records

Document Name Brief Description Format Storage Location Laboratory Request Forms Used by the laboratories to order materials, schedule shipments, and plan future level of effort (the Program Manager checks the request and distributes it to the laboratories) Hard copy and electronic Copies to SHAL and labs

Monthly Data Reports Monthly data r eports to EPA Electronic Program Office Correspondence Contractual correspondence with EPA and subcontractors Electronic Program Office

Purchase Requisitions Copies of all approved purchase orders Electric Staffnet

Conference Call Notes Notes made during conference calls between the Program Manager, DOPOs, and EPA/OAQPS Electronic Program Office

E-mail All of the Program Manager’s project-related e-mail correspondence Electronic RTI mail server/CD Program OfficeQAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 27 of 95



### A.9.1 QA/QC Records

Table A.9.2 shows the QA/QC records th at will be maintained.

Table A.9.2. QA/QC Records

Document Name Brief Description Format Storage Location Training Files Records substantiating the training and proficiency of analysts relevant to this program Hard copy Program Office

Audits, Questionnaires, and Results Results of internal QA surveys and audits Hard copy or electronic Program Office and QA Office
QAPP Master version of QAPP, including pending revisions Hard copy and electronic Program Office and QA Office SOPs Current version of all SOPs Hard copy and electronic Program Office, QA Office, and Subcontractor Intercomparison Study Results Results validating comparability of EDXRF or OC/EC results if done by two different laboratories Hard copy and electronic Program Office and QA Office

Corrective Action Response Memoranda Results of identified QA problems and their resolutions Hard copy Program Office and QA Office



### A.9.2 SHAL Records

Table A.9.3 shows the records that will be maintained by the SHAL.

Table A.9.3. SHAL’s Records

Document Name Brief Description Format Storage Location Delivery Order Instructions from DOPOs for sampling module needs Hard copy and electronic Program Office and SHAL Chain-of-Custody Forms Forms used to track sample module shipments between RTI and the states Hard copy, triplicate form (copies 1 and 3 to RTI, copy 2 to field site) SHAL

Laboratory Chain-ofCustody Forms Forms used to track groups of aliquots between the SHAL and RTI’s internal laboratories or subcontractor laboratories Hard copy; may be computerized in the future SHAL and laboratories

SHAL Schedule Schedules shipments, receipt of containers, and assembly and disassembly of modules according to delivery orders supplied by DOPO Hard copy SHAL

Sampling Module Parts Received Details parts received from states to be used at sampling sites Electronic Database

Bin Inventory Form Lists current inventory of module parts for a specific site stored in a plastic bin in the SHAL Electronic Database

Module Assembly Form Details the assembly of a module for a specific sampling event Hard copy SHALQAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 28 of 95

Document Name Brief Description Format Storage Location

Container Contents Form Inventory of modules sent in a shipping container to a specific sampling site Hard copy SHAL

Shipment Air Bill Waybill for transport of containers to sampling site or aliquots to contractor laboratories Hard copy SHAL

Incoming Shipment Form Identifies containers received at the SHAL on a particular date/time Hard copy SHAL

Incoming Container Content Form Details modules received in a container returned from a sampling site Hard copy SHAL

Analysis List for Sampling Event Details requested analysis for a particular sampling event Electronic Database

Aliquot Form Matches filter s/pieces of filters to analysis Hard copy SHAL

Aliquot Log-Out Form Lists al iquots that have left the SHAL and have been sent to a laboratory for analysis Hard copy/notebook SHAL

Incoming Aliquot Form Inventory of aliquots being returned to the SHAL from a laboratory Hard copy/notebook SHAL

Archive Bin Report Lists aliquots in a particular storage box sent to archive Electronic Database

URG Flash Card Data From URG 3000N Continuous record of flow and other operational information Flash memory cards Database



### A.9.3 Analytical La boratories’ Records RTI and subcontractor analyti cal laboratories will maintain the generally applicable records listed in Table A.9.4.

Table A.9.4. Analytical Laboratories’ Records

Document Name Brief Description Format Location Internal Tracking Forms Forms used to track sample batches between the SHAL and RTI’s internal laboratories Hard copy and electronic Returned to the SHAL

Laboratory Notebooks Includes the following types of notebooks and bound data sheets: Analysts’ notebooks Instrument maintenance logs Reagent preparation logs Materials acceptance tests Hard copy Each laboratory

Calibration Certificates and Records Includes certificates of NIST traceability and similar records Hard copy Each laboratory

Control Charts or Equipment QC information displayed in sequence to help diagnose problems with analytical instruments; usually include acceptance limits that are periodically recomputed Hard copy or spreadsheet Each laboratory

SOPs Current copies of SOPs relevant to the analyses performed in a particular laboratory Hard copy Each laboratoryQAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 29 of 95

Document Name Brief Description Format Location QAPP A current copy of this QAPP; the Lab Supervisor must ensure that each analyst has access to a current copy of the QAPP Hard copy Each laboratory

Analytical Results Database Results for each chemical analysis with identifying information Spreadsheet or DBMS —

Analytical QC Database Includ es all QC information for each weighing session including standard weights, duplicates, field blanks, and laboratory blanks Spreadsheet or DBMS —



### A.9.4 Gravimetric Mass Laboratory Records The gravimetric mass laboratory will maintain records shown in Table A.9.5.

Table A.9.5. Gravimetric Mass Laboratory Records

Document Name Brief Description Format Location Filter Inventory and Inspection Form Completed upon receipt of filter lots from the vendor; indicates the order to use filter boxes, date inspected, and number of filters rejected Spreadsheet or hard copy Gravimetric

mass laboratory

Filter Conditioning Information Indicates the dates filters were conditioned and stability test results Hard copy Gravimetric

mass laboratory
Calibration Certificates and Records Includes certificates of NIST traceability and similar records Hard copy Gravimetric

mass laboratory
Gravimetric Filter Database Includes filter ID, initial weighing information (including date, RH, temperature, cassette number), final weighing information (date, RH, temperature, and weight), and mass loading of the filter, and all QC information for each weighing session including standard weights, duplicates, field blanks, and laboratory blanks DBMS Project data server (SQL server DB)

Weighing Room Environmental Data Data logger is programmed to record “grab samples” at 5-minute intervals Data logger spool file or spreadsheet Project data

server

Internal Tracking Forms Forms used to track sample batches between the SHAL and RTI’s internal laboratories Hard copy (may be computerized in the future) Copy retained by gravimetric

mass laboratory; original returned to the SHAL Laboratory Logbooks Individual analysts’ comments; instrument maintenance logs Hard copy Each laboratoryQAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 30 of 95

Document Name Brief Description Format Location Control Charts QC information displayed in sequence to help diagnose problems with analytical instruments; usually includes acceptance limits that are periodically recomputed Hard copy or electronic spreadsheet Each laboratory



### In addition to the records shown in Tabl e A.9.5, the gravimetric mass laboratory will receive a monthly filter order from the SHAL to accommodate program sampling requests. The DOPOs receive the sampling requests from the va rious state agencies and consolidate these requests into delivery orders, which are sent to the RTI CSN program office. Information derived from the delivery orders is distributed to the SHAL, data management, and the laboratories, so that the SHAL operations, material s (e.g., filters and reagents), a nd laboratory personnel can be scheduled as necessary. Each mont h, the SHAL supervisor will calc ulate the projected number of Teflon filters that will be needed to meet that month’s sampling and field blank requirements. This projection is sent to the gravimetric mass laboratory via e-mail so that a sufficient number of filters can be ordered in advance.

A.9.5 XRF Laboratory Records The XRF laboratory will maintain records shown in Table A.9.6.

Table A.9.6. XRF Laboratory Records

Document Name Brief Description Format Location

Calibration Certificates and Records Includes certificates of NIST traceability and similar records Hard copy XRF Laboratory

“Method” Database Includes x-ray generation information and other information required to automate the XRF analyses Computer files XRF Laboratory

QC Records Results of calibr ations, SRM recoveries, and replicate precision Computer files XRF Laboratory

Raw Data Records Results of PM analyses Computer files, database files Instrument PC; database; Program Office Laboratory Notebooks Individual analysts’ co mments; instrument maintenance logs Hard copy XRF Laboratory

Instrument User’s Manual Information for setting up, using, and troubleshooting the XRF instrument Hard copy XRF Laboratory or analyst’s office



### A.9.6 IC Laboratory Records The IC laboratory will maintain records shown in Table A.9.7.QAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 31 of 95

Table A.9.7. IC Laboratory Records

Document Name Brief Description Format Location

Calibration Certificates and Records Includes certificates of NIST traceability and similar records Hard copy IC Laboratory

“Method” Database Contains the information required to automate the analyses Computer files IC Laboratory

QC Records Results of cali brations, SRM recoveries, and replicate precision Computer files IC Laboratory and database Raw Data Records Results of PM analyses and analysis of selected denuder extracts Computer files, spreadsheets, database files Instrument PC, analyst’s PC, database computer Laboratory Notebooks Individual analysts’ co mments, instrument maintenance logs Hard copy IC Laboratory

Instrument User’s Manual Information for setting up, using, and troubleshooting the IC instruments Hard copy IC Laboratory



### A.9.7 OC/EC Laboratory Records The OC/EC laboratory will maintain records shown in Table A.9.8.

Table A.9.8. OC/EC Laboratory Records

Document Name Brief Description Format Location

Calibration Certificates and Records Includes certificates for gases and other chemicals used for calibration Hard copy OC/EC Laboratory

“Method” Parameter Files Contains the information required to run the analysis Computer files OC/EC Laboratory computers
QC Records Results of instru ment blanks, calibrations, standard recoveries, and replicate precision Computer files and hard copy OC/EC Laboratory

Raw Data Records Results of PM analyses (including supporting data that are not uploaded to the database) Spreadsheets, hard copy, database OC/EC Laboratory computers, Data validation analyst’s PC, database computer Laboratory Notebooks Individual analysts’ co mments; instrument maintenance logs Hard copy OC/EC Laboratory

Instrument User’s Manual and/or Manufacturer’s Instructions Information for setting up, using, and troubleshooting the OC/EC instruments Hard copy OC/EC Laboratory



### A.9.8 Denuder Refurbishment Laboratory Records The Denuder Refurbishments Laboratory will maintain records shown in Table A.9.9.QAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 32 of 95

Table A.9.9. Denuder Refurbishment Laboratory Records

Document Name Brief Description Format Location Personnel Training Records Date and description of training or inspection Hard copy Denuder Lab

Denuder Refurbishment Information Date, number, and type of denuders refurbished and technician name Hard-copy, notebook Denuder Lab

SOP SOPs for coating various types of denuders Hard-copy, looseleaf binder Denuder Lab

Reagent Purity Records Information for denuders to be quantitatively analyzed Hard-copy, notebook Denuder LabQAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 33 of 95



## B.1 Sampling Process Design (Experimental Design)
The experimental design, including desi gn of the sampling network and sampling locations, is outside the program scope and is not addressed in this QAPP. Refer to EPA planning documents available on th e U.S. EPA’s AMTIC Web site.


## B.2 Sampling Methods Requirements
Actual collection of samples is outside the scope of this laboratory QAPP and is not addressed herein. The CSN Field QAPP prepared for OAQPS contains a full description of sample acquisition, including sample COC, which meshes closely with operations of the SHAL. The Field QAPP is availabl e on the AMTIC Web site.


## B.3 Sample Handling and Custody Requirements

Note: This section relies heavily on desi gn of RTI’s sample handling system, including the SHAL. Please refer to th e applicable SOP for more details.
This section describes the sample handling and custody process for all sampling modules to be provided to the sites, as well as sample tracking inte rnally and between RTI and its subcontractors. In this document, the term “s ampling module” is used in a generic sense to denote the sampling media and holder associated with a specific sampled air stream in a single speciation sampler. A sampling module is the sm allest unit (in one or several pieces) shipped back and forth between RTI and a sampling site.
A sampling module includes denuders (in addition to filter media) and transport hardware if either (or both) is required. All sampling modu les and associated sample media will be tracked individually in the database management syst em (DBMS). An overview of the entire sample handling system is shown in Figure B.3.1.
B.3.1 Sample Handling Delivery Order Process RTI prepares and ships appropriate sampling media (including the required filters) to each state (or sampling site within the state) as needed to meet the sampling schedule for each site covered in the consolidated request re ceived from the DOPOs. The PM checks the consolidated request and distribut es it to the SHAL and other la boratories for planning purposes. Based on the schedule defined by all the conso lidated requests, RTI schedules and sends modules to the addresses indicated for the state monitoring agencies. Deta ils of the information contained in the consolidated requests, and RT I’s interactions with the state air monitoring agencies, will be defined in collaboration with EPA. State personnel collect the required samples and return them to RTI, which logs the sample s into its tracking system, performs all required speciation analyses, enters and va lidates the data, enters data meeting Level 1 criteria into the AQS, forwards all analysis data to the states that requested the analyses, and reports all activities to the DOPOs. Provisions also are made for archiv ing samples and for resolving technical quality issues and contract dispute issues.QAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 34 of 95

Figure B.3.1. Overview of sample handling and custody system.QAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 35 of 95


### The following subsections describe the processes associated with filter and sample handling and archiving, the physical and chemical an alyses required for each filter in each type of speciation sampler, and the da ta handling and analyses required to obtain concentration data of known quality. The sample handl ing and tracking process is desc ribed in more detail in the SHAL SOP.
B.3.2 Chain of Custody

Note: An example of the field COC information sheet is shown in the Field QAPP available on the AMTIC Web site.
RTI will provide COC documentation with all sa mple shipments to track and ensure that samples are collected, transferre d, stored, and analyzed by author ized personnel; sample integrity is maintained during all phases of sample handl ing and analysis; and an accurate record is maintained of sample handling and treatment from the time of its collection, through the laboratory analytical process, to the eventual reli nquishing of all data to the DOPOs and the state clients.
The COC documentation that accompanies th e sampling modules to and from the field will include a three-part carbonless form for sending and receiv ing samples from the field sites. The COC forms are computer generated so that they are customized for each type of sampler. All media (filters and other types of sampling media, if any) will be listed on the COC form for each sampling event. The COC form will include areas in which the field operators can enter critical data, including the total sample volume for each filter channel.
Internal custody forms will also be used to di stribute individual se ts of filters to the various laboratories for analysis. These form s are computer generated based on information already entered into the database, su ch as the assigned aliquot numbers.
B.3.3 Processing System for PM Chemical Speciation Modules RTI has designated 10 laboratories that are involved in the program, and these are described below:

1. Sample Handling and Archiving Laboratory (SHAL) . Personnel in the SHAL will be responsible for assembly of components (including clean filters and refurbished denuders) into sampling modules, shipment of sampling media and modules to the states (or sampling sites within the states), receipt of samples from the states, disassembly and cleaning of sampling modules, distribution of filters (and other sampling media, if applicable) to the individual laboratories for analysis, and final archiving of filters and filter extracts for 6 months. COC and field sampling data sheets are generated by SHAL personnel, who will also log out and log in all filter samples (going to the field or laboratories and returning) and all archived filters and extracts. Flash memory cards from the URG 3000N samplers are r ead into the database as pa rt of the SHAL disassembly procedure.QAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 36 of 95



### 2. Denuder Refurbishment Laboratory (DRL) . Personnel in the DRL are responsible for refurbishment of all denuders and extrac tion of denuders employed to collect and quantify acidic and basic gases. The DRL must have a hood and sink for work with volatile solvents and for cleaning spent de nuders. The DRL will coordinate with the SHAL to prepare and track denuders as they are needed.

3. Gravimetric Mass Laboratory (GML) . Personnel in the GML are responsible for all activities associated with PM 2.5 

### gravimetric mass determinations on Teflon filters.

4. Elemental Analysis Laboratory (EAL) . Personnel in the EAL are responsible for all elemental (selected elements, sodium through lead, by atomic number) analyses. RTI will analyze the majority of the samples. CH ESTER LabNet will assist with elemental analysis support for the contract.

5. Cations/Anions Laboratory (CAL) . Personnel in the CAL are responsible for all ion analyses. This will include both anions (sulfate and nitrate) and cations (ammonium, sodium, and potassium) on sample filters and de nuder extracts. They are also responsible for acceptance testing and cleaning, if necessa ry, of nylon and other filters used for collection and measurement of target anions and cations.

6. RTI Organic Carbon/Elemental Carbon Laboratory (OC/ECL) . Personnel in the OC/ECL are responsible for total, elemental, organic, and fractions analyses on quartz filters that are done by the NIOSH method. Th e RTI OC/EC Lab is also responsible for cleaning and acceptance testing the quartz filters used in the URG 3000N samplers, which are subsequently analyzed by DRI by the IMPROVE_A method.

7. DRI OC/EC Laboratory . Personnel in DRI’s OC/EC la boratory are responsible for carbon analysis by the IMPROVE method.

8. Semivolatile Organics Laboratory (SVOL). Personnel in the DRI SVOL are responsible for measuring indivi dual SVOCs extracted from PM 2.5 

### collected on selected quartz filters and from backup sorbent traps.

9. Microscopy Laboratory (ML) . Personnel in the ML are res ponsible for all optical and electron microscopy of selected filters (with or without elemental particle analysis).

10. ICP/MS Laboratory. Personnel in RTI’s ICP/MS laborator y will analyze selected filter extracts as directed.

Figure B.3.2 shows a flow diagram for filter processing by filter type. Teflon filters are used for determination of gravimetric mass and trace elements (sodium through lead) concentrations; some Teflon filters may be analyzed for ions. Quartz filters are used for determination of total, organic, elemental, and fractional concentrations. Nylon filters are used for determination of cations (ammonium, sodi um, and potassium) and anions (sulfate and nitrate).QAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 37 of 95

Figure B.3.2. Diagram of RTI filter processi ng and analysis activities by filter type (arrangement may vary by sampler model).QAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 38 of 95


### Figure B.3.3 shows the anticipated movement of filters and extracts through RTI laboratories described above. The focal point for shipping and r eceiving sampling media and for archiving analyzed filters and extracts is the S HAL. The other laboratories, except for the DRI, are responsible for cleaning and acceptance testin g of new filters and for analyses of samples collected on those filters. The ma in items moving between the vari ous laboratories are shown in the figure, but other pathways are possible.

Figure B.3.3. Movement of filters and extracts through RTI and subcontractor laboratories.QAPP for Chemical Speciation of PM 2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 39 of 95


### After final weighing in the gravimetric ma ss laboratory, custody of the exposed Teflon filters is transferred to Ms. Andrea McWilliams, supervisor of the XRF laboratory. Ms. McWilliams distributes the filters to the two XRF laboratories, CHESTER LabNet and RTI. After XRF analysis, the filters are returned to Ms. McWilliams who sends them either to the filter archive or to the CAL if ion analysis is required.

Table B.3.1 shows the sampling media used in each type of PM 2.5 

### speciation sampler, the species collected on each type of filter, and the RTI laboratory (or laboratories) that will measure those species on that filter. All of the sampler mo dels use at least one eac h of the three types of filters (Teflon, nylon, and quartz) used in the PM 2.5 

### speciation program.
B.3.3.1 Assembly of Sampling Modules Sampling modules sent to the field must be clean, properly assembled with clean and unflawed filters and denuders, and shipped in a timely manner. Personnel in the SHAL will clean and inspect all hardware associat ed with sampling modules and visu ally inspect each filter (for a pinhole or crease, evidence of chaffing or flaking, discoloration, or any other defect) and each denuder as each module is assembled. Any items that appear flawed are rejected. SHAL personnel will carefully pack all modules for a given sampler at a given location in the same cooler for shipment to the appropriate destinat ion. All modules are assembled according to the manufacturer’s instruct ions and with the sampling component s requested by the state agencies and approved by the DOPOs. These operations are fu lly described in SOPs specific to each model of sampler.
B.3.3.2 Shipping to and from the Field Filter cassettes, sampling modules, and any a dditional required components are shipped in specially designed insulated shipping containers to each sa mpling site or other location designated by the states through the DOPOs. EPA has established an account for shipping with a national provider (currently UPS).
Scheduling of shipping dates to and from the st ate agencies is a key part of the SHAL’s operation. RTI will continue to prepare shipping schedules for all sampling locations, and the shipping schedules will be di stributed through the DOPOs.
Sufficient commercially available, leak-pr oof, “blue-ice” gel pack s are added to each cooler to maintain a transit temperature at or below 4°C. Each state agency is responsible for freezing the ice packs and packaging the shipment so that it maintains a te mperature at or below 4°C. Shipments are returned to RTI overnight by Federal Express as described above. The temperature of each shipment is determined upon delivery at the SHAL using a temperature probe with digital readout. Temperature upon rece ipt is recorded on a Level 0 validation form.QAPP for Chemical Speciation of PM2.5Filter SamplesRevision No. 10Date: May 11, 2012Page 40 of 95Table B.3.1. Sampler Component and Laboratory Speciation Analysis MatrixSamplerModuleor FlowChannelDeviceMassElementsXRF,ICP-MSAnions++SO4-2, NO3-Cations,++NH4+, Na+, K+TC, OC,ECOpticalDensitySVOCMicroscopyHNO3,and SO2(gas)++NH3(gas)++URG 3000NSequentialcarbonaerosolsamplerModule 1 Quartz filter●●SASS Channel 1 Teflon filter●●●●Channel 2 Nylon filterwith MgOcoateddenuder●●Channel3***Quartz filter●●FRM Singlechannel persampler+Teflon filter●●●●Nylon filterwith MgOcoateddenuder●●Quartz filter●●All samplertypesAnalyticalDenuders:Anychannel, asrequiredPhosphorousor citric acidcoated●MgO orNa2CO3coated●PMCOARSE To be determinedEC = elemental carbon, HNO3= nitric acid, ICP-MS = inductively coupled mass spectrometry, K+= potassium ion, Na+= sodium ion, NH3= ammonia, NH4+=ammonium ion, NO3-= nitrate ion, Na2CO3= sodium carbonate, OC = organic carbon, SO2= sulfur dioxide, SO4-2= sulfate ion, SVOC =semi-volatile organiccompound, TC = total carbon, XRF = X-ray fluorescence+Three FRM samplers can be used in parallel as three separate channels to collect PM2.5samples for speciation analyses.++Sorbed gases NH3, HNO3, and SO2are measured by using ion chromatography as NH4+, NO3-, and SO4-2, respectively.***Only used if the original CSN OC/EC analysis is to be performed.QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 41 of 95


### B.3.3.3 Disassembly of Sampling Modules Upon their return to RTI, sampling modul es are logged into the database and disassembled by SHAL personnel. Each filter is sealed in a new, cl ean, labeled petri slide holder and sent to the appropriate laboratory for an alysis. Any denuders used in the module will be refurbished or extracted and anal yzed, if required, and all other co mponents will be cleaned prior
to reuse.
B.3.3.4 Internal Tracking of Analytical Samples Figure B.3.4 shows the internal tracking form that is used to transfer batches of filters removed from the sampling modules in the SHAL to the respective RTI laboratories. Several filters are transferred in a typi cal batch, so there is not a one-to-one correspondence between the external COC form (which corres ponds to a set of modules for a single field exposure) and the internal tracking form. In typical use, filters of like type that are received on the same day are listed on a single internal tracking form. These filters need not be from the same source, so long as they are going to the same laboratory for sim ilar analyses. A similar sample request form is used to transfer samples from RTI to its external analytical subcontractors.
B.3.3.5 Archiving of Filters and Extracts

See Standard Operating Procedure for Long-Term Archiving of PM Filters and Extracts for more detailed information. After completion of the analyses, the following may remain, depending upon the model of sampler used and the arrangement of filters:

 Teflon filters (following XRF) (filters extracted for ion analysis cannot be archived)

 Teflon filter extracts in 50 mL plastic tubes (following IC)

 Denuder extracts in 50 mL plastic tubes (following IC)

 Nylon filter extracts in 50 mL plastic tubes (following IC)

 Quartz filters (following subs ampling for OC/EC analysis)

 Quartz filter extracts in glass bottles (following SVOC analysis)

 Teflon or other filters (following micros copic or optical density analysis).

Quartz filters that are analyzed by RTI are archived in petri-slide holders, sorted by location into petri-slide trays, and sorted by sa mpling date within a tray. Full trays of quartz filters are placed in heavy-duty plastic zippered bags and placed in plastic bins in a freezer maintained at or below -15 ° C. Individual filters are indexed for rapid retrieval by Archive Bin ID, Tray ID, and Aliquot ID. Co mputer-generated reports are avai lable to facilita te retrieval by sample date, site, or state. Quartz filters se nt to DRI for analysis ar e archived by DRI at their facility. At DRI, the quartz filters are stored by batch. The sample database can be queried based on batch number, RTI order number, or samp le ID, providing easy access to filters in the archive. RTI provides information to DRI on the type of filter, site, sample date, etc., which allows DRI to retrieve any quartz fi lter based on these criteria as well.QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 42 of 95

Figure B.3.4. RTI Laboratory COC form used in tracking.QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 43 of 95


### Teflon filters are archived in petri-slide holde rs, sorted by location into petri-slide trays, and sorted by sampling date within a tray. Full trays of Teflon filters are placed in heavy-duty plastic zippered bags and placed in plastic bins in a refrigerator or cold room maintained at or below 4°C (but not below freezing). Individual filters are indexed for rapid retrieval by Archive Bin ID, Tray ID, and Aliquot ID.
Filter extracts (nylon or Teflon) are archived for 6 months in extraction vials and grouped in lab batches, which are placed in heavy-duty plastic zippered bags in plastic bins in a refrigerator or cold room maintained at or below 4°C (but not below freezing). Individual extracts are located by Archive Bin ID, Batch ID, and Aliquot ID.
B.3.3.6 Denuder Preparation Denuders are placed upstream of sampler filters in certain speciation sampling configurations to remove inte rfering acidic and basic gases and gas-phase SVOCs. The acidic gases of concern to the Chemical Specia tion Network include nitric acid and SO 2 

### . The reason for removal of such gases is to prec lude their collection on the filter as reaction product artifacts. For example, if nitric acid vapor from ambient air was allowed to reach the nylon filter, it may react with basic substances there or wi th the filter itself to form nitrate salts; thus the nitrate ion concentration would be higher than that due to ni trate PM alone. In certain instances, it may also be desirable to remove SVOCs from the air st ream due to their poten tial for adsorption or reaction upon reaching the PM collection filter.
RTI will also prepare denuders specially de signated for quantitative extraction. These denuders will be prepared with special attenti on to the purity of the coating reagents, and backgrounds levels of the species to be analyz ed (ammonium, nitrate, and sulfate) will be determined for each batch of denuders. Special precautions to ensure low background levels will be taken for denuders that are to be extracted for analysis of am bient gas-phase ammonia, nitric acid, and SO 2


### . RTI will provide support for the operation and us e of denuders associat ed with all types of samplers to be used in the speciation network. Denuder specificat ions for the samplers will be provided upon start-up of this segment of the monitoring program.
The state (or local agency w ithin the state) planning to employ denuders in its PM speciation sampling scheme will inform the EPA Re gional Speciation Coordinator of this fact at the same time that a request for analytical servic es on filters is made. This initial request for denuder use should be made well in advance of the intended date of use to allow for shipment of denuder equipment to the RTI laboratory, de nuder cleaning and coating, and QC. The EPA DOPOs will notify RTI’s Program Manager of the state’s need fo r denuders (and filters) and details on special filter pack arrangements associated with th e denuders. The sampling schedule is also set. The state must provide a sufficient number of denuders and accessories to meet the demands of their sampling schedule, provide appr opriate shipping containers, and carefully pack and ship the new denuders to RTI by Federal Expre ss. Several complete sets of denuders may be required, depending upon the sampling schedule.
Upon receipt of the new denuders and accessories, RTI will clean and coat the denuder devices according to one or more of the following SOPs:QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 44 of 95

 

### Standard Operating Procedure for Coati ng and Extracting Annular Denuders with Sodium Carbonate

 

### Standard Operating Procedure for Coating Annular Denuders with Magnesium Oxide

 

### Standard Operating Procedure for Coati ng Annular Denuders with XAD-4 Resin

 

### Standard Operating Procedure for Coati ng Aluminum Honeycomb Denuders with Magnesium Oxide

 

### Standard Operating Procedure for Coating and Extracting Compact Parallel-Plate Denuders for Ammonia Determination

 

### Standard Operating Procedure for Coating and Extracting Denuders for Capture of Ammonia and Its Measurement.

All prepared, refurbished, or purchased denuders are sealed airtight and stored in a secure location free of acidic or basic gases and SVOCs. They will then be shipped to the sampling sites for installation on the samplers. The SASS samplers’ denuders are installed in the sampling module prior to shipme nt to the field.
The denuders to be installed at the site sample r are shipped to the re questing state or local agency. Denuders are listed on the COC form th at will accompany each shipment to a particular speciation sampler. A record of the number of us es or length of time in use of a particular denuder is maintained by the SHAL so that the denuder is refurbished or replaced according to schedule. All MgO denuders are currently re placed after approximately 30 exposures, and Na 2 

### CO 3 

### denuders are replaced afte r each sampling event.

The denuders, COC forms, and field data sheets are returned with the filter samples to RTI from the sampling sites by Federal Express. Upon receipt, the denuders are inspected for damage. The state is responsible for replacemen t or repair of denuder components damaged in the field; the shipping company is responsible fo r damage caused during tr ansit. RTI will repair or replace items damaged during handling in its laboratory. The denuders will then be cleaned and/or refurbished for the next round of use according to the established schedule. Unless otherwise directed, RTI will not save extracts from rinsing or cleaning the denuder surfaces and will not analyze the extracts for components. Following cleanup, the undamaged denuders will be refurbished. The newly coated denuders are s ealed airtight and stored in a clean, secure location until they are needed.


## B.4 Analytical Methods Requirements

B.4.1 Gravimetric Mass Determination Standard Operating Procedure for PM 2.5 

### Gravimetric Analysis describes the procedure to be used for gravimetric mass dete rmination in RTI’s laboratory.

B.4.2 EDXRF Analysis for Elements Standard operating procedures used by RTI and CHESTER LabNet for EDXRF analysis are listed below:QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 45 of 95



### RTI 

### Standard Operating Procedures for X- Ray Fluorescence Analysis of PM 2.5 

### Deposits on Teflon Filters

CHESTER LabNet 

### Standard Operating Procedures for the Sample Receipt and Log In Standard Operating Procedures for the Analysis of Elements in Air Particulates by XRF (Kevex 771) Standard Operating Procedures for the Analysis of Elements in Air Particulates by XRF (Kevex 770 and 772) Standard Operating Procedures for the Kevex Sp ectrometer Data Generation, Interpretation, and Reporting Standard Operating Procedure for the Kevex XRF Spectrometer Calibration
B.4.3 Extraction and Analysi s of Anions and Cations For an overview of RTI’s laboratory facility a nd procedures for extract ion and analysis of anions and cations, including nitrate and sulfate, see: Standard Operating Procedure for Cleaning Ny lon Filters Used for Collection of PM 2.5 

### Material Standard Operating Procedures for PM 2.5 

### Anion Analysis Standard Operating Procedures for PM 2.5 

### Cation Analysis
B.4.4 Carbon Analysis RTI’s laboratory facility and procedures fo r organic, elemental, carbonate, and total carbon analysis by the CSN TOT method are detailed in the Standard Operating Procedure for the Determination of Organic, Elemental, and Total Carbon in Particulate Matter Using a Thermal/Optical-Transm ittance Carbon Analyzer

. DRI’s laboratory facility and procedures for OC/EC analysis by the IMPROVE_A/TORTOT method are detailed in the DRI Standard Operating Procedure: DRI Model 2001 Thermal/Optical Carbon Analysis (TOR/TOT ) of Aerosol Filter Samples – Method IMPROVE_A

. RTI’s laboratory facility and procedures fo r OC/EC analysis by the IMPROVE_A/TORTOT method are detailed in three SOPs:

 

### Standard Operating Procedures for Temperature Calibration of the Sample Thermocouple in a Sunset Laboratory or a DRI Model 2001 Carbon Aerosol Analyzer

 

### Standard Operating Procedure for the De termination of Carbon Fractions in Particulate Matter Using the IMPROVE_A Heating Protocol on a Sunset Laboratory Dual-Mode AnalyzerQAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 46 of 95

 

### Standard Operating Procedure for the De termination of Carbon Fractions in Particulate Matter Using the IMPROVE_ A Heating Protocol on a DRI Model 2001 Analyzer
While the CSN/TOT analysis and the IMPR OVE/TOR-TOT analysis are similar in technical approach, and both re quire heating ramps under non- oxidizing conditions followed by heating ramps under oxidizing cond itions, the two methods are f undamentally different in the way they define carbon fractions. Th e CSN/TOT analysis is a timed analysis with fixed times at each temperature step in the heating profile, a nd the IMPROVE/TOR-TOT analysis is an eventdriven analysis with the sample remaining at a given temperature step until evolution of carbon from the filter drops to near zero, subject to a minimum re sidence time of 150 seconds and a maximum residence time of 580 seconds at each te mperature step. A CSN/TOT analysis runs for a total of 12 minutes; an IMPROVE_A/TOR-TOT analysis may take anywhere from about 18 minutes to 70 minutes.
The maximum temperatures for the various fracti ons are also different as are the way that “Peaks” are defined. For the CSN/TOT analysis, the five OC peaks are defined as their contributions to OC. For CSN/TOT, the sum of the five OC peaks is always equal to OC. For the IMPROVE_A/TOR-TOT method, the four OC peaks and the three EC peaks are independently calculated without regard to th e OC/EC split and pyrolyzed carbon has a negative value if the OC/EC split comes before the addition of oxygen. Table B.4.1 below describes and compares the carbon fractions measured for both methods and the conditions (e.g., non-oxidizing or oxidizing atmosphere and maximum temperat ure) under which each fraction is measured.
B.4.5 Semivolatile Organic Compounds SVOCs will be analyzed by RTI’s subcontractor DRI. The analysis is detailed in DRI’s Standard Operating Procedures for Analysis of SVOC by GC/MS.

B.4.6 Characterization of Particles by Electron and Optical Microscopy RTI will provide SEM and optical microscopy fo r characterization of particulate samples. RTI has extensive experience in the analysis of airborne PM by both optical and electron microscopy techniques, having an alyzed a large number of PM 10 

### filters by optical microscopy for several state air quality agencies and a signif icant number of air filters for commercial firms.
B.4.6.1 Scanning El ectron Microscopy SEM can be employed to characterize individual particles collected on a filter. Particles may be sized and the morphology described on an i ndividual basis. The com position of a particle may be determined by EDXRF. Characterizati on of a large number of particles provides information as to the particle size, distribution, and chemistry of the PM. Any of several filter media can be used to collect particulate material, but smooth-surface filters such as polycarbonate filters are far supe rior for the purposes of analysis by SEM. The procedures for analysis by particulate material by SEM are described in detail in Standard Operating Procedure for Sample Preparation and Analysis of PM 10 

### and PM 2.5 

### Samples by Scanning Electron Microscopy.QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 47 of 95

Table B.4.1. Carbon Fractions Reported

Atmosphere/ Fraction CSN / TOT † IMPROVE_ A / TOR-TOT ‡

Analyte Name Maximum Temperature Analyte Name Maximum Temperature
He&He-O 2 /OCT OC 900 ° C OCT 580 ° C

He&He-O 2 /OCR Not Calculated N/A OCR 580 ° C He/1st OC Peak Pk1_OC 310 ° C OC1 140 ° C He/2nd OC Peak Pk2_OC 480 ° C OC2 280 ° C He/3rd OC Peak Pk3_OC 615 ° C OC3 480 ° C He/4th OC Peak Pk4_OC 900 ° C OC4 580 ° C

He-O 2 /PCT Pyrol_C Varies PCT varies

He-O 2 /PCR Not Calculated N/A PCR varies

He-O 2 /ECT EC 920 ° C ECT 840 ° C

He-O 2 /ECR Not Calculated N/A ECR 840 ° C

He-O 2 /1st EC Peak Not Calculated 600°C EC1 580 ° C

He-O 2 /2nd EC Peak Not Calculated 675 ° C EC2 740 ° C

He-O 2 /3rd EC Peak Not Calculated 750 ° C EC3 840 ° C

He-O 2 /4th EC Peak Not Calculated 825 ° C N/A N/A

He-O 2 /5th EC Peak Not Calculated 920 ° C N/A N/A

† Chemical Speciation Network/Thermal-Optical-Tr ansmittance Analysis, adopted by EPA in 2000. Older models of Sunset carbon analyzer did not ca lculate individual EC peaks. Dual-model sunset carbon analyzers calculate the individual EC peaks. ‡ Interagency Monitoring of Protected Environment s/Thermal-Optical-Reflectance & Transmittance Analysis, adopted as IMPROVE_A in 2005.



### B.4.6.2 Optical Microscopy The RTI optical microscopy laboratory is fully equipped with both st ereo-binocular and polarizing light microscopes (PLM) capable of both reflected and transmitted light analysis. Photomicrography capabilities allow for documentati on of particle characteristics. No RTI SOP currently exists for optical examination of filter media. Procedures will be carried out at the direction of the DOPOs, and reporting criteria and formats will be established at the time of the initial requests.
Analysis by optical microscopy allows for ex amination of particles having apparent diameters less than 0.25 μm. Optical characteri stics such as color, refractive indices, birefringence, and morphology (size and shape) can be determined, which may aid in the identification of particles. The Teflon filter commonly employed in PM 2.5 

### sampling is not a suitable substrate for analysis by optical microscopy because the thickness and translucent nature of the filter severely limits the transmittal of light. Additionally, the surface of the filter is highly irregular, making it very difficult to observe in dividual particles. Other filter media such as mixed cellulose ester (MCE) or polycarbonate pr ovide substrates that are more suitable for analysis by optical microscopy.QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 48 of 95 

## B.5 Quality Control Requirements B.5.1 Quality Criteria for Gravimetric Analyses All QA/QC procedures and processes em ployed by RTI in the performance of gravimetric analysis of filters will meet or exceed the requirements outlined in EPA’s QA Handbook Guidance Document 2.12. RTI will also stay current with weighing procedures developed by other authorities such as NI ST and ASTM. RTI will assess procedural innovations, and, in consultation with EPA, will adopt changes to improve the quality of the CSN data. For example, the weighing session soft ware that has been developed by RTI for the CSN program automatically prompts for duplicate a nd standard weighings to ensure that these QC checks are performed at the required frequency in each weighing session.
A summary of nine laborator y QC samples that accompa ny gravimetric measurements and their acceptance criteria is given below.
1. At least two Class 1 working mass refere nce standards traceable to the National Institute of Standards and Technology (NIS T) are weighed at the beginning and end of each weighing session, with weights not to vary by more than 3 μg from the designated value. If the tolerance is exceed ed, corrective actions will be taken. After any problems with the balance or with the weights have been identified and addressed, any filters not bracketed by accepta ble standard checks will be reweighed.

2. At least one working standard is weighed after every tenth filter weighed, with the weight not to vary by more than 3 μg from the designated value. If this tolerance is exceeded, corrective actions will be taken as described above.

3. Standard weight measurements are m onitored by QC charts (or equivalent) throughout the year to determine if any bi as has developed in the weights or the balance.

4. Replicate weighings are made at a frequency of 33% of pr e-sampling (tare) filters and 10% of post-sampling filters; if the weights differ by more than 15 μg, the laboratory supervisor for the project will be cons ulted and corrective action will be taken.

5. At least one laboratory bla nk is weighed during each we igh session, with the weight not to vary by more than 15 μg from the in itial weight. If this tolerance is exceeded, troubleshooting of the entire weighing proce ss will be conducted in coordination with the laboratory supervisor.

6. Post-sampling weights for field blanks are not to exceed initial weights by more than 30 μg. If the weight difference of any of the field blanks exceeds 30 μg, the laboratory blanks are checked. If the labor atory blanks are within 15 μg, the state agencies will be notified to troublesh oot possible contamination in the field.

7. The microbalances are calibrated annually or more frequently, as needed, by a Mettler technician.QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 49 of 95


### 8. The 100 and 200 mg primary and working mass reference standa rds are recertified annually against NIST-traceable mass sta ndards at a state weights and measures laboratory holding a NIST certificate of traceabil ity. [Note that filters currently used for gravimetric mass determination are bracke ted by these two reference weights. If a new type of filter is adopted for the CSN program in the future, appropriate reference standards would be used to bracket the expected filter weights.]

9. The accuracy of the temperature and relative humidity (RH) recorders are verified annually. See section B.6.1 for detailed de scriptions of the temperature and RH control requirements.

B.5.1.1 Gravimetric Di saster Recovery Plan Raw weighing data, including internal QC checks, are recorded in the gravimetric database application written for the laborator y in Microsoft Access by RTI Data Management personnel. For backup and archiving purposes, th e raw data are stored on the RTI chemical speciation program’s dedicated database server. Data logger spool files are downloaded directly from each data logger to the server. Database backup and restore procedures are described in greater detail in Section B.10 of this QAPP. Hard copies of ra w data will also be printed for backup purposes.
In addition to the program’s database bac kup and recovery plan, the gravimetric mass laboratory will have a severe weather/utilities in terruption response plan. This plan will be filed in the Microanalytical Sciences Department’s administrative office and will instruct laboratory personnel in the response actions to be taken in the event of pow er outage, water outage, severe inclement weather, and so forth. The intent of this plan will be to minimize the impact of unavoidable weather events or utilities interru ption on laboratory opera tion, sample throughput, and data quality.
B.5.2 Quality Criteria for Ion Analysis The quality criteria applicab le to analysis of cations and anions are provided in Table B.5.1.QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 50 of 95

Table B.5.1. QC Criteria for Ion Ch romatography (Anions and Cations)

QC Sample Frequency A cceptance Criteria Corrective Action Multipoint calibration Daily, before analysis of field samples Acceptable agreement with previous calibration results plotted on a control chart Identify and correct the problem before analyzing field sample

Method Detection Limit (MDL) Annually or after major instrument change Acceptable agreement with instrument manufacturer’s specification Troubleshoot IC instrument

QC samples prepared with laboratory reagents at concentrations higher and lower than expected sample concentrations (one high, one low) 1) Daily, before analysis of field samples, and 2) After every 10 field samples during a

run ± 10% of nominal value 1) Identify and correct the problem before analyzing field samples, and 2) Field samples not bracketed by acceptable QC samples must be reanalyzed after corrective actions

Commercial, NISTtraceable standard solution Daily, before analysis of field samples ± 10% of nominal value Identify and correct the problem before analyzing field samples

Reagent blanks 1) Daily, before analysis of field samples, and 2) After every 20 field samples during a

run (1 and 2) less than the MDL for each ion 1) Identify and correct the problem before analyzing field samples, and 2) Field samples not bracketed by acceptable QC samples must be reanalyzed after corrective actions Duplicates (of field samples) After every 20 field samples during a run Relative difference less than 10% for concentrations $ 10 times the MDL (less than 100% for concentrations at the MDL) Field samples not bracketed by acceptable QC samples must be reanalyzed after corrective actions

Spiked duplicates One for every 20 field samples during a run Spike recovery between 90% and 110% Field samples not bracketed by acceptable QC samples must be reanalyzed after corrective actions have been taken



### B.5.2.1 Ion Disaster Recovery Plan for Data The Ion Lab supervisor or analys t copies raw data (.txt) and calculated data (.csv) files from the hard drives of each lab computer to a 1GB disk storage partition on an NT file server located in a separate RT I building. Data stored on the NT file server are backed up nightly. Other data security measures include copying data file s to the lab supervisor’s PC for data analysis, validation, and reporting and fre quent backups to CD-R media. At least two archive CDs are burned before any data are deleted from either a lab PC or the NT file server (typ ically done to free up disk storage space), and the two archive CDs are kept in separa te buildings at RTI.
B.5.3 Quality Criteria for EDXRF

B.5.3.1 RTI QC elements practiced by RTI are shown in Table B.5.2.QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 51 of 95

Table B.5.2. RTI QC Procedures to Analyze EDXRF Elements

Item Inspection Frequency Inspection Parameter Control Limits Corrective Action

Calibration As needed — — —

Calibration verification Weekly Measure elements on NIST SRMs 1832 and Micromatter QC standards 90%–110% Investigate and recalibrate; reanalyze any affected filters

Instrument precision Every tray of samples Comparison of measured value and value at time of calibration for 6 elements Relative % of error is < 5% Tray reanalysis

Reproducibility 5% Duplicate analysis of 5% of batch Difference of < 50% for values with original value < 3x its uncertainty Investigate: and possible reanalysis of entire batch



### B.5.3.1.1 XRF Disaster Recovery Plan for Data 

### Data safety and security are ensured by frequent transfer of computerized raw data from the XRF PC in RTI’s Building 6 to portable hard drive media, which is stored in Building 7, Room 219.

B.5.3.2 CHESTER LabNet QC procedures for the analysis of elements by EDXRF, their frequency of application and control limits, and corrective actions as performed by CHESTER LabNet are shown in Table B.5.3.

Table B.5.3. CHESTER LabNet’s QC Procedures Used to Analyze EDXRF Elements

Item Inspection Frequency Inspection Parameter Control Limits Corrective Action

Calibration As needed -- -- --

Calibration verification Weekly Measure elements on NIST SRMs 1832 and Micromatter QC standards 90 to 110% Investigate, possible recalibrate

Instrument precision Every tray of samples Comparison of measured value and value at time of calibration for 6 elements Relative % of error -

< 5% Tray reanalysis

Reproducibility 5% Duplicate analysis of 5% of batch Difference of < 50% for values with original value < 3x its uncertainty Investigate and possible batch reanalysisQAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 52 of 95


### The two-sigma (95% confidence level) detection limits in units of ng/cm 2 

### are calculated from the analysis of a blank Teflon filter as follows:


## ( )

t s B

i i 2 1

1 2 2 2 I element for limit detection = = δ



### where, B i 

### = the background counts for element I,

s i 

### = the sensitivity factor for element I, and t = the counting livetime.

Theoretically, detection limits may be d ecreased by simply increasing the counting livetime. In practice, a point of diminishing returns is reached for real-world samples in which the background increases along with the analyte signal. At this point, further improvement in detection limits by increasing the counting time is not possible.

Note: CHESTER LabNet’s MDLs are being reported as 3-sigma limits for compatibility with other STN MDLs.
B.5.4 Quality Criteria for OC/EC Analysis The QC criteria applicable to the carbon sp eciation analysis in RTI’s OC/EC Laboratory are provided in Table B.5.4.a for RTI and B.5.4b for DRI.

Table B.5.4a. QC Criteria for OC/EC Analysis by CSN/TOT and IMPROVE_A/TOR-TOT Methods in RTI’s OC/EC Laboratory

QC Element Frequency Acceptance Criteria Corrective Action RTI CSN/TOT Analysis

Method Detection Limit (MDL) Annually MDL # 0.5 μ g C/cm 2 Investigate the source of the problem and initiate corrective action, if necessary, to correct the problem before analyzing samples

Calibration peak area Every Analysis Within 95%–105% of average calibration peak area for that day Discard the results of that analysis and, if necessary, repeat the analysis with a second punch from the same filter

Instrument blank Daily Blank # 0.3 μ g/cm 2 Determine if the problem is with the filter or the instrument and, if necessary, initiate corrective action to identify and solve any instrument problem before analyzing samples Three-point calibration Weekly Correlation Coefficient (R 2 )
≥ 0.998 [with force-fit through 0,0] Determine the cause of the nonlinearity and initiate actions that will identify and solve any problem that may have arisen; then repeat the three-point calibration, which must yield satisfactory results before samples are analyzed

Calibration check Daily 1) 90%–110% recovery, and 2) Calibration peak area 90%– 110% of average for the weekly 3-point calibration Initiate corrective action, if necessary, to solve the problem before analyzing samplesQAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 53 of 95

QC Element Frequency Acceptance Criteria Corrective Action Duplicate analyses 10% of Samples 1) TC Values greater than 10
μ g/cm 2 —less than 10% RPD, 2) TC Values 5–10 μ g/cm 2

— less than 15% RPD, 3) TC Values less than 5
μ g/cm 2 —within 0.75 μ g/cm 2 Flag analysis results for that filter with non-uniform filter deposit (LFU) flag

RTI IMPROVE_A/TOR-TOT Analysis

Method Detection Limit (MDL) Annually MDL ≤ 0.6 μ g C/cm 2 Investigate the source of the problem and initiate corrective action, if necessary, to correct the problem before analyzing samples

Calibration peak area Every Analysis Within 95%–105% of average calibration peak area for that day Discard the results of that analysis and, if necessary, repeat the analysis with a second punch from the same filter

Instrument blank Daily Blank ≤ 0.6 μ g/cm 2 Determine if the problem is with the filter or the instrument and, if necessary, initiate corrective action to identify and solve any instrument problem before analyzing samples

Full Calibration [sucrose(aq) , KHP (aq), CH 4 /He and CO 2 /He] Six Months Slope [force-fit through 0,0], recovery, and calibration peak area all within 95% to 105% of average slope, average recovery, and average peak area for each run and for each standard. Determine the cause of the problem and initiate actions that will identify and solve any problem that may have arisen; then repeat the calibration with the standard that appeared to be most different. The individual calibrations for the four standards and their collective results must yi eld satisfactory results before samples are analyzed

Auto Cal Check Daily Peak area for each of the three CH 4 /He injections must be within 95% and 105% of the average for the three. Determine the cause of the problem and initiate corrective action, if necessary, to correct the problem; and obtain acceptable Auto Cal results before analyzing samples.

Calibration check (15 μL

sucrose standard) Daily 1) 90%–110% recovery, and 2) Calibration peak area 90%– 110% of average for the weekly 3-point calibration Initiate corrective action, if necessary, to solve the problem before analyzing samples

Duplicate or replicate analyses 10% of Samples 1) OC or TC ≥ 10 μ g/cm 2 —less than 10% RPD, 2) OC or TC < 10 μ g/cm 2

— within 1.0 μ g/cm 2

, 3) EC ≥ 10 μ g/cm 2 —less than 20% RPD, 4) EC < 10 μ g/cm 2 —within 2.0
μ g/cm 2 Flag analysis results for that filter with non-uniform filter deposit (LFU) flag.QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 54 of 95

Table B.5.4b. QC Criteria for OC/EC Analysis by IMPROVE_A/TOR-TOT Methods in DRI’s OC/EC Laboratory
Requirement Calibration Standard Calibration Range Calibration Frequency Performe d By A cceptance Criteria Corrective Action System Blank Check N/A N/A Beginning of analysis day. Carbon Analyst ≤ 0.2 μg C/cm 2 . Check instrument and filter lots. Leak Check N/A N/A Beginning of analysis day. Carbon Analyst Oven pressure drops less than 0.52 mmHg/s. Locate leaks and fix.

Laser Performance Check N/A N/A Beginning of analysis day. Carbon Analyst Transmittance >700 mV; Reflectance >1500 mV Check laser and filter holder position.

Calibration Peak Area Check NIST 5% CH 4 /He gas standard. 20 μg C (Carle valve injection loop, 1000 μl). Every analysis. Carbon Analyst Counts >20,000 and 95-105% of average calibration peak area of the day. Void analysis result and repeat analysis with second filter punch. Auto-Calibration Check NIST 5% CH 4 /He gas standard. 20 μg C (Carle valve injection loop, 1000 μl). Beginning of analysis day. Carbon Analyst 95-105% recovery and calibration peak area 90-110% of weekly average. Troubleshoot and correct system before analyzing samples.

Manual Injection Calibration NIST 5% CH 4 /He or NIST 5% CO 2 /He gas standards. 20 μg C(Certified gastight syringe, 1000 μl). End of analysis day. Carbon Analyst 95-105% recovery and calibration peak area 90-110% of weekly average. Troubleshoot and correct system before analyzing samples

Sucrose Calibration Check 10 μ L of 1800 ppm C sucrose standard. 18 μg C. Thrice per week (began March, 2009). Carbon Analyst 95-105% recovery and calibration peak area 90-110% of weekly average. Troubleshoot and correct system before analyzing samples

Multiple Point Calibrations 1800 ppm C Potassium hydrogen phthalate (KHP) and sucrose; NIST 5% CH 4 /He, and NIST 5% CO 2 /He gas standards. 9-36 μg C for KHP and sucrose; 2-30 μg C for CH 4 and CO 2

. Every 6- months or after major instrument repair. Carbon Analyst All slopes ±5% of average. Troubleshoot instrument and repeat calibration until results within stated tolerances.

Sample Replicates N/A N/A Every 10 analyses. Carbon Analyst on

same or different analyzer ±10% when OC, EC, TC ≥ 10 μg C/cm 2 or <±1 μg/cm 2 when OC, EC, TC <10 μg C/cm 2 Investigate instrument and sample anomalies and rerun replicate when difference > ±10%. Temperature Calibrations Tempilaq (Tempil, Inc., South Plainfield, NJ, USA). Three replicates each of 121, 184, 253, 510, 704, Every 6- months, or whenever the Carbon Analyst Linear relationship between thermocouple Troubleshoot instrument and repeat calibration untilQAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 55 of 95

Requirement Calibration Standard Calibration Range Calibration Frequency Performe d By A cceptance Criteria Corrective Action and 816 °C. thermocoup le is replaced. and Tempilaq values with R 2 >0.99. results are within stated tolerances. Oxygen Level in Helium Atmosphere Certified gas-tight syringe. 0-100 ppmv. Every 6- months, or whenever leak is detected. Carbon Analyst using a GC/MS system. Less than the certified amount of He cylinder. Replace the He cylinder and/or O 2 scrubber.



### B.5.4.1 RTI OC/EC Lab Disaster Recovery Plan for Data At RTI, copies are regularly made of the raw data (.txt) and calculated data (.csv) files from the hard drives of each lab computer a ttached to a Sunset Lab analyzer and the Access database of each lab computer attached to a DRI Model 2001 analyzer. These files are saved to a 1-GB disk storage partition on a f ile server located in a separate RTI building. Data stored on the file server are backed up nightly. Other data secu rity measures include co pying all lab data files to the PC of the staff member responsible for performing data analysis, validation, and reporting, and making frequent backups to CD-R or DVD-R media. At leas t two archive CDs or DVDs are burned before data are deleted from either a lab PC or the file server (typically done to free up disk storage space), and the two ar chive CDs or DVDs are kept in se parate buildings at RTI. At DRI, data is archived as per their st andard archival and back-up procedures.
B.5.5 Quality Criteria for Denuder Refurbishments Denuders are used for the CSN program in two different applications. The first application is the stripping of acid gases (e.g., sulfur dioxide and nitrogen oxides) from the airstream upstream of nylon filters. If not rem oved prior to sampling, these gases can appear as anion artifacts when the filters are analyzed. Magnesium oxide (MgO) is used with the SASS honeycomb denuder to remove these gases. The sorb ent material is not analyzed after use, and QC criteria relate primarily to adequacy and uniformity of coating.

The second potential application for denuders in the CSN program is for quantitative sampling of ammonium gas. As of this wr iting (August 2011), ammonia sampling has not been performed for routine CSN sampling. Conse quently, the sampling uncertainties and QC requirements applicable to prepar ing and testing these denuders ha ve not been fully assessed and tested, or approved by EPA.

Quality control steps applicable to acid ga s denuder refurbishment and quantitative denuders for ammonia gas are provided in Table B.5.5.QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 56 of 95

Table B.5.5. QC Criteria for Denuder Refurbishments

QC Element Frequency A cceptance Criteria* Corrective Action Coating solution storage After each coating session Sodium carbonate solutions to be refrigerated at ~4°C. MgO slurry to be stored tightly

capped while stirring Prepare fresh coating solution if not refrigerated or if MgO slurry has dried

Absence of MgO-clogged

denuder passage ways After each coating Visually inspect each denuder for clogged passage ways Remove the obstructions; use nitrogen gas to clean debris; if necessary, clean and recoat Final inspection After each coating As applicable, check each denuder for damage,

O-ring quality, and absence of debris affecting proper seating of denuder Remove damaged denuders from service; replace aged, cracked, ormissing O-rings; clean Oring surfaces with damp lab wipe Denuder Storage After denuder coating is dry To protect denuders from exposure before installation in module, cap or bag them Reclean and recoat denuders exposed to room air for more than 4 days Reagent purity For denuders to be analyzed quantitatively – upon opening new containers of coating material Phosphorous Acid 99% other reagents as specified in SOP** Use different reagent source; optionally recrystallize in the laboratory

Denuder lot background contamination For denuders to be analyzed quantitatively –

each preparation lot should have 1 or 2 reextracted TBD* (Background levels approaching 1.0 μ g NH 3 per denuder have been achieved during method

development tests***) Reject denuder lot; determine source of contamination; re-make the denuder lot

Field Blank denuder ion background For denuders to be analyzed quantitatively -- Minimum of one per shipment TBD* Investigate source of field contamination

Denuder extraction effectiveness For denuders to be analyzed quantitatively TBD* (90%–110% goal) Investigate effectiveness of extraction protocol *Final QC criteria for quantitative measurement of ammo nia gas will be developed in cooperation with EPA. **Standard Operating Procedure for Coating and Ex tracting Compact Parallel-Pl ate Denuders for Ammonia Determination, RTI International, March 1, 2010.

*** Eaton, W. Cary, Wall, Constance V., and Walters, Steven J., October 2009. “Refinement and Field Testing of Denuder Technology for Quantification of Basic and Acidic Gases to Support EPA PM2.5 and CASTNET Ambient Air Monitoring Network Research.” RTI International Institutional Research and Development Final Report.


### B.5.6 Uncertainty Determination Uncertainty values reported to AQS with each concentration record will include components of both analytical and the volumet ric uncertainty. The reported uncertainties are estimated “1-sigma” valued (one standard devi ation). No blank correc tions are assumed other than laboratories’ instrumental baseline corrections, which are an integral part of each analysis. The equations to calculate the total uncerta inty for the CSN analytes are included in Appendix 1

.QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 57 of 95



### B.5.7 Method Detection Limits The method detection limits (MDLs) for the PM 2.5 

### CSN analytes are shown in Appendix 2 and are reported annually in the data summary re ports provided to EPA and posted on AMTIC. MDLs are typically reported as three times the standard deviation of seven or more replicate measurements of a reagent blank, matrix bla nk, or low-level calibration standard. MDLs for gravimetric mass are determined from net weights (post-weight minus pre- weight) for historical QC blanks and lot stability blanks. MDLs for PM 10 

### and PM coarse 

### , and for new analytical methods will be added to this QAPP when they become available. In some cases these may be identical to those for PM 2.5


### .



## B.6 Instrument/Equipment Testing, Inspection, and Maintenance Requirements B.6.1 Gravimetric Mass Laboratory Two different relative humidity and temper ature recording devices are used in the gravimetric mass laboratory to verify that meas urements are correct and that variances around the chamber are taken into account. Table B.6.1 details chamber environment inspection criteria, including how to appropriately document the insp ection and troubleshoot if the inspection fails.

Table B.6.1. Inspection Criteria for Gravimetric Mass Laboratory

Item Inspection Frequency Inspection Parameter Action if Item Fails Inspection Documentation Requirement Weigh Chamber temperature Daily 20°–23°C 1) Contact RTI HVAC Department 2) Call service provider that holds maintenance agreement 1) Document in weigh room log book 2) Notify Lab Manager

Weigh Chamber humidity Daily 30%–40% 1) Contact RTI HVAC Department 2) Call service provider that holds maintenance agreement 1) Document in weigh room log book 2) Notify Lab Manager



### EPA Document 2.12 states that filters will not be weighed if the relative humidity and temperature measurements in the weighing enviro nment are not within ac ceptance criteria (RH = 30%–40% with a control of " 5% and temperature = 20 E –23 E C with a control of ±2 E ) for the preceding 24 hours. Critical crit eria tables included in Marc h 2000 guidance from OAQPS on the use of data flags for PM 2.5 

### AQS data offer slightly relaxe d acceptance criteria (RH = 30%–40% with a control of ±5% standard deviation and temperature = 20 E –23 E C with a control of ±2 E standard deviation ). Gravimetric lab personnel will ensure that filters are equilibrated for at least 24 hours before weighing. In the event of prot racted chamber downtime that would cause the laboratory holding time to be exceeded, the anal yst must decide whether to weigh the filters without the full 24 hours of equilibration, to weig h the filters when relative humidity and/or temperature measurements in the weighing enviro nment have exceeded accep tance criteria, or to wait until the chamber controls are functional, thus exceeding holding time limits. This choice has little impact on overall data validity, as the consequence of each choice is the same: an AQSQAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 58 of 95


### validity status flag of 2, “operati onal criteria exceeded.” In each case, the analyst must specify the data flag and insert a brief e xplanation of the problem in the sp readsheet that is sent to data management.

Table B.6.2 details the weigh room schedule and who will be responsible for performing the maintenance.

Table B.6.2. Gravimetric Mass Laboratory Maintenance Schedule and Responsibility

Item Maintenance Frequency Responsible Party

 Multi-point Micro-balance

 Internal calibration

 Maintenance

 External calibration Daily Yearly or as needed Yearly or as needed  Balance Analyst

 Mettler Toledo service representative

Comparison of NIST Standards to laboratory working and primary standards Yearly or as needed RTI Laboratory Supervisor

Cleaning weigh room Monthly Balance Analyst Sticky floor mat (just outside weigh room) Monthly or as needed Balance Analyst

HVAC system preventive maintenance Yearly RTI HVAC Personnel



### B.6.2 Ion Chromatographic Laboratory In the ion chromatographic labo ratory, several different inst ruments are routinely tested and maintained . Table B.6.3 details the items to inspect, how to appropriately document the inspection, and action items if the inspection fails. Table B.6.4 details the IC maintenance schedule and who will be responsible for performing the maintenance.

Table B.6.3. Inspection Criteria for Ion Analysis Laboratory

Item Inspection Frequency Inspection Parameter A ction if Item Fails Inspection Documentation Required

IC column back pressure Each day of

use Columnspecific; supplied by Dionex 1) Check for blockage 2) Replace column if necessary Record pressure in instrument log book

IC background conductivity Each day of

use Eluent specific; within control limits 1) Check eluent flow 2) Check suppressor 3) Call Dionex tech support if necessary Record conductivity in instrument log book

Baseline Each day of

use Steady; no “pulsing” 1) Check for leaks 2) Check for air bubbles in conductivity cell 3) Call Dionex tech support if necessary Record corrective action in instrument log bookQAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 59 of 95

Table B.6.4. Ion Analysis Laboratory Maintenance Schedule and Responsibility

Item Maintenance Frequency Inspection Parameter Responsible Party IC system preventive maintenance Yearly Check all valves, fittings, flows; replace as needed Dionex service representative

Check for leaks at valves and column fittings Daily Check for leaks IC analyst

Ultrasonic bath Monthly Check for power IC analyst



### B.6.3 EDXRF Laboratory

B.6.3.1 RTI In RTI’s XRF laboratory, the XRF instrume nt is subjected to routine testing and maintenance. Table B.6.5 details the items to inspect, docum entation to record inspection, and the action items if the inspection fails. Table B.6.6 details RTI’s XRF maintenance schedule and the responsibilities of the pers on performing the maintenance.

Table B.6.5. Inspection Criteria for RTI EDXRF Laboratory

Item Inspection Frequency Inspection Parameter A ction if Item Fails Inspection Documentation Required Energy calibration Daily Wavelength alignment of the instrument This is an automated process Document in instrument’s run log book.

Calibration verification Weekly Percent recovery of seven elements on thin-film NIST standards Adjust instrument calibration factors Document in instrument’s run log book; the results are stored in XRF database. Ongoing calibration verification Run with every tray of samples 90%–110% recovery using a multi-element sample containing Ti, Fe, Cd, Se, Pb, and SiO deposits of 5-10μg/cm 2 Re-check instrument calibration and adjust if necessary; re-analyze samples Document in instrument’s run log book

Fast Discriminator (FD) As needed FD value is located on the system status; if the FD is set too low, low energy peaks can be lost; if the FD is set too high, the dead time readings can be inaccurate and higher than normal Service required Document in service notebookQAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 60 of 95

Table B.6.6. RTI EDXRF Laboratory Ma intenance Schedule and Responsibility

Item Maintenance Frequency Responsible Party Vacuum pump maintenance and oil level check Monthly, as needed XRF analyst

Stability test As needed, depends on Ecal; this test checks for instability due to changes in the x-ray tube output or peak shift both of which will be detected XRF analyst

State-mandated radiation safety checks Semi-annually Safety Officer and XRF analyst



### B.6.3.2 CHESTER LabNet In the EDXRF laboratory, the EDXRF instrume nt is subjected to routine testing and maintenance. Table B.6.7 details the items to inspect, how to appropriately document the inspection, and action items if the inspection fails. Table B.6.8 details the EDXRF maintenance schedule and who will be responsible for performing the maintenance.

Table B.6.7. Inspection Criteria fo r CHESTER LabNet EDXRF Laboratory

Item Inspection Frequency Inspection Parameter A ction if Item Fails Inspection Documentation Required

Fundamental calibration Weekly Percent recovery of 11 elements on thin-film NIST standards Instrument recalibration Document in instrument log book

Ongoing calibration Every 10 samples 95%–105% recovery of six elements Reanalysis, check fundamental calibration Document in instrument log book

Excitation condition check Every sample Within analysis uncertainty Reanalysis Document in instrument log book

Table B.6.8. CHESTER LabNet XRF Laborat ory Maintenance Schedule and Responsibility

Item Maintenance Frequency Responsible Party Pump maintenance and oil level check Weekly XRF analyst

Chiller maintenance and coolant level check Weekly XRF analyst

Replenish liquid nitrogen in Dewar Weekly XRF analyst



### B.6.4 ICP/MS Laboratory Selected filters will be analyzed by ICP/MS to achieve higher sensitivity than is possible with the XRF method used for the bulk of the f ilter samples. The list of elements analyzed by ICP/MS is shown in Table B.6.9.QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 61 of 95

Table B.6.9. Elements to be Analyzed by ICP/MS

Aluminum* Antimony Arsenic Beryllium Cadmium Chromium Cobalt Copper Barium Lead Manganese Mercury Nickel Selenium Silver *ICP-MS analysis is not recommended using Whatman Tefl on filters due to background levels present in the stiffening ring.



### Filter samples are removed from cold storage or received after analysis by XRF. Sample information is entered into the extraction l ogbook. The filters are loaded into 50 mL, acidcleaned centrifuge tubes, with the loaded side facing inward. A 25 mL aliquot of extraction solution is added to cover the filter in the t ube. The tubes are capped and placed in a heated ultrasonic bath for 3 hours to extract the metals on the filter. The samples are allowed to cool, centrifuged, and a 5 mL aliquot of the supernatant liquid is rem oved for ICP-MS analysis. The ICP-MS is optimized daily with a tuning soluti on, and the samples are analyzed against a new calibration curve for each analytical sequence.

Two Thermo X-Series Inductivel y Coupled Plasma Mass Spectrometers are used for this procedure. Both instruments are equipped with co llision cell technology and the following major components:

 

### Torch box, RF generator, lens stack, quadra pole, and electron multiplier detector

 

### Personal computer with the Thermo PlasmaLab software

 

### Vacuum pump and turbo pump

 

### Refrigerated water recirculator

 

### Uninterruptible Power Supply (UPS), which supplies the entire instrument, PC, and chiller with 15 minutes of uninterruptible power in full operation and 2 hours of vacuum support in standby mode

 

### 240-position autosampler housed in a HEPA -filtered enclosure to protect against atmospheric contamination.

Standards are prepared from NIST-traceable, commercially purchased stock solutions. A series of concentrations ranging from 0.25 ppb to 500 ppb along with a blank are prepared to bracket expected analyte concentrations. The ra nge of calibration standards will be adjusted based on the indigenous concentration of individual elements in the samples.
A check standard is prepared from a sec ond source of commercially purchased NISTtraceable stock standards to verify the validity of the calibration curve. The check standard is prepared at a concentration that is not a point on the calibration curve an d near the midpoint of the calibration range. The check standard is an alyzed following calibration and before the analysis of any samples at a frequency of one pe r every 10 samples, and at the end of analysis. All sample results to be reported must be bracketed by passing standard checks.
Calibration is performed at the beginning of each analytical run. The correlation coefficient must be ≥ 0.995 for each element. The result for each standard concentration on the curve must be +/– 10% of the expected value fo r the point to be valid. The initial calibration check, which is prepared from a separate standa rd source than the calibrants, must pass at +/–QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 62 of 95


### 10% of the expected concentration for each elemen t. The initial calibration blank must be less than the reporting limit for each el ement. If an element fails to meet the calibration criteria, a new calibration must be run and the associated samples reanalyzed for the given element.
Several different quality control activities are performed as part of the analysis procedure. These activities, their freque ncy, and the measures of accepta ble performance are given in Table B.6.10.

Table B.6.10. Quality Control Activities for ICP/MS Analysis Sequences

Activity Frequency Measure of Acceptable Performance Calibration Every sequence Correlation coefficient of ≥ 0.995 QC blank Analyzed after calibration, every 10 samples, and at the end of the sequence All elements below method reporting limit

QC check sample Analyzed after calibration, every 10 samples, and at the end of the sequence 90%–110% recovery

MDL Every 6 months n/a Duplicate analysis One per 20 sa mples n/a – flag LDU if > 20%



### The detection limit for each element is calcul ated by analyzing seven replicates of a known standard concentration and multiplying the st andard deviation of the replicates by three. The uncertainty for the measurement is the pe rcent relative standard deviation, which is calculated by the instrument operating software fo r the triplicate readings taken on each sample.
B.6.5 Organic/Elemental Carbon (OC/EC) Laboratory B.6.5.1 RTI OC/EC Laboratory In the RTI OC/EC laboratory, the two S unset Laboratory CSN thermal-optical transmittance (TOT) analyzers and the two IMPROVE_A/TOR-TOT analyzers (a Sunset Laboratory dual mode and a DRI Model 2001) are routinely tested and maintained. Table B.6.11 details the analyzer maintenance schedule a nd who will be responsible for performing the maintenance.

Table B.6.11. OC/EC Laboratory Ma intenance Schedule and Responsibility

Item Maintenance Frequency Responsible Party OC/EC analyzers As needed (daily checks are performed on key components) RTI OC/EC analyst

Analytical balance Yearly or as needed Mettler Toledo, Inc., service representative Muffle furnace As required RTI OC/EC Analyst



### B.6.5.2 DRI OC/EC Laboratory In the DRI OC/EC laboratory, the twelve dual reflectance/transmittance (TOR/TOT) analyzers are routinely tested and maintained. Table B.6.12 details the analyzer maintenance schedule and who will be responsible for performing the maintenance.QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 63 of 95

Table B.6.12. OC/EC Laboratory Ma intenance Schedule and Responsibility

Item Maintenance Frequency Responsible Party TOR or TOR/TOT Analyzer As needed (daily checks are performed on key components) DRI OC/EC analyst

Analytical balance Yearly or as needed Quality Control Services (routine) or Mettler Toledo, Inc., service representative (as needed)



## B.7 Instrument Calibration and Frequency B.7.1 Gravimetric Mass Laboratory The microbalances are externally calibrated and serviced, if necessary, at least annually or as needed when problems are detected. RTI keeps records on the serv ice dates and calibration results. NIST-traceable standards are tracked to de termine if any bias is entering into the system. These standards are recertifie d annually. Control charts base d on a standard weight are maintained to track long-term drift and ot her time-dependent changes in microbalance performance.
Calibrations in RTI’s analytical laboratories are performed on each day of analysis. See the respective SOPs for more details.
B.7.2 Ion Chromatography Laboratory Multipoint calibration (0.05 to 25.0 ppm) is performed daily. Calibration is followed by analysis of QA/QC samples. Included are:

 QC samples containing anions/cations at conc entrations typical of those found in the midrange of actual filter extract concentrations

 QC sample containing anions/cations at concen trations typical of t hose found in the lower end of actual filter extract concentrations

 A commercially prepared NIST-traceable QA sample containing known concentrations of anions/cations.

Initially, only the calibration curve from 0.05 to 10.0 ppm is used for the calculation of the anion/cation concentrations. All field sample ion concentrations that exceed 10.0 ppm are recalculated with the 25.0 ppm standa rd added to the calibration curve.

B.7.3 EDXRF Laboratory

RTI and CHESTER LabNet obtain their calib ration standards from the same supplier (Micromatter Co.). Both labs analyze a multi-element standard that is prepared by Micromatter containing Si, Ti, Fe, Se, C d, and Pb at levels of 5–10 μ g/cm 2 

### . The multi-element standard is analyzed with each tray of samples.QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 64 of 95



### B.7.3.1 RTI Energy calibration is performed using a copper calibration standard provided by ThermoNoran. This is an automated test to adjust the pulse processor gain so that the detected xrays appear at the correct ener gy. Failure to perform this test daily could result in inaccurate quantitative results, misidentification, or failure to detect one or more elements. Peak calibration is performed by analyzing the following thin-film standards:

Purchased from Micromatter, Co. Table B.7.1 lists the elements and compounds on thin Mylar film that are to be analyzed for the CSN.

Table B.7.1. Elements Present on Micromatter, Co. Standard

Analyte A nalyte A nalyte
Sodium or Chlorine as NaCl Chromium as Cr metal Rubidium or Iodine as RbI

Magnesium as Mg metal Manganese as Mn metal Strontium as SrF2

Aluminum as Al metal Iron as Fe metal Silver or Mercury as Ag-Hg Amalgam
Silicon as SiO Cobalt as Co metal Cadmium or Selenium as CdSe Gallium or Phosphorus as GaP Nickel as Ni metal I ndium as In metal

Sulfur as CuSx Copper as Cu metal Tin as Sn metal
Potassium or Iodine as KI Zinc as ZnTe Anti mony as Sb metal

Calcium as CaF2 Arsenic as GaAs Barium as BaF2
Titanium as Ti metal Selenium as Se metal Cerium as CeF3

Vanadium as V metal Bromine or Cesium as CsBr Lead as Pb metal



### Calibration verification is pe rformed weekly by analyzing the following NIST thin-film standards provided by EPA. The expected value and the uncertainties are published with the NIST standards:

NIST SRM 1832 multi-elemental XR F thin film standard certif ied values are shown in Table B.7.2.QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 65 of 95

Table B.7.2. Certified Values of Elements Present on NIST Standard Reference Material No. 1832

Analyte Certified Value (μg/cm 2 )

SRM 1832

Aluminum 15.1 ± 0.98

Silicon 35.5 ± 1.14

Calcium 20.1 ± 1.30

Vanadium 4.83 ± 0.49 Manganese 4.62 ± 0.49

Cobalt 1.05 ± 0.06 Copper 2.45 ± 0.16



### Re-calibration is performe d on an as-needed basis.

B.7.3.2 CHESTER LabNet Energy calibration is performed using Kevex Standard No. 2036 and the IXRF software calibration option in which a low-ener gy line is measured at the Al K 2 

### line (1.487 KeV) and a high-energy line is measured at the Cr K 2 

### line (8.047 KeV). The program will then assign channel number 149 as the Al peak centroid and channel 805 as the Cu peak centroid, thereby calibrating each channe l increment at 10 eV.
Peak calibration is performed by analyz ing the following thin-film standards: 1. Micromatter, Inc., vapor deposit of si ngle or two non-interfering elements onto thin mylar film 2. EPA organo-metallic acetate film, usua lly with two non-interfering elements 3. NIST SRMs 1832 and 1833 multi-element vapor deposits on glass films.

Peaks should be Gaussian-shaped with at least 2,000 counts in the central channel (centroid). Methods for calcula ting peak location da ta, calibration factor s, and interference factors correction for PM 2.5 

### particle size are presented in Chester LabNet SOPs and accompanying discussion.
Recalibration is performed on an as-needed basis. Calibration verification is performed weekly using Calibration Veri fication Standards (NIST SRMs 1832 and 1833). Control limits are the uncertainties published with the NIST standa rds; for results outside of control limits, fundamental recalibration of the instrument is performed, followed by reanalysis of the NIST standards.

B.7.4 OC/EC Laboratories B.7.4.1 RTI OC/EC Laboratory

As shown in Table B.7.3, calibration of a CSN/TOT analy zer is checked daily using an external standard and during every analysis using an internal sta ndard. The external standard is prepared by spiking a clean section of quartz fi lter with 10 μL of a standard sucrose solution, which corresponds to a filter loading of about 21 μgC. The internal NIST-traceable standard isQAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 66 of 95



### 5% methane in helium. A set of three concentrat ions of sucrose external standards (10 μL of each, giving a range corresponding to about 4-42 μgC) of filter is run weekly.

Also shown in Table B.7.3, calibration of an IMPROVE_A/TOR-TOT analyzer is checked daily using both an intern al standard and an external st andard and during every analysis using an internal standard. The da ily internal standard check consists of automated injections of the internal standard (5% CH 4 

### /He) in a non-oxidizing atmosphe re (pure He), an oxidizing atmosphere (2% O 2 

### /He), and at the end of the run. The da ily external standard is prepared by spiking a clean section of quartz filter with about 27 μgC in 15-μL of a standard sucrose solution. The NIST-traceable internal standard is 5% methane in helium. A set of five injections (5 to 20 μL, giving a range corresponding to about 9-36 μgC) each of a sucrose external standard and a KHP external standard and six injecti ons (100 to 1500 μL, giving a range corresponding to about 2-36 μgC) each of NIST-traceable external CH 4 

### /He and CO 2 

### /He gas standards are used for a full calibration semi-annually or after significant instrument repairs.

Table B.7.3. RTI OC/EC Instrument Calibration and Frequency

Laboratory Instrument Calibration: Frequency

RTI OC/EC Laboratory CSN/TOT carbon analyzer Three-point external calibration: run init ially to demonstrate linearity; run once a week thereafter One-point external calibration check: run daily to confirm that FID response has not changed by more than + 10% since the last three-point calibration End-of-run calibration peak with 5% CH 4 /He: every analysis (counts within 95% to 105% of average for the day)

RTI OC/EC Laboratory IMPROVE_A /TOR-TOT carbon analyzer Semi-Annual calibration with four separate standards: separate 6-pt cals with 5% CH 4 /He and 5% CO 2 /He and separate 5-pt cals with a sucrose solution and a KHP solution (average slopes for the four separate calibrations within 95%-105% of average slope; recovery and internal standard counts for each run within 95%-105% of average for that standard) Daily Auto Cal check: Injection of CH 4 /He standard in He, He/O 2 , and end of run (area counts for the 3 injections must be within 95%-105% of the average for the three) Daily calibration check: mid-level inje ction of sucrose standard (recovery 90- 110%, internal standard counts within 90%-110% of average counts for last full semi-annual calibration) End-of-run calibration peak with 5% CH 4 /He standard, every analysis (counts must be >20,000 and within 95%-105% of average counts for the day)



### B.7.4.2 DRI OC/EC Laboratory

As shown in Table B.7.4, the DRI carbon analyzers are calib rated in three ways in this order:
1. Semi-annual (or after instrument repai r) full calibration using KHP, sucrose, CH 4 

### /He, and CO 2 

### /He standards; 2. Daily calibration checks using inject ions of the two gas standards (CH 4 

### /He, and CO 2 

### /He); and 3. Automatic injection of the CH 4 

### /H 2 

### gas standard as an internal standard at the end of each analysis.QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 67 of 95

Table B.7.4. DRI OC/EC Instrument Calibration and Frequency

Laboratory Instrument Calibration: Frequency

DRI OC/EC Laboratory IMPROVE_A /TOR-TOT carbon analyzer Semi-Annual: Separate 5-pt cals with 5% CH 4 /He, 5% CO 2 /He, sucrose solution, and KHP solution (average slopes for the four separate calibrations; new slope 90%–110% of 5% previous slope if no instrument repairs) Calibration injections of the two NIST traceable gas standards; reverse two cal gases and the carrier gases (O 2 /He and He) between morning and afternoon injections (counts should be same) End-of-run calibration peak with 5% CH 4 /He calibration gas performed as part of routine program (counts > 20,000)



## B.8 Inspection/Acceptance Requirements for Supplies and Consumables
Supplies and consumables are inspected by the laboratory superv isor or laboratory technicians to determine if they ar e acceptable for use on the project.

B.8.1 Filters RTI will purchase, inspect, and verify filter lots to be used for the CSN according to specific procedures applicable to each type of filter and for other sampling media such as reagents used to prepare denuders.
RTI will purchase the appropriate number of filters and other sampling media to supply the needs of the monitoring organizations, as directed by the DOPO. Th e quantity of filters ordered will be sufficient to provide spares to replace defective filters and to satisfy all QA/QC needs (e.g., laboratory blanks and field blanks). Cassettes, if required, are provided by the state sampling authority responsible for field monitori ng. The number of cassettes must be sufficient to allow for shipments to the sampling sites as well as preparation of upcoming shipments from RTI.
Regardless of the filter type or the project’s sp ecific analytical requirements, filters of all types must be examined individually prior to us e to ensure that one or more of the following defects does not exist:

 Pinholes. A small hole or tear in the filter matr ix that appears when examined over a light table.

 Loose material. Any extra loose material or partic ulate contamination on the filter surface.

 Separation of reinforcing ring

. Any separation or discontinuity of the seal between the filter matrix and the outer retaining or reinforcing ring.

 Discoloration. Any visible discolorati on that indicates proble ms during the filter’s manufacture or packaging.

 Filter non-uniformity. Any obvious difference in the spatial uniformity of the filter matrix structure or color. Analytical tec hniques that rely on the uniformity of aerosol deposition (e.g., XRF) are particularly sens itive to filter defects of this type.

 Other. Defined as any other defect (e.g., wri nkling, warping) that might prevent a filter from providing accurate measurement data.QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 68 of 95


### The other acceptance criteria a pplicable to the different filt er types are described in the following sections.

B.8.1.1 Teflon Filters RTI will purchase the appropriate number of Teflon filters (Whatman, Catalog No. 7592- 004) as directed by the DOPOs. The quantity of filters ordered will be sufficient to provide spares to replace defective filte rs and to satisfy all QA/QC needs (e.g., laboratory blanks and field blanks). Cassettes, if re quired, must be provided by the state sampling authority. The number of cassettes should be sufficient to allo w for shipments to the sampling sites as well as preparation of upcoming shipments from RTI. A cceptance testing of Teflon filters (and other filter types) to be used for ion sampling should be based on analysis of a minimum of 2% per lot (or two filters). Lots must be rejected when the levels of individual anion or cation species exceed 1μg/filter.
B.8.1.2 Nylon Filters Nylon filters (Whatman, 47 mm diameter, 1 micron pore size) are purchased from the McConnell Group (Cat. No. TM185967). These filters are prepared as follows: 1. Rinse twice in deionized water, approximately one minute per rinse 2. Using TCLP apparatus, rotate for 7 hours in a 2-liter polypropylene jar completely filled with deionized water; drain and repeat for approximately 24 hours 3. Dry in a 40 ° C oven for 1⁄2 to 1 hour.

Nitrate, sulfate, sodium, ammonium, and potassi um levels in each lot should be less than 1μg/filter each based on 2% anal ysis per lot. Prepared nylon filters should be sealed and refrigerated until needed for field sampling.

B.8.1.3 Quartz Filters The Whatman 47 mm diameter quartz filters and the Pall Tissuquartz 25mm diameter filters are prepared by RTI in-house. The procedure is as follows:

 

### The 47 mm filters are typically prefired in batches of 100, in a muffle furnace at 900°C for 3 hours. The 25mm filters are pr efired typically in batches of 100 for 4 hours.

 

### The filters are acceptance tested once they have cooled for at least 2 hours, under a low flow of nitrogen in the furnace which has been turned off.

 

### Either 2% or a minimum of 2, whichever is more, of the filters are randomly selected from the cleaned batch for total carbon te sting according to National Institute for Occupational Safety and Health (NIO SH) Method 5040. The results of the acceptance testing show evidence of inadequa te cleaning or contamination that may have occurred during transport.QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 69 of 95

 

### If any filter analyzed gives, a measured blank total carbon level exceeding 1μg/cm2 for the 47mm filters and 1.5μg/cm2 for the 25 mm filters, the filters from that batch will be rejected or recleaned.

 

### Batches of the 25mm quartz filters that pass the acceptance-testing criterion ( ≤ 1.5 μg/cm 2 

### total carbon) are assigned a Batc h Number. Batches of acceptancetested filters are placed individually in petri slide holders, which are placed in a resealable plastic bag labeled with the Batc h Number. The resealable plastic bag is stored in a freezer at ≤ -15 ° C until the filters are used.

 

### Batches of the 47mm quartz filters that pass the acceptance-testing criterion ( ≤ 1 μg/cm 2 

### total carbon) are assigned a Batch Numb er, which is used to associate the history of the filters with the batch and to track the batch until the filters are assigned individual identifica tion numbers in the Sample Hand ling and Archiving Laboratory. Batches of acceptance-tested filters are pl aced individually in petri dish holders, which are placed in a resealable plastic bag labeled with the Batch Number. The resealable plastic bag is stored in a freezer at ≤ -15 ° C until the filters are used.

 

### Filters are kept in a freezer until just prior to loading into modules.

The reason for the difference in the acceptance criteria is the size of the filter punch used for the analysis: The 25mm diameter filter us ed for the IMPROVE_A OC/EC method requires a punch that has an area of about 0.5 cm 2 

### , and the 47 mm diameter filter used for the CSN/TOT OC/EC method requires a punch that has an area of about 1.5 cm 2 

### . RTI will store batches of prepared filters in a freezer until they are needed in prepar ation for field sampling. Before loading onto the cartridges or modules for fiel d sampling, each quartz filter is carefully inspected for uniformity in size, shape, thickness, and appear ance. Any filters that are visually flawed will be discarded.

B.8.2 Criteria for Other Materials Other RTI laboratories for Ion Analysis, Carbon Analysis, and Denuder Refurbishment will use the types and quality of reagents, purifie d water, and other materials specified in the respective SOPs.


## B.9 Data Acquisition Requirements (Non-direct Measurements)
This work does not involve the use of any hist orical databases, liter ature files, etc. Any supplemental, non-direct measurement data supplied by the monitoring organizations or subcontractors for inclusion in the database will be subject to limited validation to ensure that data have been correctly entered and identified.


## B.10 Data Management
This section describes Data Management System (DMS) Quality Control/Quality Assurance (QC/QA) as well as how the DMS promotes overall QC/QA program activities.QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 70 of 95



### B.10.1 Overview
The core of the DMS is a custom database, using Microsoft SQL Server as a relational database server. Custom user programs for da ta entry and processing were written in Access 2000. To minimize data entry errors, the system imports laboratory data directly from electronic data files produced by laborator y instrumentation systems.
RTI created preset sampling c onfigurations to ensure th at samples were scheduled, prepared, and processed consistently. Each samp ling event is scheduled for a specific sampling configuration. These configurations specify wh ich sampling media are used by specific sampler channels, what flow rates are appropriate for sampling, which analyses are to be performed on each sampling medium, and how the calculations for each analysis are to be performed.
The system tracks each sampling module, ev ent, and sampling medi um with a unique identification number (ID). To prevent data entr y errors, barcode reader s are used extensively and each ID contains a check digit to reduce errors in manual entry.
Data reports are copied to a separate extern al Web server for review by the site data contacts. Data revisions are submitted via e-mail a nd incorporated into the SQL Server database. An AQS-ready data file is then prepared for import into AQS.
B.10.2 DMS Design Features Careful identification of each sampling m odule and sampling event is essential in combining the correct analytical results with the correct sampling event. Many features have been designed into the DMS to prevent common data entry errors. Unique identifiers are generated for each sampling event, module, and sa mpling medium. These identifiers are used to link modules with configurations , sampling events, and analyses. Barcode scanners are used for data entry to reduce the chance of data entry errors. In addition, a ll identifiers have check digits to permit the data entry program s to immediately catch most manua l data entry errors. Database referential integrity also preven ts linkage of any sampling modul e, event, or sampling medium that has not been previously cr eated in the database system.

B.10.2.1 Sample Identifiers Each item that is tracked by the DMS is as signed a unique identification number (ID). Tracked items include record sheets such as the Field Sampling Chain-of-Custody Form, as well as equipment such as sampler modules, shipping c ontainers, and analysis a liquots in storage. ID numbers that are not automatically generated at the time of data en try (i.e., those that are entered from a local workstation) are obtained from preprinted barcod e stickers. The stickers are generated with a unique leading character that specifies the ty pe of item being generated and with a trailing checksum character. The leading ch aracter is used by data entry applications to prevent entry of a data item’s ID into the wrong field on a form. As an example, a module ID cannot be entered into the aliquot (analytical sa mple) ID field because module IDs begin with “I” and aliquot IDs begin with “A.” The trailing checksum character is used by data entry applications to detect and prevent most comm on transposition and single character entries. Table B.10.1 shows the labels currently in use by the CSN Program.QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 71 of 95

Table B.10.1. Label Identifiers for Tracking CSN Records and Equipment

Prefix Label Type

Q Field Sampling Chain of Custody A Aliquot I Sampler Module (“Inventory”) R Measurement Request ID C Shipping Container (Cooler) B Storage Bins L Bin Storage Location H Aliquot Shipment Batches (to laboratories) Y Aliquot Archiving Box



### B.10.2.2 Barcode Scanners Handheld laser scanning barcode readers are used at all SHAL processing stations to read barcode ID labels. These readers are inserted into th e client workstation’s keyboard connection and provide a rapid and reliable means of enteri ng ID labels used in sample processing.
B.10.2.3 Relational Integrity SQL Server permits establishment of foreign key constraints between fields in related tables. These constraints provide automatic enforcement of database referential integrity. Enforcement occurs at the server level and is not dependent on app lication-level programs. Referential integrity constraints prevent entry of a record in a dependent (child) record without a corresponding record in the independent (parent) ta ble. This prevents entr y of records that are not linked to other database items. Similarly, an independent (parent) re cord cannot be deleted while records that depend on that record exist. This prevents the creati on of orphaned records.
As an example of referential integrity, laborat ory results for a laboratory sample (aliquot) cannot be entered unless the labo ratory sample number was previ ously entered into the Aliquots Table (at the time the sample was created). Thus, attempts to enter laboratory results from other programs or from programs that have incorrect sample identification would be prevented. Attempts to delete an aliquot that has analytic al data would also be prevented, as this would orphan the analytical results (i.e ., leave results that have no co rresponding sample information).

B.10.2.4 Double Entr y of Field Data Sample event information (such as elapsed sample time, volume, barometric pressure, temperature, and sampler QC information) for scheduled events are transmitted from the field on a multi-copy Field COC Form. To prevent data entry errors, information on these forms are double entered and compared by a comparison progr am. Any discrepancies are resolved before transfer of the double-entered data to the main database.
B.10.2.5 Direct Transfer of Laboratory Data All laboratory data are sent from the laborat ory to the DMS as an electronic file via email. The laboratory data are obtained directly from instrument data syst em outputs that containQAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 72 of 95


### the sample identifier and the measured valu e. Laboratory personnel add additional QC information during their QC review process. The resulting laboratory data files are directly transferred into the database using custom import programs. This direct tr ansfer prevents data entry errors that could result from manually retyping data into the DMS.
B.10.2.6 Training and D evelopment Databases Separate training and development databases ha ve been established for operator training and program development purposes, respectively. Th is permits us to train operators and develop new software without risk of modifying the actu al program database. All output (forms, reports, etc.) from these databases contain clear labels to identify them as training or development reports. This prevents their accidental usage in the actual program. In addition, all data entry forms are color coded to clearly identify when a database other than the actual program database is in use. This prevents accident al entry of data into the training or development database when it was intended to be entered into the actual database.
B.10.2.7 Database Backup and Recovery The information contained in the SQL Server database is backed up to tape on a nightly basis. Tape copies are maintained off site by RTI’s IT department. Detailed procedures are covered in RTI’s Speciation Data Disaster Recovery Plan.

B.10.3 Automated and Semi-Automated QC Limit Checks for Outlier Detection The database contains provisions to add data quality flags to most data records. These data flags allow the annotation of data to i ndicate specific problems and or c onditions that might affect data quality. Flags may be added to entire sampli ng events, individual sampler flow channels, analytical samples (aliquots), or individual analysis results. The flags are expanded during the reporting process so that flags that reflect an en tire sampling event apply to all results in that event, flags affecting a sampler flow channel ap ply to all results usi ng that channel, etc.
A number of automated range checks are curre ntly in place. Outli er checks, also known as “Level 1 checks,” are done based on mass bala nce, anion-cation balance ratios, and other metrics. Assigning the limits for these outlier checks required the development of sufficient historical data to establish a base line to set appropriate QC limits. Tables B.10.2 and B.10.3 show the statistical QC limits that have been developed for PM 2.5 

### based on experience during the mini-trends pilot program. The upper and lower li mits were based on the 2nd and 98th percentile points on the distributio ns of the mini-trends data. For blanks , the concentrations were flagged at the upper 95 th 

### percentile. Similar validation limits will be developed for speciated PM 10 

### and PM coarse 

### when sufficient data has been gathered.
Additional strategies for establishing acceptan ce limits should be discussed between RTI and EPA.QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 73 of 95

Table B.10.2. Statistical Validation Limits for Routine Data

Percentile Tail Validation Test Sample Type Limit, μ g Analyte(s) Outlier Flag

2.0 LOWER PM 2.5 Mass Conc. ROUTINE 2.98 PM 2.5 Mass Conc. QL1

2.0 LOWER Anion/Cation Ratio ROUTINE 0.86 All ions QAC

98.0 UPPER Anion/Cati on Ratio ROUTINE 2.82 All ions QAC

2.0 LOWER Mass Ratio ROUTIN E 0.60 All analytes QMB

98.0 UPPER Mass Ratio ROUTIN E 1.32 All analytes QMB

2.0 LOWER Sulfur/Sulfate Ratio RO UTINE 0.25 Sulfate ion, XRF QCR

98.0 UPPER Sulfur/Sulfate Ratio RO UTINE 0.45 Sulfat e ion, XRF QCR

Table B.10.3. Statistical Validation Limits for Blanks

Tail Analyte(s) Sample Type Limit
μ g Analyte Outlier Flag

UPPER PM 2.5 Mass FIELD BLANK 50.00 PM 2.5 Mass QL1

UPPER PM 2.5 Mass TRIP BLANK 50.00 PM 2.5 Mass QL1



### The Internal Flags shown in the last column are used to keep track of flagged data within the RTI database and are also shown on the m onthly data reports; however, these are not accepted by AQS and must be converted into va lid AQS validity status codes and AQS null value codes prior to delivery to AQS. Table B.10.4 shows how different types of internal flags are converted into AQS codes. There is no one-t o-one correspondence between the Internal Flags and the AQS Codes, so the QC reviewer or SHAL supervisor will assign the AQS Codes based on the identified reason for the violation of the screening limits. Because the causes for outliers is often unknown even after caref ul review of the available do cumentation, “generic” AQS codes must be used in these cases, as shown in the table.QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 74 of 95

Table B.10.4. Mapping of Outlier Flags onto AQS Codes

Objective Cause Found for Level 1 Outlier A QS codes assigned

If NOT Invalid (Suspicious) If Invalid Lab Error [1] AR Filter Damage [1] AJ Module Assignment Error (N/A) AQ or AR Sampler Malfunct ion (N/A) AN Unusual Conditions Noted by Operator [1] [2]

Unknown Cause 5 AS or AM Range Checks (Table 10.3) (N/A) 5 [1] = Use the applicable AQS validity status code [2] = Use the applicable AQS null value code (N/A) = Not Applicable



### Additional range checks based on fixed criter ia are also performed and AQS flags are assigned as shown in Table B.10.5.

Table B.10.5. Automated Checks Based on Fixed Criteria

Paramete r Limits A QS Null Value Code Exposure Duration, t exp 23 < t exp < 25 hrs AN – Machine malfunction AQ – Collection error AV – Power failure Other code as appropriate Holding Time before removal from sampler, t p ick-u p t pick-up < 48 hrs None – As per EPA direction

Average Flow Rate, F av g Within 10% of target flow rate AH – Flow rate out of range



### B.10.4 Report Preparation and QA Screening Monthly data reports are screened carefully as described in the follo wing sections prior to delivery to the state mo nitoring organizations.
B.10.4.1 Data Set Completeness and Integrity Crosstab Reports showing site locations (rows) and sampling dates (columns) are generated and examined to get an overall picture of data comp leteness and integrity of data assignments. Missing or anomalous results are investigated and co rrected by the data processing staff with the assistance of SH AL and QA personnel. The following crosstab tables are generated to facilitate this screening process:

1. COC Form number for each event – Field and trip blanks, routine samples, and unscheduled blanks are displayed in a rect angular table. Missi ng cells in the table indicate missed exposures or missing data. When empty cells are observed, the data processing manager should be contacted to determine why the data have not been reported. If an investigation indicates that no data were received, then the SHAL supervisor should be consulted to find out if there was a problem with the shipment.QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 75 of 95



### 2. Total counts of AQS-deliverable records – Each sampler type should generate a specific number of AQS record counts. Ex ceptions typically are the result of missing analytical results or of processing record s. RTI tries to hold reporting on events until all analysis results have been received. If no additional anal ysis data are expected for a particular exposure, the data manager will fill the records with “missing data” flags so that the data can be delivered and the exposure purged from the data delivery
queue.

3. Counts of invalid or suspicious analyte records – Systematic stretches of invalid data for a site may indicate that a site is having problems or that filter shipments to the site should be discontinued.

4. Sampled date vs. scheduled date – Any event where these “date” records do not agree is investigated by examining the Field Sample COC (FSCOC) form and by contacting the monitoring agency, if necessa ry. If a sample was actually run on the wrong date, the data are transmitted to AQS w ith the date actually run. If the date is incorrect due to a typographical or other error, it is corrected.

B.10.4.2 Entry and Verification of Data Changes from the States Changes requested by the state agencies are entered into RTI’s database by the data processing staff as the comments are received from the respective DOPOs.
When the acceptance period for comments closes for a particular data delivery batch, the text-formatted AQS file is generate d. This is checked for integrity using crosstab tables and other simple reporting methods. Record counts per even t and sampling date checks are particularly helpful in detecting problems with the record set. After any anomalie s are corrected, the AQS text file is regenerated and transmitted to EPA’s AQS database as discussed in the next section.
B.10.5 AQS Data Entry Routine (actual sampled), Field, Trip, and 24-H our Blank data are currently sent to AQS. Table B.10.6 summarizes all of the AQS parame ter codes applicable to the PM 2.5 

### Chemical Speciation analytes. Table B.10.7 presents the AQS parameter c odes for field data parameters. Units for all analytes are mi crograms per cubic meter under ambient conditions (i.e., not corrected to standard temperature and pressu re). The nominal sampling period is 24 hours. Similar tables for PM 10 

### and PM coarse 

### will be developed when the QAPP is finalized or when the parameter codes become available.
The validity status of AQS data is reported in two ways: Data that are qualified in some way but still may be useful for some purposes are assigned Validit y Status Codes. These codes, shown in Table B.10.8, do not overwrite the data value, which provides data users with the option to include the data item in their analyses. Alternatively, data that are judged to be invalid receive an AQS Null Value Code. In the curren t AQS system, the Null Value Code overwrites the data value such that the AQS user cannot ac cess the data. The Null Valu e Codes applicable to the CSN Program are shown in Table B.10.9.QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 76 of 95

Table B.10.6. Analytes and AQS Parameter Codes (PM 2.5 Only)

AQS Parameter Codes: PM2.5 (LC) Analyte Symbol Analysis

88102 Antimony Sb EDXRF (trace elements)

88103 Arsenic As EDXRF (trace elements)

88104 Aluminum Al EDXRF (trace elements)

88107 Barium Ba EDXRF (trace elements)

88109 Bromine Br EDXRF (trace elements)

88110 Cadmium Cd EDXRF (trace elements)

88111 Calcium Ca EDXRF (trace elements)

88112 Chromium Cr EDXRF (trace elements)

88113 Cobalt Co EDXRF (trace elements)

88114 Copper Cu EDXRF (trace elements)

88115 Chlorine Cl EDXRF (trace elements)

88117 Cerium Ce EDXRF (trace elements)

88118 Cesium Cs EDXRF (trace elements)

88126 Iron Fe EDXRF (trace elements)

88128 Lead Pb EDXRF (trace elements)

88131 Indium In EDXRF (trace elements)

88132 Manganese Mn EDXRF (trace elements)

88136 Nickel Ni EDXRF (trace elements)

88140 Magnesium Mg EDXRF (trace elements)

88152 Phosphorus P EDXRF (trace elements)

88154 Selenium Se EDXRF (trace elements)

88160 Tin Sn EDXRF (trace elements)

88161 Titanium Ti EDXRF (trace elements)

88164 Vanadium V EDXRF (trace elements)

88165 Silicon Si EDXRF (trace elements)

88166 Silver Ag EDXRF (trace elements)

88167 Zinc Zn EDXRF (trace elements)

88168 Strontium Sr EDXRF (trace elements)

88169 Sulfur S EDXRF (trace elements)

88176 Rubidium Rb EDXRF (trace elements)

88180 Potassium K EDXRF (trace elements)QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 77 of 95

AQS Parameter Codes: PM2.5 (LC) Analyte Symbol Analysis

88184 Sodium Na EDXRF (trace elements)

88185 Zirconium Zr EDXRF (trace elements)

88301 Ammonium NH 4 + Ion Chromatography, Cations

88302 Sodium Na + Ion Chromatography, Cations

88303 Potassium K + Ion Chromatography, Cations

88305 Organic Carbon STN OC_TOT OC/EC TOT

88306 Nitrate NO 3- Ion Chromatography, Nitrate

88307 Elemental Carbon STN EC_TOT OC/EC TOT

88332 PK1_OC STN PK1_OC OC/EC TOT

88333 PK2_OC STN PK2_OC OC/EC TOT

88334 PK3_OC STN PK3_OC OC/EC TOT

88335 PK4_OC STN PK4_OC OC/EC TOT

88336 PYROLC STN PKYROLC OC/EC TOT

88355 OC IMPROVE TOT OCT Organic and elemental carbon IMPROVE_A

88357 EC IMPROVE TOT ECT Organic and elemental carbon IMPROVE_A

88370 OC IMPROVE TOR OCR Organic and elemental carbon IMPROVE_A

88374 O1 IMPROVE OC1 Organic and elemental carbon IMPROVE_A

88375 O2 IMPROVE OC2 Organic and elemental carbon IMPROVE_A

88376 O3 IMPROVE OC3 Organic and elemental carbon IMPROVE_A

88377 O4 IMPROVE OC4 Organic and elemental carbon IMPROVE_A

88378 OP IMPROVE TOR PCR Organic and elemental carbon IMPROVE_A

88380 EC IMPROVE TOR ECR Organic and elemental carbon IMPROVE_A

88383 E1 IMPROVE EC1 Organic and elemental carbon IMPROVE_A

88384 E2 IMPROVE EC2 Organic and elemental carbon IMPROVE_A

88385 E3 IMPROVE EC3 Organic and elemental carbon IMPROVE_A

88388 OP IMPROVE TOT PCT Organic and elemental carbon IMPROVE_AQAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 78 of 95

Table B.10.7. Field Data and AQS Parameter Codes

AQS Parameter Code Property Units 68103 Min Ambient Temp E C 68104 Max Ambient Temp E C 68105 Avg Ambient Temp E C

68106 Min Barometric Pressure torr

68107 Max Barometric Pressure torr 68108 Avg Barometric Pressure torr

Table B.10.8. AQS Validity Status Codes

AQS Validity Status Code Flag Name

IA African Dust

IB Asian Dust IC Chem. Spills and Industrial Accidents ID Cleanup After a Major Disaster

IE Demolition

IF Fire – Canadian

IG Fire – Mexico/Central America

IH Fireworks II High Pollen Count IJ High Winds IK Infrequent Large Gatherings

IL Other

IM Prescribed Fire IN Seismic Activity IO Stratospheric Ozone Intrusion

IP Structural Fire
IQ Terrorist Act IR Unique Traffic Disruption IS Volcanic Eruptions

IT Wildfire – U. S.

IU Wildland Fire Use Fire – U. S.

1 Critical Criteria Not Met 2 Operational Criteria Not Met

3 Possible Field Contamination

4 Possible Lab Contamination

5 Outlier – Cause Unknown 6 Data Prior to QAPP Approval A High Winds C Volcanic EruptionsQAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 79 of 95

AQS Validity Status Code Flag Name

E Forest Fire

F Structural Fire H Chemical Spills & Indust. Accidents I Unusual Traffic Congestion

J Construction/demolition O Infrequent Large Gatherings Q Prescribed Burning R Clean up after a Major Disaster S Seismic Activity T Multiple Flags; Misc.

V Validated Value W Flow Rate Average out of Spec. X Filter Temperature Difference out of Spec. Y Elapsed Sample Time out of Spec.

Table B.10.9. AQS Null Value Codes

AQS Code Flag Name BI Sample Lost or Damaged in Shipment AA Sample Pressure out of Limits

AB Technician Unavailable AC Construction/repairs in Area AD Shelter Storm Damage AE Shelter Temperature Outside Limits

AF Scheduled but Not Collected AG Sample Time out of Limits AH Sample Flow Ra te out of Limits AI Insufficient Data (Cannot Calculate) AJ Filter Damage

AK Filter Leak AL Voided by Operator

AM Miscellaneous Void

AN Machine Malfunction

AO Bad Weather

AP Vandalism
AQ Collection Error

AR Lab Error AS Poor Quality Assurance Results

AT Calibration AU Monitoring Waived AV Power Failure (Powr)QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 80 of 95

AQS Code Flag Name AW Wildlife Damage AX Precision Check (Prec) AY QC Control Points (Zero/span) AZ QC Audit (Audt) BA Maintenance/routine Repairs

BB Unable to Reach Site BC Multi-point Calibration

BD Auto Calibration BE Building/site Repair BF Precision/zero/span



### B.10.6 Data Management in the Laboratories The individual analytical labo ratories are responsible for ma naging their data prior to its entry into the CSN Program’s database. The proc edures for data management vary significantly between laboratories and are described in the respective SOPs.

B.10.7 Management and Repor ting of Field Audit Data RTI will provide data entry and reporting support for field calibration and audit data. These will include parameters of flow rate, temperature, pressure, and clock time checks. Details regarding data input and reporti ng have not been worked out as of the time of this writing, however principles described above will be followed in developing the data management processes and procedures for these new data.QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 81 of 95



### C.1 Assessments and Response Actions

RTI will participate in any laboratory assessment or proficiency program established by EPA, and will maintain any analyst or labor atory certification required for the program.

The QA Manager for this project, Dr. Jame s Flanagan or his designee, will perform periodic technical systems audits of the RTI activities. These a udits will cover all aspects of RTI's work, including sample receipt, cust ody, conditioning, weighing, shipping, data reduction and reporting. These audits are sche duled to be performed annually.

Prior to each audit, a checklist will be prepared, based on this QAPP, the SOPs, and applicable guidance documents. After the audits , the QA Manager will su mmarize the results in a memorandum to Dr. Jayanty within two weeks. These memoranda will clearly spell out any areas in which corrective action is necessary. If any se rious problems are identified that require immediate action, such as a large, systematic an alytical bias, the QA Manager will convey these to Dr. Jayanty verbally or through electronic ma il the day that such problems are identified. Corrective actions are the responsibility of Dr. Jayanty and will be documented in a memorandum to the file and all relevant proj ect staff, including the QA Manager. The QA Manager will verify the effectiveness of any formal corrective actions and summarize these in memoranda to Dr. Jayanty.

Since these memoranda constitute the corr ective action system fo r this project, all memoranda will be retained in the QA Manager's files, where they will be available for internal or external review.

As SPM, Dr. Jayanty will conduct ongoing inform al surveillance of proj ect activities. If new staff members eventually perform some of the activities that others ar e initially responsible for, the experienced personnel and/or technical supervisors will perform ongoing surveillance of the new persons’ work to ensure th at the quality of the results is comparable with the previous results.

C.1.1 External Quality Assurance Assessments

RTI's PM speciation laboratories, including subcontractor laboratories, participate in external QA assessments as requested by EPA. Th e on-site audits and assessments as of this writing are listed below. The most current assessments and re ports are available at the PM2.5 Speciation Quality Assurance s ection of EPA's AMTIC website, http://www.epa.gov/ttn/amtic/pmspec.html.

 

### EPA/NAREL:

‐ Experimental Inter-comparison of Sp eciation Laboratories (June 15, 2011), (accessed 5/7/2012).

‐ 2010 DRI laboratory Technical Systems a udit (June 1, 2011), (accessed 5/7/2012).QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 82 of 95



### ‐ UC Davis Laboratory Audit (January 11, 2011), http://www.epa.gov/ttn/amtic/pmspec.html accessed 8/10/2010).

‐ Experimental Inter-comparison of Sp eciation Laboratories (June 15, 2010) , http://www.epa.gov/ttn/amtic/pmspec.html accessed 8/10/2010).

‐ October 2009 Technical Systems Audit Report of South Coast AQMD Chemical Speciation Laboratory (April 2, 2010), (http://www.epa.gov/ttn/amtic/pmspec.html accessed 8/10/2010).

‐ Technical Memorandum: Report of the Sept 2009 Technical Systems Audit of RTI's PM2.5 Speciation and Support laboratories (November 24, 2009), (http://www.epa.gov/ttn/amtic/pmspec.html accessed 8/10/2010).

‐ Technical Memorandum: Experimental Inte r-comparison of Speciation Laboratories (September 9, 2009), (http://www.epa.gov/ttn/amtic/pmspec.html accessed 8/10/2010).

‐ Multilab Speciation PE Re port (November 24, 2008), (http://www.epa.gov/ttn/amtic/pmspec.html accessed 8/10/2010).

- May, 2007 Technical Systems Audit of DRI's Laboratory

- July 2005 EPA audit of RTI Ch emical Speciation Lab Operations

- October 2003 PM2.5 Chemical Speciat ion Trends Network Lab Audit Report 12/05/03, www.epa.gov/ttn/amtic/files/a mbient/pm25/spec/audit03.pdf

– EPA audit of RTI Chemical Spec iation Laboratory Operations 03/20/02, www.epa.gov/ttn/amtic/files/ambient/pm25/spec/rtiaudit2.pdf

– A report on the study to evaluate specif ic laboratory performance as part of the QA oversight of the PM2.5 speciation program 01/30/02, www.epa.gov/ttn/amtic/files/ambient/pm25/spec/pememo.pdf

– "Chemical Speciation Labor atory Audit Report", 02/02/01, www.epa.gov/ttn/amtic/files/ambient/pm25/spec/audit.pdf

– "Performance Evaluation Samples fo r PM2.5 Chemical Speciation Network", 02/02/01, www.epa.gov/ttn/amtic/files/amb ient/pm25/spec/pesreport.pdf

– "PM2.5 Chemical Speciation Labo ratory Audit Report", 09/01/00, www.epa.gov/ttn/amtic/files/ambient/pm25/spec/pereport.pdfQAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 83 of 95


### – "Performance Evaluation Samples fo r PM2.5 Chemical Speciation Network", 09/01/00, www.epa.gov/ttn/amtic/files/ambient/pm25/spec/

 

### The State of Louisiana audits the Gravimetry Laboratory under the Louisiana Environmental Laboratory Accreditation Program. RTI performs PM2.5 filter weighings for the State. The most recent on-site assessment was performed November 13-14, 2008.

C.2 Reports to Management

Within 20 business days from receipt of the last sample in a monthly delivery batch, RTI posts the results of filter analyses together with the level 0 and level 1 validation flags to web site where they can be accessed by the EPA DOPO an d State or local contact who submitted the delivery order. Upon approval by the State or local agency contacts, the data are posted to the AQS electronic data base. Draft and final comp osite annual data summary reports are issued by RTI to the EPA Project Officer.

The SPM or designee approves the monthly data postings and th e annual reports. The SPM and the QA Manager are notified whenever th ere is a QA problem and will be apprised of corrective actions taken to solv e the problem. The QA Manager wi ll perform yearly technical audits and will submit a report to the project office within two weeks of the audits. Annual determinations of limit of detection, precision, an accuracy and a summary of results of analysis of external performance evaluation samples will also be submitted as part of the Annual Data Summary Report.

The following is a list of regularly scheduled technical and quality- related reports that will be provided to EPA:

1. Level 0 Validation Report (Checklist) . Data entry checking of the Custody Forms and Level 0 validation checklist is perf ormed by double entry, with comparison done at RTI. This provides better accuracy than manually reviewing sampler forms to catch errors. Data flags generated during the Level 0 validation process are attached to each data record and are reported monthly to the DOPOs and monitoring agencies as part of regular monthly reporting descri bed in items 3 and 4, below.

2. Level 1 Validation Report (Checklist). Cation/anion balance, sulfur/sulfate balance, and reconstructed mass balance reports (spr eadsheets) are generated from the DBMS. Other statistical reports are done using data from the DBMS during monthly validation to assist validati on personnel in identifying pr oblems. Additional statistical reports are being developed as needed based on experience with the chemical speciation data. Data flags generated dur ing the Level 1 validation process are attached to each data record and are re ported monthly to the DOPOs and monitoring agencies monthly as part of items 3 and 4, below.

3. Monthly Traceability Report. A report to show traceability between components and analytical results for each sampling event is produced using the DBMS. “Traceability” means correctly relating the identity of filte rs, analytical results, etc.,QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 84 of 95


### to the correct event. Electronic copies of th is report are prepared and made available to each of the following: the state agen cies submitting the delivery orders, the DOPOs, and the EPA Regional QA Laborator y. The information for the monthly traceability report is included as part of the Monthly Anal ytical Reports described in the next item.

4. Monthly Analytical Reports (Electronic and hard copies). Data for this report are generated from RTI’s DBMS using the fiel d and analytical data and the flags produced during Level 0 and Level 1 valida tion. RTI has developed SQL queries to produce the reports and spreadsheets. Electr onic copies of these reports are made available to the DOPOs, the state agenci es submitting the delivery orders, and EPA/OAQPS through RTI's password-protec ted website. These data users are notified by e-mail of the availability of ne w data sets as soon as they have been approved by the QA Officer and have been moved to the website.

5. Quarterly Metadata Summary Reports of laboratory/field ch anges and issues that impact data quality will be prepared by RTI with input from its subcontractors. These reports will include a complete listing of field changes (e.g., sites that shut down or changes to sampler types and dates of opera tion), laboratory changes (e.g., changes to lab procedures or operations and specific dates for the samples affected); and data collection or analysis issues and dates for samples affected or invalidated. Reports will be chronological and will succinctly describe the issues or changes, and the samples that were affected. One electroni c copy of the report will be prepared and delivered to EPA OAQPS for posting on an EPA web site.

6. Annual Data Summary Report. RTI worked closely with EPA during the initial PM 2.5 

### CSN contracts to develop a comprehensive report responsive to data users’ needs without being unnecessarily complex. This report provides a comprehensive overview of performance and summarizes quality issues, corrective actions, data completeness, MDLs, operational problems, blank levels, laboratory QC results, and precision estimated using data from sites where collocated samplers are situated. Other information such as reports of external TSAs and performance audits also may be included as available. An electronic copy of the fi nalized annual report is posted to AMTIC after EPA approval.QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 85 of 95 

## D.1 Data Review, Validation, and Verification Requirements
The following describes RTI’s approach to da ta review, validation, and verification for PM 2.5 

### filter analysis. Similar procedures will be de veloped for the other forms of PM as the new program progresses. The QC criteria given elsewh ere in this QAPP will be used as the data validation requirements. Any data that fails rou tine validation checks will be flagged for review by the monitoring agencies. Large or systematic exceedance criteria may al so trigger a corrective action investigation by the RTI QA Manager.
Analytical data are validated using data from laboratory blanks, calibration checks, standard spikes, and laboratory duplicates. Based on QC verification data, a filter or other sample may be invalidated prior to submitting results to AQS, or the result may be flagged. Reasons for invalidation may include, but are not limited t o, damaged filter, laboratory or field blank contamination, balance malfunction, and invalid holding times. Table B.10.8 provides the data validity flags currently available for PM 2.5 

### data in AQS. RTI will implement any additional or alternative flags that may be defined for PM 2.5 

### chemical speciation data.



## D.2 Validation and Verification
RTI is responsible for validating analytic al data produced in its laboratories. Subcontractor laboratories will apply Level 0 and Level 1 screening to data produced in their laboratories. RTI is responsible for overall, fina l data review, validation, and verification and for data reporting.

D.2.1 Level 0 Validation

Level 0 data sets contain all available ambi ent data and may contain nonambient data in the form of QC checks and/or fl ags indicating missing or invalid data. Any missing data will be retrieved from the source, if available, and any problems related to chain of custody, shipping integrity, sample identifications, and inspections will be rectified to the extent possible. The initial identification of thes e problems will be the responsibility of the Sample Handling Supervisor, who works closely with the Data Manager and other personnel to document systematic problems and to take or recommend corrective actions. Data will be flagged or invalidated if problems are identified during Le vel 0 validation but cannot be rectified.

Sources for the information used to screen data for Level 0 validation include the analyst’s notes (logbooks and data forms), sample labels, COC forms, package shipping labels, and inspection results for filters and other sample media. Validation flags in the Level 0 data will also include the data flags for items such as pow er failures, temperature flags, and insufficient data for the averaging period generated by the speciation sampler in the field.
Occasionally, RTI personnel may become awar e of an excessive rate of problematic samples from a particular monitoring organi zation. Such problems might include inadequate packing, excessive numbers of damaged filter medi a, and incorrectly or inadequately completed forms. RTI will work with the monitoring organi zation to bring about corrective action. Also, the RTI PM will contact the DOPOs (or the appropriate contact desi gnated by the DOPOs) to inform him/her of the problem.QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 86 of 95



### D.2.2 Level 1 Validation Level 1 data are reviewed more fully for t echnical acceptability and reasonableness based on information such as routine QC sample resu lts, data quality indi cator (DQI) calculations, performance evaluation (PE) sample s, internal and external audits, statistical screening, internal consistency checks, and range checks. Unacceptabl e long-term performance of the analytical system can also be uncovered in the proce ss of documenting the DQIs of completeness, precision, accuracy, and detection limits, and co mparing those indicators with the program’s goals or DQOs.
In response to major or systematic probl ems identified by any of these procedures, corrective actions will be taken and data may be flagged or invalidated. Corrective actions based on Level 1 screening results will in clude, for example, the following:

 

### Investigating the specific c onditions that contributed to an anomalous results for a single laboratory sample or related group of samples

 

### Contacting the site operator or monitoring agency to find out if there were any meteorological or other conditions that might lead to anomalous results

 

### Increasing the number of routine instrument checks such as multipoint calibrations, blanks, duplicates, and spikes

 

### Repeating analyses for the affected samples, if possible

 

### Reviewing logs and other records for transc ription errors and ev idence of operational problems or equipment malfunction.

Level 1 screening is conducted primarily after the data have been loaded into the data management system but before the data sets ar e transmitted to the state agencies for review. Initial screening of data is performed by data management personnel us ing screening criteria developed by the QA Manager and the laborator y personnel. Data validation flags generated during Level 1 screening are reviewed by the QA Manager; however, the QA Manager often requires input from one of the Technical Ar ea Supervisors to address the problem. Data problems that originate outside the scope of RTI’s operations ar e reported to the appropriate DOPO.
RTI will take any necessary corrective acti ons on problems identified during Level 0 and Level 1 data review activities and input from the state monitori ng agencies during their review cycle..
Level 1 designation will be assigned to a set of data after the laboratory has performed all QC activities and has addressed all identified is sues. Level 1 data will be transmitted to AQS along with AQS codes generated during the data validation process, as well as the changes requested by the monitoring ag encies during their review.
D.2.3 Screening of Subcontractor Data Although CHESTER LabNet will conduct their ow n Level 0 and Level 1 screening of the EDXRF data, RTI must further validate its results at Level 0 to ensure a c onsistent data set. In doing so, RTI will ensure that the sample id entifications and COC information from the subcontractor are consistent with RTI’s records. This process will consist primarily of comparingQAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 87 of 95


### the original sample numbers, dates, types, and so on, with the data received from the subcontractor. Of particular importance is ensuri ng that sample results from the subcontractor match up exactly with data from the other analys es for each exposure. Discrepancies in sample attribution uncovered during Level 0 screening will be investigated and rectified before the data are reported.
RTI will not perform detailed Level 1 screen ings on the subcontractor’s EDXRF data because this would duplicate efforts already e xpended. However, data from EDXRF are included in certain Level 1 checks such as reconstr ucted mass balance and sulfur/sulfate ratio.
RTI's screening of DRI's OC/EC includes assi gnment checks based on date, site, and the various ID numbers assigned to f ilters, aliquots and sampling even ts. Monthly validation queries are run that incorporate the DRI data, including reconstructed ma ss balance, invalid data counts by site and date. Data from DRI are also scan ned for unusually high blank values and possible filter swaps between routinely sampled filters and blanks.

D.2.4 Data Corrections RTI will investigate and attempt to make corrections to all laboratory problems. Corrections to quantitative data such as concentrations will not be applied unless they are defensible and are based on documented info rmation. Questionable data will be flagged appropriately. The following paragraphs briefly di scuss the types of data corrections that are typically encountered in this work.

D.2.4.1 Mass

Mass measurements will not be corrected for blank levels. Early in the development of the fine particulate program, a problem was encount ered with Teflon filters with rings in which the manufacturer used an adhesive to attach th e rings. Solvent continued to volatilize from the adhesive over several weeks, making it difficult to achieve constant weight. The filter manufacturer has since corrected this problem . If any other examples of time-dependent variances in mass measurements are found through analysis of blank filters, RTI will address these in consultation with EPA.
D.2.4.2 Elemental Analysis EDXRF is subject to interferences and arti facts that are corrected for as follows:

 Escape peaks from secondary targets (e.g., chlorine K ∝ from the titanium secondary target, titanium K ∝ from the iron secondary target) are corrected by the instrument software.

 Inter-element interference corrections are carried out as described in the XRF SOPs.

 Attenuation corrections for light elements (Na through S) will be applied. The appropriate values for the correction fact ors differ by particulate size fraction (PM 2.5 

### , PM 10 

### , or PM 10-2.5 

### ), and XRF instrumental conditions.

 Filter lot-specific background levels will be a ccounted for in the instrumental method.QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 88 of 95



### D.2.4.3 Ions RTI’s experience has indicated that artifacts and interferences pose no problem to the analysis of PM 2.5 

### ions using state-of-the-art IC system s. High-resolution columns and excellent chromatographic data processing software pr ovide acceptable precision and accuracy. Precision and accuracy results for ions on filters similar to those used in the CSN are included in the ion analysis SOP.

D.2.4.4 OC/EC This method is subject to a number of poten tial interferences. RTI will use its best judgment in applying corrections, will fully doc ument any such corrections, and will discuss them with EPA before the data are submitted to AQS. RTI does not apply corrections or adjustments to account for the OC sampling artif act; however, if EPA provi des the equations to be used for making such a correction, RTI will pr ocess the data back to 2009 and will post it to AQS.
Carbonates and bicarbonates present in some filter samples may cause interference in the OC/EC analysis. Two alternative procedures may be used to measure carbonate carbon. The first approach includes analysis of a second portion of the filter sample after it has been acidified (i.e., exposed to HCl vapor, which removes carbonate as CO 2 

### ) and takes carbonate carbon as the difference between the pre- and post-acidificati on results. The second approach estimates carbonate carbon by integrating sepa rately the carbonate peak in the thermogram and using the instrument’s software to calcu late the mass of carbonate carbon volatilized. Carbonate carbon is not generally present in PM 2.5 

### on quartz filters at loadings ab ove the absolute error of the measurement; therefore, carbonate ca rbon was not included in the list of analytes for the current
contract.

D.2.4.5 SVOCs
As with IC, state-of-the-art GC/MS provides high resolution of compounds (i.e., accurate qualitative analysis). Artifacts and interferences are more likely to be encountered in the sample extraction and cleanup stages. The following activities should ensu re that artifacts such as analyte loss and poor recovery do not pose a sign ificant risk to achieving acceptable analysis results:

 Field blanks

 Method blanks

 Field controls or matrix spikes

 Laboratory controls (spi ked sample matrices)

 Method controls (spiked extraction solvent)

 Replicate extract analyses.QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 89 of 95 

## D.3 Reconciliation with User Requirements
RTI will ensure that its measurement data meet requirements as expressed in this QAPP and in the Chemical Speciation Guidance documents. RTI and its subcontractors will work closely with EPA to ensure that all required pe rformance characteristics are met. RTI will do the following to ensure that our performance meets c ontract requirements and client expectations:

 Regular communications between the Pr ogram Manager and the DOPOs, the EPA Project Officer, and EPA technical leader. Communications will include conference calls scheduled biweekly or as neede d, e-mail and written correspondence, and meeting with EPA/OAQPS personnel in th e Research Triangle Park, NC, area.

 An organized system of co rrective action notific ation and follow-through. Significant quality-related problems will be assigned corrective action request (CAR) numbers. The CARs will be tracked by the area supervisor and the QA Manager to ensure that quality problems are addressed in a systematic way. This system will enable the Program Manager to allocate the resources necessary to resolve problems, to prioritize corrective actions, and to track the accomplishment of corrections.

Another key aspect of ensuring the smooth operation of the CSN laboratories is the handling of communications with the various participants in the program. Most programmatic communications with outside participants in cluding EPA/OAQPS, the DOPOs, and the state agencies flow through the Program Manager. The only exceptions to this rule will be dealings on a technical level with EPA personnel (e.g., to defi ne data delivery formats for AQS) and contacts between shipping/receiving personnel at RTI and th e state agencies for the purpose of expediting or locating specific shipments. No one at RTI ot her than the Program Manager is authorized to alter schedules, increase or d ecrease the number of samples to be analyzed, or change the schedule of shipments to/from a state agenc y. All such requests must go through the RTI Program Manager.QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 90 of 95



## Appendix 1: Uncertainty Calculations
Uncertainty values reported to AQS with each concentration record will include components of both the analytical and the volum etric uncertainty. The re ported uncertainties are estimated “1-sigma” values (one standard devi ation). No blank correc tions are assumed other than laboratories’ instrumental baseline corrections, which are an integral part of each analysis. The equations below describe how RTI will calcul ate the total uncertainty for the CSN analytes. A list of symbols is given at the en d of this section. Uncertainties for PM 10 

### are likely to be determined in the same manner as for PM 2.5 

### . Uncertainties for PM coarse 

### will initially be determined by statistically combining the uncertainties of the two filters (PM 10 

### and PM 2.5 

### ) used to calculate the PM 10 

### –PM 2.5 

### fraction. The reasonableness of all uncertainties is subject to verification by techniques such as statistical analysis of data from collocated sites.
1.1 General Equation for Uncertainty The mass uncertainty (micrograms per filter) wi ll be calculated as shown in equation (1) for XRF elements, Ion Chromatography, and OC/EC [mass uncertainties for gravimetric analysis are shown in equations (3) and (4), below]. The use of the max function prevents the calculated uncertainty for an exposed filter from being less th an the average uncertainty for blanks. In most cases, the first term should be the larger. 

# ( ) σ σσ σ

M i j Ai Vk Bi 

### M

, 

### max ,

= +⋅ 222 

### (1) The mass uncertainty is converted to concen tration units (micrograms per cubic meter) according to equation (2).



### σ σ C i j M i j 

### V

, , 

### / = (2) 1.2 Gravimetric Analysis Determination of gravimetric mass requires two separate weighings, each of which contributes to the total uncertainty. A 47 mm Te flon filter used in the STN program weighs 145,000 micrograms, while the deposits on the filter are typically on the orde r of a few hundred micrograms. The total mass of loaded and clean f ilters is thus approximately the same (i.e., on the order of 145,000 micrograms). RTI has conducte d experiments demonstrating that loaded filters have approximately the same repeatability as blank filters. Therefore, a constant value is assumed for the analytical uncertainty, σ Ai, 

### used in equation 1, independent of filter loading.
Data obtained from filter lot acceptance bla nks have provided a good data set on which to calculate uncertainties for clean filters. The stan dard deviation of a larg e population of replicate filter weighings from 2002 and 2003 was determined in order to set the baseline parameters σ Ai 

### and σ Bi 

### in equation 1. These are multiplied by a factor of th e square root of 2 to account for the fact that two weighings are involved for each reportable mass concentration value.QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 91 of 95



### 1.3 XRF Elements For XRF elements, an analytical uncertainty value for each analyte is calculated by the manufacturers’ software, using an algorithm based on counting statistics for each sample. RTI has found that in order to report more consistent uncertainties for data generated by different analyzers, the manufacturer’s uncertainties mu st be harmonized to ensure that the same components of uncertainty are used. This process is described in two documents that have been prepared by RTI and are pos ted on the AMTIC Web site: Harmonization of Interlaboratory X-ray Fluorescence Measurement Uncertainties – Overview – http://www.epa.gov/ttn/amtic/files/ ambient/pm25/spec/xrfuncertov.pdf Harmonization of Interlaboratory X-ray Fluor escence Measurement Uncertainties – Detailed Discussion – http://www.epa.gov/ttn/amtic/file s/ambient/pm25/spec/xrfdet.pdf

For the RTI XRF Lab, the XRF software does no t calculate an uncertainty for an analyte when the peak and concentration values ar e zero. The formula shown in equation 3 was developed to calculate an uncertainty when the peak or concentration values are zero. This formula takes into account the background count rate in counts per second (B), livetime (t), and scaling factor (A). Uncertainty = slope * A * sqrt (3 * sqrt ( B * t ) + B * t ) / t (3) 1.4 Ion Chromatography Equation 1 is used for anions and cations (sulfate, nitrate, sodium, ammonium, and potassium), with the analytical uncertainty assumed to be a lin ear function of concentration, as shown. The intercept at low concentrations, σ B 

### , is determined from a replicate set of reanalyses of a low-level standard. We attempted to base our initial analytical uncertainty values ( σ Ai 

### ) on replicate analysis of an up-scale QC standa rd; however, large a nd difficult-to-reproduce variability was found, so that we assumed a multiplier, σ REL 

### , of 5% for all analytes and all instruments. Equation 3 is used to calculate the analytical uncertainty, σ Ai, 

### as a function of concentration.

1.5 OC/EC Original NIOSH TOT Analysis - Sunset Labs, which manufactures the OC/EC instrument that was used by RTI for TOT meas urements, provides the formulas used by their software to calculate uncertainties, which include constant uncertainty components of


## ± 0.20 μ gC/cm2 for OC and EC and 

## ± 0.30 μ gC/cm2 for TC, and a proportional uncertainty component of 5% for all three speci es. Assuming a filter area of 11.76 cm 2 

### , the constant loadings are 2.35 μ gC/filter for OC and EC, and 

## ± 3.53 μ gC/filter for TC. See Appendix 2 to this QAPP for more details. Equation 4 is used for calcul ating analytical uncertainty for OC/EC.


## δ δ δ

Ai CONST PROP 

## M M = + • ( )/ (4)QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 92 of 95



### where: δ Ai 

### = estimated uncertainty of measurement 1 

### (use in Eqn. 1), micrograms δ CONST 

### = [constant uncertainty][11.76], micrograms

δ PROP 

### = proportional uncertainty multiplier [5% for OC, EC, and TC]

RTI independently extended the Sunset Labor atory uncertainty estimates to include the OC Peaks. For all reported carbon fractions , the constant and proportional components of uncertainty defined for each fraction below incl ude at least 95% of replicate measurements across three analyzers for 127 f ilters analyzed over a three- year period in RTI’s OC/EC Laboratory.

Carbon Fraction Constant Uncertainty Component ( 

### δ CONST , μgC/filter) Proportional Uncertainty Component ( 

### δ PROP ,%) OC 2.35 5%*OC EC 2.35 5%*EC TC 3.53 5%*TC Pk1 C 2.35 5%*Pk1 C Pk2 C 2.35 5%*Pk2 C Pk3 C 3.53 5%*Pk3 C Pk4 C 3.53 10%*Pk4 C Pyrol C 2.35 140%*Pyrol C



### IMPROVE_A Analysis – The equations to be used to calculate uncertainties for the IMPROVE_A results have not been provided to RTI. This sec tion will be updated when that guidance becomes available.

1.6 Determination of Volume Uncertainty The relative uncertainty associated with sa mpled volume and other shipping and handling components of sampling error is often the predomin ant part of the total measurement uncertainty. However, RTI has no way to determine these, base d on any of the field data that we routinely receive. A nominal value of 5%, which is us ed by the IMPROVE program (see IMPROVE SOP 351, Data Processing and Validation ), is probably in the right orde r of magnitude for most of the CSN samplers. More accurate valu es for relative volume uncertainty would require statistical assessment of field audit results, which have no t been consistently available for the CSN in previous years. Studies using data from collocat ed samplers and other means for assessing whole system variability for both the CSN and IMPROVE ne tworks have shown that the value of 5% is probably an underestimate for the majority of ch emical species, though it is reasonably accurate for high-level species that are re latively immune from contamination, such as sulfate and sulfur by XRF.

1 Values are consistent with the Expanded Uncertainty concept used for measurements related to health or safety as described in Taylor, B.N.; Kuyatt, C.E. NIST Technical Note 1297: Guidelines for Evaluating and Expressing the Uncertainty of NIST Measurement Results. Ex panded Uncertainty section. Available at http://physics.nist.gov/Document/tn1297.pdf (accessed April 2008).QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 93 of 95



### 1.7 Definitions I = Index for analytes j = Index for indivi dual sampling events k = Index for sampler type (SASS, IMPROVE, FRM, etc.)

σ = Standard deviation M = Analytical mass (micrograms per filter) V = Sampled volume (cubic meters)

σ Mi,j 

### = Std. dev. of mass for analyte I for event j (micrograms per filter)

σ Ci,j 

### = Relative standard deviation for analyt e I from lab QC samples (dimensionless)

σ Bj 

### = Blank std. dev. from lab QC blanks (micrograms per filter)

σ G 

### = Std. dev. for replicate gravimetri c analyses (micrograms per filter)

σ Vk 

### = Relative std. dev. of sampler vo lume (dimensionless) [typically 5%]QAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 94 of 95



## Appendix 2: Method Detection Limits

Laboratory method detection limits (MDLs) ar e reported annually and are subject to periodic updates by each of the analytical laboratories. Th e MDLs shown in this Appendix are from the 2010 CSN Annual Data Report. Labora tory MDLs are conver ted to concentration units by dividing the sampled volume for the respectiv e sampler type and channel. Note that the resulting MDL in concentration units will not include any allowance for uncertainties related to field operations, including uncerta inty in the measurement of vol ume, contamination, or other field-related issues. Because AQS does not di stinguish the instrument used to analyze a particular filter sample, the tables in the sections below only incl ude the maximum reported MDL during calendar 2010 for all instruments used to analyze CSN filters.

2.1 X-Ray Fluorescence

RTI operates three ThermoNoran XRF instrument s that have been approved for used on the CSN program. Chester Labnet operates tw o Kevex XRF instruments that have been approved for analysis of CSN filters. As noted above, the maximum MDL value over calendar 2010 is shown in the table.

2.2 Gravimetry

Gravimetric MDLs are determined by multiple re -weighings of blank filters. A factor of the squre root of two is included in the calculation to account for th e fact that each filter must be weighed twice to produce a net weight. The RTI laboratory typically operates 3-4 balances during the course of a year. The value show n in the table is the maximum reported MDL over all balances for calendar 2010. Th e MDLs shown in the table appl y to 47 mm Teflon filters.

2.3 Anion and Cation Analysis

RTI operates the anion and ca tion analysis laboratory. MD Ls shown in the table below were determined for the analysis of ions on 47 mm nylon filters.

2.4 Organic and Elemental Carbon by Thermal Optical Analysis

The great majority of CSN OC/EC samples are analyzed by Desert Research Institute (DRI) using the IMPROVE_A analysis protocol. EPA has not provided the formulas to be used for calculating MDLs, uncertainties, or artifact co rrections for the IMPROVE_A data as of thisQAPP for Chemical Speciation of PM2.5 Filter Samples Revision No. 10 Date: May 11, 2012 Page 95 of 95


### writing. The MDLs listed below are "typical" si nce MDLs can vary between instruments and over time. In addition, the MDLs in concentratio n units (micrograms per cubic meter) can vary slightly according to the sampled volume for each filter. MDLs are not provided for the OC/EC by the IMPROVE_A method because the equations ha ve not been provided to RTI as of this writing.

Analysis Species Mass_MDL (ug/filter) Concentration (ug/m^3) by sampler type SASS Gravimetry Particulate matter 2.5μ 7.5 0.82 Anions and Cations Ammonium 0.24 0.027 Nitrate 0.21 0.023 Potassium 0.23 0.025 Sodium 0.35 0.036 Sulfate 0.17 0.018 Trace Elements (XRF) Aluminum 0.24 0.027 Antimony 0.5 0.056 Arsenic 0.026 0.0028 Barium 0.57 0.06 Bromine 0.022 0.0024 Cadmium 0.22 0.024 Calcium 0.073 0.0084 Cerium 0.84 0.088 Cesium 0.44 0.047 Chlorine 0.11 0.011 Chromium 0.025 0.0028 Cobalt 0.019 0.002 Copper 0.024 0.0027 Indium 0.32 0.035 Iron 0.032 0.0034 Lead 0.061 0.0064 Magnesium 0.18 0.019 Manganese 0.028 0.0029 Nickel 0.018 0.0019 Phosphorus 0.15 0.018 Potassium 0.11 0.012 Rubidium 0.025 0.0028 Selenium 0.025 0.0028 Silicon 0.18 0.02 Silver 0.36 0.04 Sodium 0.53 0.058 Strontium 0.034 0.0038 Sulfur 0.095 0.011 Tin 0.35 0.039 Titanium 0.051 0.0058 Vanadium 0.037 0.0042 Zinc 0.034 0.0037 Zirconium 0.22 0.024