RTI/0212053/01QA May 11, 2012 

Quality Assurance Project Plan 

Chemical Speciation of PM2.5 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 PM2.5 Filter Samples 

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Date: May 11, 2012 

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A.2 Table of Contents 

Section Page

A.1 QA Project Plan Identification and Approval .................................................................................................. 2

A.2 Table of Contents ............................................................................................................................................ 3

A.3 Distribution ..................................................................................................................................................... 7

A.4 Project/Task Organization ............................................................................................................................... 7

A.4.1 Key Personnel ................................................................................................................................ 9

 A.4.1.1 Program Manager and Administrative Program Coordinator .................................. 9

 A.4.1.2 QA Manager ........................................................................................................... 10

A.4.2 Analytical Subcontractors ........................................................................................................... 10

 A.4.2.1 CHESTER LabNet ................................................................................................. 11

 A.4.2.2 Desert Research Institute ....................................................................................... 11

A.5 Problem Definition/Background ................................................................................................................... 13

A.6 Project/Task Description ............................................................................................................................... 14

A.6.1 Schedule ...................................................................................................................................... 14

A.6.2 Sample Types and Quantities ...................................................................................................... 14

A.7 Quality Objectives and Criteria for Measurement Data ................................................................................ 15

A.7.1 Data Quality Objectives Process ................................................................................................. 15

A.7.2 Quality Objectives for Total Measurement Error ........................................................................ 16

A.7.3 Measurement Quality Objectives ................................................................................................ 18

A.7.4 References ................................................................................................................................... 19

A.8 Special Training Requirements/Certification ............................................................................................... 20

A.8.1 Current Personnel ....................................................................................................................... 21

A.8.2 Summary of Experience and Training ......................................................................................... 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 Laboratories’ Records ............................................................................................... 28

A.9.4 Gravimetric Mass Laboratory Records ....................................................................................... 29

A.9.5 XRF Laboratory Records ........................................................................................................... 30

A.9.6 IC Laboratory Records ............................................................................................................... 30

A.9.7 OC/EC Laboratory Records........................................................................................................ 31

A.9.8 Denuder Refurbishment Laboratory Records .............................................................................. 31

B.1 Sampling Process Design (Experimental Design) ......................................................................................... 33

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

B.3 Sample Handling and Custody Requirements ............................................................................................... 33

B.3.1 Sample Handling Delivery Order Process ................................................................................... 33

B.3.2 Chain of Custody ......................................................................................................................... 35

B.3.3 Processing System for PM Chemical Speciation Modules .......................................................... 35

 B.3.3.1 Assembly of Sampling Modules ............................................................................ 39

 B.3.3.2 Shipping to and from the Field ............................................................................... 39

 B.3.3.3 Disassembly of Sampling Modules ........................................................................ 41

 B.3.3.4 Internal Tracking of Analytical Samples ............................................................... 41

 B.3.3.5 Archiving of Filters and Extracts .......................................................................... 41

 B.3.3.6 Denuder Preparation .............................................................................................. 43
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B.4 Analytical Methods Requirements ................................................................................................................ 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 Analysis .......................................................................................................................... 45

B.4.5 Semivolatile Organic Compounds ............................................................................................... 46

B.4.6 Characterization of Particles by Electron and Optical Microscopy ............................................. 46

B.4.6.1 Scanning Electron Microscopy .................................................................................................... 46

B.4.6.2 Optical Microscopy ..................................................................................................................... 47

B.5 Quality Control Requirements ....................................................................................................................... 48

B.5.1 Quality Criteria for Gravimetric Analyses .................................................................................. 48

B.5.1.1 Gravimetric Disaster Recovery Plan ........................................................................................... 49

B.5.2 Quality Criteria for Ion Analysis ................................................................................................. 49

B.5.2.1 Ion Disaster Recovery Plan for Data ........................................................................................... 50

B.5.3 Quality Criteria for EDXRF ........................................................................................................ 50

 B.5.3.1 RTI ......................................................................................................................... 50

B.5.3.2 CHESTER LabNet ...................................................................................................................... 51

B.5.4 Quality Criteria for RTI OC/EC Analysis ................................................................................... 52

B.5.4.1 RTI OC/EC Lab Disaster Recovery Plan for Data ...................................................................... 55

B.5.5 Quality Criteria for Denuder Refurbishments ............................................................................. 55

B.5.6 Uncertainty Determination .......................................................................................................... 56

B.5.7 Method Detection Limits ............................................................................................................. 57

B.6 Instrument/Equipment Testing, Inspection, and Maintenance Requirements ............................................... 57

B.6.1 Gravimetric Mass Laboratory ...................................................................................................... 57

B.6.2 Ion Chromatographic Laboratory ................................................................................................ 58

B.6.3 EDXRF Laboratory ..................................................................................................................... 59

 B.6.3.1 RTI ......................................................................................................................... 59

 B.6.3.2 CHESTER LabNet ................................................................................................. 60

B.6.4 ICP/MS Laboratory ..................................................................................................................... 60

B.6.5 Organic/Elemental Carbon (OC/EC) Laboratory ........................................................................ 62

 B.6.5.1 RTI OC/EC Laboratory .......................................................................................... 62

 B.6.5.2 DRI OC/EC Laboratory ......................................................................................... 62

B.7 Instrument Calibration 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 ......................................................................................................................... 64

 B.7.3.2 CHESTER LabNet ................................................................................................. 65

B.7.4 OC/EC Laboratories .................................................................................................................... 65

 B.7.4.1 RTI OC/EC Laboratory .......................................................................................... 65

 B.7.4.2 DRI OC/EC Laboratory ......................................................................................... 66

B.8 Inspection/Acceptance Requirements for Supplies and Consumables .......................................................... 67

B.8.1 Filters ........................................................................................................................................... 67

B.8.1.1 Teflon Filters .......................................................................................................... 68

B.8.1.2 Nylon Filters .......................................................................................................... 68

B.8.1.3 Quartz Filters ......................................................................................................... 68

B.8.2 Criteria for Other Materials ......................................................................................................... 69

B.9 Data Acquisition Requirements (Non-direct Measurements) ........................................................................ 69

B.10 Data Management ......................................................................................................................................... 69

B.10.1 Overview ..................................................................................................................................... 70

B.10.2 DMS Design Features .................................................................................................................. 70

 B.10.2.1 Sample Identifiers .................................................................................................. 70
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 B.10.2.2 Barcode Scanners ................................................................................................... 71

 B.10.2.3 Relational Integrity ................................................................................................ 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 Development Databases .................................................................... 72

 B.10.2.7 Database Backup and Recovery ............................................................................. 72

B.10.3 Automated and Semi-Automated QC Limit Checks for Outlier Detection ................................. 72

B.10.4 Report Preparation and QA Screening ........................................................................................ 74

 B.10.4.1 Data Set Completeness 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 ......................................................................................... 80

B.10.7 Management and Reporting of Field Audit Data ......................................................................... 80

C.1 Assessments and Response Actions .............................................................................................................. 81

C.1.1 External Quality Assurance Assessments .................................................................................... 81

C.2 Reports to Management................................................................................................................................. 83

D.1 Data Review, Validation, and Verification Requirements ............................................................................ 85

D.2 Validation and Verification ........................................................................................................................... 85

D.2.1 Level 0 Validation ....................................................................................................................... 85

D.2.2 Level 1 Validation ....................................................................................................................... 86

D.2.3 Screening of Subcontractor Data ................................................................................................. 86

D.2.4 Data Corrections .......................................................................................................................... 87 

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

List of Tables 

Table Page

 A.3.1. QAPP Distribution List ...................................................................................................................................... 7

 A.4.1. Personnel Responsibilities and Lines of Communication .................................................................................. 9

 A.6.1. Families of SVOCs to be Quantitated by GC/MS Methodologies ................................................................... 12

 A.6.2. Sample Quantities for Base Period January 26, 2009 through January 25, 2012 ............................................. 14

 A.7.3. Recommended MQOs for Total Measurement 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 Laboratories’ Records .................................................................................................................... 28

 A.9.5. Gravimetric Mass Laboratory Records ............................................................................................................ 29

 A.9.6. XRF Laboratory Records ................................................................................................................................. 30

 A.9.7. IC Laboratory Records ..................................................................................................................................... 31

 A.9.8. OC/EC Laboratory Records ............................................................................................................................. 31

 A.9.9. Denuder Refurbishment Laboratory Records .................................................................................................. 32

 B.3.1. Sampler Component and Laboratory Speciation Analysis Matrix ................................................................... 40

 B.4.1. Carbon Fractions Reported .............................................................................................................................. 47

 B.5.1. QC Criteria for Ion Chromatography (Anions and Cations) ............................................................................ 50

 B.5.2. RTI QC Procedures to Analyze EDXRF 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 CSN/TOT and IMPROVE_A/TOR-TOT Methods in RTI’s 

OC/EC Laboratory .......................................................................................................................... 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 Refurbishments ........................................................................................................ 56
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 B.6.1. Inspection Criteria for Gravimetric Mass Laboratory ...................................................................................... 57

 B.6.2. Gravimetric Mass Laboratory Maintenance Schedule and Responsibility ....................................................... 58

 B.6.3. Inspection Criteria for Ion Analysis Laboratory .............................................................................................. 58

 B.6.4. Ion Analysis Laboratory Maintenance Schedule and Responsibility ............................................................... 59

 B.6.5. Inspection Criteria for RTI EDXRF Laboratory .............................................................................................. 59

 B.6.6. RTI EDXRF Laboratory Maintenance Schedule and Responsibility ............................................................... 60

 B.6.7. Inspection Criteria for CHESTER LabNet EDXRF Laboratory ...................................................................... 60

 B.6.8. CHESTER LabNet XRF Laboratory Maintenance Schedule and Responsibility ............................................ 60

 B.6.9. Elements to be Analyzed by ICP/MS ............................................................................................................... 61

 B.6.10. Quality Control Activities for ICP/MS Analysis Sequences .......................................................................... 62

 B.6.11. OC/EC Laboratory Maintenance Schedule and Responsibility ..................................................................... 62

 B.6.12. OC/EC Laboratory Maintenance Schedule and Responsibility ..................................................................... 63

 B.7.1. Elements Present on Micromatter, Co. Standard ............................................................................................. 64

 B.7.2. Certified Values of Elements Present on NIST Standard Reference Material No. 1832 ................................ 65

 B.7.3. RTI OC/EC Instrument Calibration and Frequency ......................................................................................... 66

 B.7.4. DRI OC/EC Instrument Calibration and Frequency ........................................................................................ 67

 B.10.1. Label Identifiers for Tracking CSN Records and Equipment ........................................................................ 71

 B.10.2. Statistical Validation Limits for Routine Data ............................................................................................... 73

 B.10.3. Statistical Validation Limits for 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 (PM2.5 Only) ........................................................................................ 76

 B.10.7. Field Data and 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 PM2.5 filter 

samples. ............................................................................................................................................. 8 

 B.3.1. Overview of sample handling and custody system. ......................................................................................... 34 

 B.3.2. Diagram of RTI filter processing and analysis activities by filter type (arrangement may vary by 

sampler model). ............................................................................................................................... 37 

 B.3.3. Movement of filters and extracts through RTI and subcontractor laboratories. ............................................... 38 

 B.3.4. RTI Laboratory COC form used in tracking. ................................................................................................... 42 
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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 Assurance 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 Assurance Manager RTI/EISD 

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

13 P. Pressler Jur* Gravimetric Mass 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 where procedures are performed. 

A.4 Project/Task Organization 

This QAPP describes quality planning for contract number EP-D-09-010 with the U.S. 

Environmental Protection Agency (EPA) Office 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 International’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 perform 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: and semivolatile organic compounds (SVOC), and 
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optical density (OD) analysis on selected filters. Sound management requires a clear 

understanding of the roles, functions, and assignments 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 PM2.5 filter samples. 

 
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Table A.4.1. Personnel Responsibilities and Lines of Communication 

Position Responsibilities Lines of Communication

Program Manager

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 Manager

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 Staff Performs technical tasks. 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 activities with EPA/OAQPS and with the State, 

Local, and Tribal (SLT) agencies. Lab QA auditing and technical assistance are provided by 

EPA/ORIA as described in the Field QAPP (Quality 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 Administrative 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 performed in accordance with the EPA statement of 

work and according to this QAPP. 

The RTI Program Manager’s responsibilities include: 
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1. Maintaining cooperative working relationships with the EPA Project 

Manager, Delivery Order Project Officer (DOPO), and QA Manager in the 

following ways: 

Conference calls to be held biweekly initially, 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 techniques and procedures are followed 

4. Ensuring that reporting requirements 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 for the CSN program and 

is responsible for financial and other project coordination activities within RTI. 

A.4.1.2 QA Manager 

Dr. James B. Flanagan is the RTI QA Manager 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. For the purposes of this project, he will report 

to Mr. Bruce Harvey, EISD Division Director, and to Dr. Jayanty, the Program Manager. Dr. 

Flanagan will monitor quality assurance/quality control (QA/QC) for the project. Dr. Flanagan 

selected staff members will investigate problems and recommend corrective actions, perform 

periodic in-lab and data review audits, host external auditors during anticipated visits, and 

distribute EPA-provided Performance 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 laboratories providing analytical services for this program have 

contributed to this project-specific QAPP and must provide their SOPs for EPA approval. If 

requested by EPA, subcontractors will undergo technical systems audits of their facilities and 

will analyze EPA-provided PE samples. RTI 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 coordinates a filter reanalysis program in which 

selected filters are reanalyzed by the participating XRF laboratories (currently just RTI and 

Chester Labnet). Intercomparison results are summarized in annual quality assurance data 

reports. Subcontractors are also required to provide input for the quarterly metadata reports and 

the annual quality assurance data report. 
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The capabilities of each subcontractor are briefly 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, sample turnaround, and cost requirements for this 

program. The initial throughput capacity using the CHESTER LabNet Kevex 770 XRF for 

Protocol #6 was 25 samples per day. To boost productivity, CHESTER LabNet purchased a 

second Kevex XRF, numbered 771. Samples were 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 per day. CHESTER LabNet has purchased a third 

Kevex XRF for serving its other clients, but this instrument is not used for CSN analyses because 

no equivalency study has been performed. 

RTI and Chester obtain their calibration standards 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 μg/cm2

. The multi-element standard is analyzed with 

each tray of samples. 

A.4.2.2 Desert Research Institute 

The Desert Research Institute is the nonprofit 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 (Dandini 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 the Center for Watersheds and Environmental 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 analytical protocol, known as IMPROVE_A, was developed by DRI 

using the DRI Model 2001 Thermal/Optical Carbon 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 technical 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 consists of essentially the same components 

as the Sunset Laboratory instrument used by RTI, although the configuration is quite different. 

The basic components of the system include a sample oven fitted with a laser-photodiode sensor, 

an oxidizer oven, a methanator, a flame ionization detector (FID), other components used to 

control oven temperature and gas composition and flows, and a computer workstation running 

software through which analysis parameters are controlled and data from the FID, photodiode 
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sensor, and oven thermocouples are collected. All carbon volatilized from the filter is converted 

to CO2 in the oxidizer, and the CO2 is converted to methane (CH4) in the methanator before 

passing into the FID, where it is measured. The laser is used to track and correct for the pyrolysis 

of OC that occurs during the inert 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 light is transmitted through the filter. The laserphotodiode sensors are used to monitor 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 Reflectance (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 SVOC 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 extract 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, several filters may be 

combined for extraction to yield a more concentrated extract solution. Extracts will be analyzed 

for semi-volatile organic aerosol compounds using gas chromatography/mass spectroscopy 

(GC/MS) methodology. All analytical 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 requested 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-hentracontane, iso-dotracontane 

anteiso-alkanes anteiso-triacontane, 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 the difference in the logarithms of the transmitted 
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light is proportional to the absorption of the particle deposit. Transmittance is standardized using 

photographers’ neutral-density filters that are commonly used for light attenuation in camera 

lenses and photographic enlargers. A high correlation between OD and IMPROVE EC has been 

found. 

A.5 Problem Definition/Background 

In 1997, the EPA promulgated the new National Ambient Air Quality Standards 

(NAAQS) for particulate matter (PM). The regulations (given in 40 CFR Parts 50, 53, and 58) 

apply to the mass concentrations (:g/cubic meter of air) of particles with aerodynamic diameters 

less than 10 micrometers (the PM10 standard) and to particles with aerodynamic diameters less 

than 2.5 micrometers (the PM2.5 standard). To support these standards, a 1500-site mass 

measurements network and a smaller PM2.5 Chemical Speciation Network (CSN) were 

established. Gravimetric mass and chemical speciation analyses will also be performed for PM10

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 PM10 minus PM2.5 ( PM10-2.5) based on separate PM10 and PM2.5 filter samples, or as coarse 

PM obtained by dichotomous sampling. 

The ambient air data from the network, which 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 supporting designation of an area as attainment or non-attainment. 

The CSN consists of a set of core sites and additional non-core sites. Chemically speciated data 

are used to serve needs associated with development 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 exposure 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 associated with RTI’s role in filter scheduling 

and distribution, performing the filter analyses, and validating and 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 the continental U.S. Each site had two or more PM2.5 chemical 

speciation monitors to enable various sampler intercomparisons. The mini-trends network ran 

from February 2000 to August 2000. RTI is currently 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 using the 3000N sampler are analyzed by the 

IMPROVE_A method by subcontractor DRI. Outfitting the remaining sites in the CSN with 

URG 3000N samplers was complete in FY10. Sampling of quartz filters on the MetOne SASS 

sampler and analysis by the CSN method continued past the end of FY10 to support an 

intercomparison special study being conducted by EPA. Legacy CSN sampling and analysis also 

continued into 2011 at a small number of sites at the request of the air agencies. 
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Beginning with the laboratory contract that began in 2009, gravimetric and chemically 

speciated measurements were added for PM10 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/mass spectrometry (ICP/MS), SVOC 

analysis, and optical density (OD); as well as determination of gas phase ammonia, nitric acid, 

and SO2 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 schedule specified by the DOPO. 

2. Receiving the samples from the field sites and analyzing the sample media for mass 

and for an array of chemical constituents including elements (by EDXRF), soluble 

anions and cations, and carbonaceous species. Analysis of SVOCs, OD, gas-phase 

ammonia, ICP/MS, and examination of particles by electron or optical microscopy 

will be provided for selected samples. 

3. Assembling validated sets of data from the analyses, preparing data reports for EPA 

management and the states, and entering data 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 comprehensive QA/QC system. RTI’s Quality 

Management Plan, this QAPP, and associated SOPs provide the documentation for 

RTI’s quality system. 

RTI will provide all the staff, facilities, analytical instrumentation, computer hardware 

and software, and consumable supplies necessary to carry out tasks from these work areas and 

will ensure that all contractual specifications are met. 

A.6.1 Schedule 

The present contract period 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 the 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 contract years, and this level of activity is expected to continue 

for the remainder of the contract unless program funding is reduced. 
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Table A.6.2. Sample Quantities for Base Period January 8, 2009 through January 7, 2010 

Line Item Description Each No. Samples

0001 PM2.5 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 Total 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 activity 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 sufficient for the data’s intended use, while 

simultaneously ensuring that resources are not wasted collecting unnecessary, redundant, or 

overly precise data. The formal DQO process consists of seven steps that allow an experimental 

design to be developed to meet decision criteria specified by stakeholders 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 PM2.5 CSN. The primary DQO, detection of trends 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 trend 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 collected at the CSN sites and other chemical 

speciation sites were identified, but these were not evaluated quantitatively by the 

workgroup. Five important secondary data uses are as follows: 

 Model evaluation, verification, and/or validation 

 Emission inventory 
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 Source attribution 

 Spatial and seasonal characterization of aerosol distributions 

 State Implementation Plan (SIP) attainment and strategy development 

The desirable data quality characteristics for these secondary objectives are significantly 

different from those applicable to trend assessment. 

A.7.2 Quality Objectives for Total Measurement Error

The DQO study also concluded that with sampling 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, the annual trend must exceed ±6.3% to be detected 

with a power of 80%. The workgroup members concluded that this was not sufficiently different 

from the 5% goal to require adjustment to the sampling design. Sampling daily instead of every 

third day provides little improvement in the ability 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 interpreted as the total coefficient of variation 

(CV) attributable to sampling and analysis, are summarized in Table A.7.3. Analysis of the 

IMPROVE data and the model indicated 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 there is no MQO-specified 

bias. In terms of completeness, the trend detection 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 1999b 

 
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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 analysis of data from 

sites that operate collocated monitors. Estimates based on results from six CSN sites where 

collocated samplers are operated are included in the Annual Data Summary Reports. 

Work during the first two CSN contracts (2000–2008) has helped to identify some 

additional quality issues that were 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 total 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 Table A.7.4, which reports the MQOs for total 

measurement error. 

 Sensitivity issues – The majority of the PM2.5 sampling for the CSN is being 

performed using the MetOne SASS sampler, which operates at a flow rate of 6.7 liters 

per minute and uses 46.2 mm filters. Compared 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 immaterial for gravimetric mass and species 

present in large amounts, such as sulfate, 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, because 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 μg/m3

 or more, which can bias the results by 

20%–30% on a typical sample. Methods for correcting 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 taken with the URG 3000N or the IMPROVE 

samplers are much smaller than for those taken with the MetOne SASS. Samples 

taken with higher flow samplers, such as the PM2.5 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 consistent definitions of uncertainty to be 

reported to the AQS database. The original formulation of uncertainty was based on 

the IMPROVE program’s propagation of errors approach and relied on uncertainty 

values provided by the analytical instruments 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 analyzers. 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 uncertainties reported between different XRF 
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instruments. In the process, we also ensured that the total uncertainties for the other 

CSN analytical techniques (gravimetry, ion chromatography, OC/EC) were 

comparable with those for XRF and were realistic, based on the collocation results. 

DQOs and MQOs for Speciated PM10 and PMcoarse

PMcoarse involves subtraction of results from two different filters. A straightforward 

approach to calculating precision would be to combine the individual uncertainties reported for 

the PM2.5 and the PM10 filter, assuming additivity of variance. This may turn out to be a valid 

approach for simple species such as gravimetric mass; however, this approach is likely to 

significantly underestimate the random variability for other chemical species for a variety of 

reasons. Research necessary to develop expressions for accuracy and precision and the 

corresponding DQOs and MQOs applicable to PMcoarse 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 measurement error is the component that can be 

controlled and/or quantified most readily through the QA/QC program, even though it is 

significantly smaller than either the day-to-day variability in environmental pollutant levels (U.S. 

EPA, 1998) or the errors associated with sampling and handling (Flanagan et al., 2006). 

The original set of MQOs for laboratory analyses 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 Error

a Completeness Goalb

Cations and Anions ±10% if C > 10HMDLc

or 

±MDL if < 10HMDL 

90% 

Carbon Species ±20% if C > 10HMDL 90% 

Filter Weight ±10% if Wt > 6 μg/m3 90% 

Elements (EDXRF) ±20% if C > 10HMDL 90% 

SVOCsd ±10% if C > 10HMDL 

or 

±MDL if < 10HMDL 

90% 

SEM and Optical Microscopic Examinationd N/A 90% 

Denuder Analysis for Ions TBDe 90% 

Optical Density TBDe 90% 

Elements (ICP/MS) TBDe 90% 
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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 successfully exposed and returned to RTI for the specified 

analysis. Historically, the CSN laboratories have achieved 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 calibration 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 random 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 aggregate 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 operated on either 1-in-3-day 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). PM2.5

Speciation trends network: evaluation of whole-system uncertainties using data from sites 

with collocated samplers. Journal of the Air and Waste Management Association 56:492–

499. April. 

U.S. EPA (1999a). Particulate Matter (PM2.5 ) Speciation Guidance Document (Third Draft), 

U.S. EPA, Research Triangle Park, NC. January 5, 1999. 

U.S. EPA (1999b). Strategic Plan: Development of the Particulate Matter (PM2.5) Quality 

System for the Chemical Speciation Monitoring 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 PM2.5 Speciation 

Network, U.S. EPA, Research Triangle Park, NC, 1999. Available on AMTIC at 

http://www.epa.gov/ttn/amtic/files/ambient/pm25/spec/dqo3.pdf. (Accessed 08/09/2011) 

U.S. EPA (1994). Guidance for the Data Quality Objectives 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. 
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A.8 Special Training Requirements/Certification 

It is important that the analytical results produced by each analyst meet MQOs. 

Attainment of MQOs will be measured by attainment 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 required to be experienced with the basic 

measurement techniques relevant to the analyses that they are to perform. These techniques 

include the operation of an analytical 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 analyst to be trained (hereafter referred to 

in Section A.8 as “the analyst”) will read and understand the appropriate SOP. Under the 

direction of an analyst experienced in the method, the analyst will follow the SOP and use the 

method to analyze reference samples and, if available, samples that have been analyzed 

previously by an experienced analyst. These samples might include split filters, filter extracts, 

and whole filters for XRF and electron microscopy. This effort will be continued until the analyst 

achieves MQOs for recovery (or bias) and precision. 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 keeping. 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 under 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 review of analytical data, which are identified 

by the analyst. 

RTI will require gravimetric analysts to pass a test similar to the certification test 

administered to analysts working on the EPA’s PM2.5 Federal Reference Method Performance 

Evaluation Program (FRM PEP), which RTI helped to develop under another contract. 

Permanent RTI employees, including high-level personnel and Technical Area 

Supervisor, are eligible to attend training courses relevant to the project areas. Both in-house and 

extramural training opportunities are provided to RTI’s employees 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 reading and utilizing the SOP and verification by the 

Technical Area Supervisor and/or mentor that acceptable method performance has been 

demonstrated. These folders will include records of all performance standard analyses, formal 

training, and in-house training and testing. 
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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 SOPs 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 experience, including currently managing 

RTI’s PM Gravimetry Laboratory ensuring that 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 experience, 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 experience, 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 laboratory 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 for the National Park Service, the American 

Lung Association, the EPA, and the California Air Resources Board. 

Christine Van Hise – 15 years of relevant experience in sample handling and 

preparation, including over 3 years of experience in air filter extraction. 

Dorrie Pickett – Over 20 years of relevant experience in sample handling and 

preparation, including over 4 years of experience in air filter extraction. 
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Metal Analysis 

Andrea McWilliams – 10 years of relevant experience, including 8 years of experience 

operating, maintaining, and troubleshooting the ThermoNoran QuanX (EDXRF). 

Paul Duda – (CHESTER LabNet) 20 years of relevant experience including 9 years of 

experience in air filter analysis by EDXRF and 9 years of experience as a LIMS 

administrator. 

Richard Sarver – (CHESTER LabNet) 23 years of relevant analytical experience, 

including 17 years of experience in environmental air quality 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 protocols, and their differences. 

Melville Richards – More than 25 years of relevant experience, including experience in 

ion chromatography and carbon analysis. Also, 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 experience in conducting air quality studies 

and performing statistical data 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 quality criteria document that pertained to 

chemical analysis and source emissions. Co-principal investigator on evaluation of 

aerosol measurement methods, sampling strategies, and databases for the U.S. EPA’s 

guidance document on network design, continuous particulate monitoring, and 

aerosol measurement methods. 

D. L. Trimble – (DRI) More than 16 years of experience in ambient air quality 

measurements and quality assurance. Serves 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 experience 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 fluorescence. Also manages field studies, 

maintains a vast array of field sampling equipment, and supervises three laboratory 

technicians. Before coming to DRI, Mr. Kohl developed immunochemical pesticide 
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assays for use in fiber optic biosensors for environmental monitoring applications for 

EPA. Mr. Kohl will serve as DRI’s EAF Laboratory Coordinator. 

Richard Tropp – (DRI) More than 30 years of experience conducting air quality studies, 

statistical data analysis, and quality assurance. Project Manager for PM2.5 FRM 

laboratory support to the states of Texas and Oklahoma. Provides coordination among 

laboratory groups, field personnel, contractors, and subcontractors. Provided technical 

support to EPA in preparing PM2.5 regulatory proposal and promulgation packages. 

Outside reviewer of Section 2.12 of EPA’s QA Handbook. 

John Watson – (DRI) More than 30 years in environmental sciences, including the 

planning and conducting of major air pollution studies. Serves as QA Manager and 

senior technical advisor for the EAF. Has undertaken reviews 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 experience with scanning electron microscopy 

(SEM) and transmission electron microscopy. Specifically experienced in analysis of 

PM10 and PM2.5 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 collection and analysis methods for trace 

atmospheric organic species present in both gaseous and particulate phases. Work 

includes the development of analytical methods for measuring biologically active 

compounds in primary and secondary particulate organic matter; atmospheric 

transformations of organic compounds; ozone precursors; and particle-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 (CASAC) 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 logistics of shipping and receiving large numbers 

of samples through EPA radon proficiency testing program and American Industrial 

Hygiene Association Environmental Lead Proficiency Analytical Testing program. 

Jessie Deal – 9 years of relevant experience supporting the PM2.5 chemical speciation 

project, which includes handling, packaging, and maintaining records for different 

types of air filters used for air sampling studies. Serves as assistant supervisor of the 

sample handling laboratory and oversees operations in Mr. O’Rourke’s absence. 
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Database Development/Management 

Edward Rickman – More than 20 years of relevant experience in design and 

implementation of environmental and QA databases, including a database for EPA’s 

OAQPS PM2.5 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 dictionaries for database documentation. Also 

responsible for final flagging and uploading CSN data to AQS after review by the 

SLT air agencies. 

Quality Assurance 

James Flanagan – More than 20 years of relevant experience 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 field 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. Experience 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 American Industrial Hygiene 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, and 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 training, and results of performance audits. 

Highlights of the present status of experience and training of RTI personnel include the 

following: 

 Gravimetric mass laboratory staff have given instructional workshops and prepared SOPs 

to train analysts for the PM2.5 Performance Evaluation Program. 

 The RTI ion chromatographic team has performed air filter analysis for the National Park 

Service for the IMPROVE program. PM2.5 ion analysis has been performed in support of 

EPA evaluation of PM2.5 samplers, for the California Air Resources Board, and for a 

variety of other clients. 
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 Three staff members have trained other personnel in the use of single channel PM2.5

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 participated in operating them at sites across the 

country. 

 At least three members of the staff have served 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 successfully completed training courses in 

the operation and application of the ThermoNoran EDXRF unit and understands the 

problems associated with the analysis. 

 CHESTER LabNet personnel have successfully 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 analysis method for carbon species have shown good 

agreement with other laboratories through sample analysis intercomparisons 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 Archiving 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 program 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 credentials carefully assessed with regard to 

prior experience and aptitude for the assigned task. Candidates are 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 Technical Area Supervisor in another area. 

 RTI regular and temporary personnel to be hired for sample shipping and receiving in the 

SHAL must have excellent work habits and must be particularly careful 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 qualifications with regard to work habits. 

 New hires in the analytical laboratories must have experience or aptitude equivalent to 2 

years of experience, but individuals are assessed on a case-by-case basis by the Technical 
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Area Supervisor. References are contacted to verify that the applicant has the required 

laboratory skills and aptitude. 

 For individuals hired as permanent RTI employees, a probationary period of 6 months is 

provided, at which time the employee may be terminated for failing to meet required job 

standards; temporary employees may be dismissed at any time. The majority of training 

is on-the-job and is provided by the Technical 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 experience to perform the task. Any departures from the written 

SOPs will require consultation with the Technical Area Supervisor for that area. 

Departures from SOPs necessitated by systematic or recurring problems should result in 

corrective actions, which may include revision of the SOP. 

 All new hires will work under close supervision of the Technical Area Supervisor. The 

individual may work unsupervised only after the Technical Area Supervisor provides a 

memo to the individual’s training file. Analysts 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 reports 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 Office 
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A.9.1 QA/QC Records 

Table A.9.2 shows the QA/QC records that 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 SHAL 
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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 filters/pieces of filters to 

analysis 

Hard copy SHAL 

Aliquot Log-Out Form Lists aliquots 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 Laboratories’ Records 

RTI and subcontractor analytical 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 laboratory 
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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 Includes 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 

laboratory 
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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 Table 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 various 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, materials (e.g., filters and reagents), and laboratory personnel can be 

scheduled as necessary. Each month, the SHAL supervisor will calculate 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 calibrations, 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’ comments; 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. 
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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 calibrations, 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’ comments, 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 instrument 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’ comments; 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. 
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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 Lab 
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B.1 Sampling Process Design (Experimental Design) 

The experimental design, including design 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 the 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 available on the AMTIC Web site. 

B.3 Sample Handling and Custody Requirements 

Note: This section relies heavily on design of RTI’s sample handling system, 

including the SHAL. Please refer to the 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 internally and between RTI and its 

subcontractors. In this document, the term “sampling 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 smallest 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 modules and associated sample media will be tracked 

individually in the database management system (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 received from the DOPOs. The PM checks the 

consolidated request and distributes it to the SHAL and other laboratories for planning purposes. 

Based on the schedule defined by all the consolidated requests, RTI schedules and sends 

modules to the addresses indicated for the state monitoring agencies. Details of the information 

contained in the consolidated requests, and RTI’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 samples into its tracking system, performs all required 

speciation analyses, enters and validates 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 archiving samples and for resolving technical quality 

issues and contract dispute issues. 
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Figure B.3.1. Overview of sample handling and custody system. 

 
QAPP for Chemical Speciation of PM2.5 Filter Samples 

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The following subsections describe the processes associated with filter and sample 

handling and archiving, the physical and chemical analyses required for each filter in each type 

of speciation sampler, and the data handling and analyses required to obtain concentration data 

of known quality. The sample handling and tracking process is described 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 sample shipments to track and ensure that 

samples are collected, transferred, stored, and analyzed by authorized personnel; sample integrity 

is maintained during all phases of sample handling 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 relinquishing of all data to the DOPOs and the state 

clients. 

The COC documentation that accompanies the sampling modules to and from the field 

will include a three-part carbonless form for sending and receiving 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 distribute individual sets of filters to the 

various laboratories for analysis. These forms are computer generated based on information 

already entered into the database, such 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 read into the database as part of the SHAL disassembly 

procedure. 
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2. Denuder Refurbishment Laboratory (DRL). Personnel in the DRL are responsible for 

refurbishment of all denuders and extraction 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 denuders. 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 PM2.5 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. CHESTER 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 denuder extracts. They are also responsible 

for acceptance testing and cleaning, if necessary, 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. The 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 laboratory are responsible for 

carbon analysis by the IMPROVE method. 

8. Semivolatile Organics Laboratory (SVOL). Personnel in the DRI SVOL are 

responsible for measuring individual SVOCs extracted from PM2.5 collected on selected 

quartz filters and from backup sorbent traps. 

9. Microscopy Laboratory (ML). Personnel in the ML are responsible 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 laboratory 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, sodium, and potassium) and anions (sulfate and 

nitrate). 
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Figure B.3.2. Diagram of RTI filter processing and analysis activities by filter type 

(arrangement may vary by sampler model).
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Figure B.3.3 shows the anticipated movement of filters and extracts through RTI 

laboratories described above. The focal point for shipping and receiving sampling media and for 

archiving analyzed filters and extracts is the SHAL. The other laboratories, except for the DRI, 

are responsible for cleaning and acceptance testing of new filters and for analyses of samples 

collected on those filters. The main items moving between the various 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. 
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After final weighing in the gravimetric mass 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 PM2.5 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 models use at least one each of the three types of 

filters (Teflon, nylon, and quartz) used in the PM2.5 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 associated with sampling modules and visually 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 destination. All modules are assembled according to the 

manufacturer’s instructions and with the sampling components requested by the state agencies 

and approved by the DOPOs. These operations are fully 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 additional required components are shipped 

in specially designed insulated shipping containers to each sampling 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 state 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 distributed through the DOPOs. 

Sufficient commercially available, leak-proof, “blue-ice” gel packs 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 temperature 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 receipt is recorded on a Level 0 validation form. 
QAPP for Chemical Speciati

Table B.3.1. Sampler Component and Laboratory Speciation Analysis Matrix 

Sampler 

Module 

or Flow 

Channel Device Mass 

Elements 

XRF, 

ICP-MS 

Anions++

SO4-2, NO3-

Cations,++

NH4+, Na+, K+

TC, OC, 

EC 

Optical 

Density SVOC 

Mic

co

URG 3000N Sequential carbon aerosol sampler 

Module 1 Quartz filter ● ●

SASS Channel 1 Teflon filter ● ● ● 

Channel 2 Nylon filter 

with MgO coated denuder 

● ●

Channel 3*** 

Quartz filter ● ●

FRM Single 

channel per sampler+

Teflon filter ● ● ● 

Nylon filter with MgO coated denuder 

● ●

Quartz filter ● ●

All sampler types 

Analytical Denuders: Any channel, as required 

Phosphorous or citric acid coated MgO or Na2CO3 coated 

PMCOARSE To be determined EC = elemental carbon, HNO3 = nitric acid, ICP-MS = inductively coupled mass spectrometry, K+ = potassium ion, Na+ = sodium ion, NH

ammonium ion, NO3- = nitrate ion, Na2CO3 = sodium carbonate, OC = organic carbon, SO2 = sulfur dioxide, SO4-2 = sulfate ion, SVOC = 

compound, TC = total carbon, XRF = X-ray fluorescence 

+ Three FRM samplers can be used in parallel as three separate channels to collect PM2.5 samples for speciation analyses. ++ Sorbed gases NH3, HNO3, and SO2 are 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. 
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B.3.3.3 Disassembly of Sampling Modules 

Upon their return to RTI, sampling modules are logged into the database and 

disassembled by SHAL personnel. Each filter is sealed in a new, clean, labeled petri slide holder 

and sent to the appropriate laboratory for analysis. Any denuders used in the module will be 

refurbished or extracted and analyzed, if required, and all other components 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 typical batch, so there is not a one-to-one correspondence between the 

external COC form (which corresponds 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 similar 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 subsampling for OC/EC analysis) 

 Quartz filter extracts in glass bottles (following SVOC analysis) 

 Teflon or other filters (following microscopic 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 sampling 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. Computer-generated reports are available to facilitate retrieval by 

sample date, site, or state. Quartz filters sent to DRI for analysis are 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 sample 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 filter based on these criteria as well. 
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Figure B.3.4. RTI Laboratory COC form used in tracking. 

 
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Teflon filters are archived in petri-slide holders, 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 interfering acidic and basic gases and gas-phase SVOCs. The acidic 

gases of concern to the Chemical Speciation Network include nitric acid and SO2. The reason for 

removal of such gases is to preclude 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 with the filter itself to form nitrate salts; thus the nitrate ion 

concentration would be higher than that due to nitrate PM alone. In certain instances, it may also 

be desirable to remove SVOCs from the air stream due to their potential for adsorption or 

reaction upon reaching the PM collection filter. 

RTI will also prepare denuders specially designated for quantitative extraction. These 

denuders will be prepared with special attention to the purity of the coating reagents, and 

backgrounds levels of the species to be analyzed (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 ambient gas-phase ammonia, nitric 

acid, and SO2. 

RTI will provide support for the operation and use of denuders associated with all types 

of samplers to be used in the speciation network. Denuder specifications for the samplers will be 

provided upon start-up of this segment of the monitoring program. 

The state (or local agency within the state) planning to employ denuders in its PM 

speciation sampling scheme will inform the EPA Regional Speciation Coordinator of this fact at 

the same time that a request for analytical services 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, denuder cleaning and coating, and QC. The EPA 

DOPOs will notify RTI’s Program Manager of the state’s need for denuders (and filters) and 

details on special filter pack arrangements associated with the 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 appropriate shipping containers, and carefully pack 

and ship the new denuders to RTI by Federal Express. 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: 
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 Standard Operating Procedure for Coating and Extracting Annular Denuders with 

Sodium Carbonate 

 Standard Operating Procedure for Coating Annular Denuders with Magnesium Oxide 

 Standard Operating Procedure for Coating Annular Denuders with XAD-4 Resin 

 Standard Operating Procedure for Coating 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 shipment to the field. 

The denuders to be installed at the site sampler are shipped to the requesting state or local 

agency. Denuders are listed on the COC form that will accompany each shipment to a particular 

speciation sampler. A record of the number of uses 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 replaced after approximately 30 exposures, and 

Na2CO3 denuders are replaced after 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 replacement or repair of denuder components damaged in 

the field; the shipping company is responsible for damage caused during transit. 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 sealed 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 PM2.5 Gravimetric Analysis describes the procedure to 

be used for gravimetric mass determination 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: 
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RTI 

Standard Operating Procedures for X-Ray Fluorescence Analysis of PM2.5 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 Spectrometer Data Generation, Interpretation, 

and Reporting 

Standard Operating Procedure for the Kevex XRF Spectrometer Calibration 

B.4.3 Extraction and Analysis of Anions and Cations 

For an overview of RTI’s laboratory facility and procedures for extraction and analysis of 

anions and cations, including nitrate and sulfate, see: 

Standard Operating Procedure for Cleaning Nylon Filters Used for Collection of PM2.5

Material 

Standard Operating Procedures for PM2.5 Anion Analysis 

Standard Operating Procedures for PM2.5 Cation Analysis 

B.4.4 Carbon Analysis 

RTI’s laboratory facility and procedures for 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-Transmittance 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 for 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 Determination of Carbon Fractions in 

Particulate Matter Using the IMPROVE_A Heating Protocol on a Sunset Laboratory 

Dual-Mode Analyzer 
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 Standard Operating Procedure for the Determination 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 IMPROVE/TOR-TOT analysis are similar in 

technical approach, and both require heating ramps under non-oxidizing conditions followed by 

heating ramps under oxidizing conditions, the two methods are fundamentally different in the 

way they define carbon fractions. The CSN/TOT analysis is a timed analysis with fixed times at 

each temperature step in the heating profile, and 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 residence time of 150 seconds and a 

maximum residence time of 580 seconds at each temperature 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 fractions 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 the 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 temperature) 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 for characterization of particulate samples. 

RTI has extensive experience in the analysis of airborne PM by both optical and electron 

microscopy techniques, having analyzed a large number of PM10 filters by optical microscopy 

for several state air quality agencies and a significant number of air filters for commercial firms. 

B.4.6.1 Scanning Electron Microscopy 

SEM can be employed to characterize individual particles collected on a filter. Particles 

may be sized and the morphology described on an individual basis. The composition of a particle 

may be determined by EDXRF. Characterization 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 superior 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 PM10 and PM2.5 Samples by Scanning Electron 

Microscopy. 
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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-O2/OCT OC 900°C OCT 580°C 

He&He-O2/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-O2/PCT Pyrol_C Varies PCT varies 

He-O2/PCR Not Calculated N/A PCR varies 

He-O2/ECT EC 920°C ECT 840°C 

He-O2/ECR Not Calculated N/A ECR 840°C 

He-O2/1st EC Peak Not Calculated 600°C EC1 580°C 

He-O2/2nd EC Peak Not Calculated 675°C EC2 740°C 

He-O2/3rd EC Peak Not Calculated 750°C EC3 840°C 

He-O2/4th EC Peak Not Calculated 825°C N/A N/A 

He-O2/5th EC Peak Not Calculated 920°C N/A N/A 

† Chemical Speciation Network/Thermal-Optical-Transmittance Analysis, adopted by EPA in 2000. 

Older models of Sunset carbon analyzer did not calculate individual EC peaks. Dual-model sunset 

carbon analyzers calculate the individual EC peaks. 

‡ Interagency Monitoring of Protected Environments/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 stereo-binocular and 

polarizing light microscopes (PLM) capable of both reflected and transmitted light analysis. 

Photomicrography capabilities allow for documentation 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 examination of particles having apparent 

diameters less than 0.25 μm. Optical characteristics 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 PM2.5 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 individual particles. Other filter media such as 

mixed cellulose ester (MCE) or polycarbonate provide substrates that are more suitable for 

analysis by optical microscopy. 
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B.5 Quality Control Requirements 

B.5.1 Quality Criteria for Gravimetric Analyses 

All QA/QC procedures and processes employed 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 NIST 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 software that has been developed by RTI for the 

CSN program automatically prompts for duplicate and standard weighings to ensure that these 

QC checks are performed at the required frequency in each weighing session. 

A summary of nine laboratory QC samples that accompany gravimetric measurements 

and their acceptance criteria is given below. 

1. At least two Class 1 working mass reference standards traceable to the National 

Institute of Standards and Technology (NIST) 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 exceeded, 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 acceptable 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 monitored by QC charts (or equivalent) 

throughout the year to determine if any bias has developed in the weights or the 

balance. 

4. Replicate weighings are made at a frequency of 33% of pre-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 consulted and corrective action will be taken. 

5. At least one laboratory blank is weighed during each weigh session, with the weight 

not to vary by more than 15 μg from the initial weight. If this tolerance is exceeded, 

troubleshooting of the entire weighing process 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 laboratory blanks are within 15 μg, the state 

agencies will be notified to troubleshoot possible contamination in the field. 

7. The microbalances are calibrated annually or more frequently, as needed, by a Mettler 

technician. 
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8. The 100 and 200 mg primary and working mass reference standards are recertified 

annually against NIST-traceable mass standards at a state weights and measures 

laboratory holding a NIST certificate of traceability. [Note that filters currently used 

for gravimetric mass determination are bracketed 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 descriptions of the temperature and RH 

control requirements. 

B.5.1.1 Gravimetric Disaster Recovery Plan 

Raw weighing data, including internal QC checks, are recorded in the gravimetric 

database application written for the laboratory in Microsoft Access by RTI Data Management 

personnel. For backup and archiving purposes, the 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 raw data will also be printed for 

backup purposes. 

In addition to the program’s database backup and recovery plan, the gravimetric mass 

laboratory will have a severe weather/utilities interruption 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 power 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 interruption on laboratory operation, sample throughput, 

and data quality. 

B.5.2 Quality Criteria for Ion Analysis 

The quality criteria applicable to analysis of cations and anions are provided in 

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

QC Sample Frequency Acceptance 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 analyst 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 RTI building. Data stored on the NT file server are backed up nightly. Other 

data security measures include copying data files to the lab supervisor’s PC for data analysis, 

validation, and reporting and frequent 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 (typically done to 

free up disk storage space), and the two archive CDs are kept in separate 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. 
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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 

reanalysis 
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The two-sigma (95% confidence level) detection limits in units of ng/cm2 are calculated 

from the analysis of a blank Teflon filter as follows: 

( )

st

B

i

i

2

1

1

2 2 detection limit for element I = 2δ =

where, 

 Bi = the background counts for element I, 

 si = the sensitivity factor for element I, and 

 t = the counting livetime. 

Theoretically, detection limits may be decreased 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 speciation 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 μg C/cm2 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 μg/cm2 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 (R2) 

≥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 samples 
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QC Element Frequency Acceptance Criteria Corrective Action 

Duplicate 

analyses 

10% of 

Samples 

1) TC Values greater than 10 

μg/cm2

—less than 10% 

RPD, 

2) TC Values 5–10 μg/cm2

—

less than 15% RPD, 

3) TC Values less than 5 

μg/cm2

—within 0.75 μg/cm2

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 μg C/cm2 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 μg/cm2 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), 

CH4/He and 

CO2/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 yield satisfactory results 

before samples are analyzed 

Auto Cal 

Check 

Daily Peak area for each of the three 

CH4/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 μg/cm2—less 

than 10% RPD, 

2) OC or TC < 10 μg/cm2

— 

within 1.0 μg/cm2

, 

3) EC ≥ 10 μg/cm2

—less than 

20% RPD, 

4) EC < 10 μg/cm2

—within 2.0 

μg/cm2

Flag analysis results for that filter with non-uniform 

filter deposit (LFU) flag. 
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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 

Acceptance 

Criteria 

Corrective

Action 

System Blank 

Check 

N/A N/A Beginning 

of analysis 

day. 

Carbon 

Analyst 

≤0.2 μg C/cm2. 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% CH4/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% CH4/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% CH4/He 

or NIST 5% 

CO2/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 

10μL 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% 

CH4/He, and 

NIST 5% CO2/He 

gas standards. 

9-36 μg C for 

KHP and 

sucrose; 2-30 

μg C for CH4

and CO2. 

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/cm2

 or <±1 

μg/cm2

 when 

OC, EC, TC <10 

μg C/cm2 

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 until 
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Requirement Calibration 

Standard 

Calibration

Range 

Calibration

Frequency

Performe

d By 

Acceptance 

Criteria 

Corrective

Action 

and 816 °C. thermocoup

le is 

replaced. 

and Tempilaq 

values with 

R2

>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 

O2 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 attached 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 file server located in a separate RTI building. Data stored on the 

file server are backed up nightly. Other data security measures include copying 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 least 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 archive CDs or DVDs are kept in separate buildings at RTI. At 

DRI, data is archived as per their standard 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 removed 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 sorbent 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 writing (August 2011), ammonia sampling has not been 

performed for routine CSN sampling. Consequently, the sampling uncertainties and QC 

requirements applicable to preparing and testing these denuders have not been fully assessed and 

tested, or approved by EPA. 

Quality control steps applicable to acid gas denuder refurbishment and quantitative 

denuders for ammonia gas are provided in Table B.5.5. 

 
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Table B.5.5. QC Criteria for Denuder Refurbishments 

QC Element Frequency Acceptance 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, or 

missing 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 μg NH3

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 ammonia gas will be developed in cooperation with EPA. 

**Standard Operating Procedure for Coating and Extracting Compact Parallel-Plate 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 volumetric uncertainty. The reported uncertainties are 

estimated “1-sigma” valued (one standard deviation). No blank corrections are assumed other 

than laboratories’ instrumental baseline corrections, which are an integral part of each analysis. 

The equations to calculate the total uncertainty for the CSN analytes are included in Appendix 1. 
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B.5.7 Method Detection Limits 

The method detection limits (MDLs) for the PM2.5 CSN analytes are shown in Appendix 2 and 

are reported annually in the data summary reports 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 blank, 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 PM10 and PMcoarse, 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 PM2.5. 

B.6 Instrument/Equipment Testing, Inspection, and Maintenance 

Requirements 

B.6.1 Gravimetric Mass Laboratory 

Two different relative humidity and temperature recording devices are used in the 

gravimetric mass laboratory to verify that measurements 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 inspection 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 environment are not within acceptance criteria (RH = 

30%–40% with a control of "5% and temperature = 20E–23EC with a control of ±2E) for the 

preceding 24 hours. Critical criteria tables included in March 2000 guidance from OAQPS on the 

use of data flags for PM2.5 AQS data offer slightly relaxed acceptance criteria (RH = 30%–40% 

with a control of ±5% standard deviation and temperature = 20E–23EC with a control of ±2E

standard deviation). Gravimetric lab personnel will ensure that filters are equilibrated for at least 

24 hours before weighing. In the event of protracted chamber downtime that would cause the 

laboratory holding time to be exceeded, the analyst must decide whether to weigh the filters 

without the full 24 hours of equilibration, to weigh the filters when relative humidity and/or 

temperature measurements in the weighing environment have exceeded acceptance 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 AQS 
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validity status flag of 2, “operational criteria exceeded.” In each case, the analyst must specify 

the data flag and insert a brief explanation of the problem in the spreadsheet 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 laboratory, several different instruments 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 

Action 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 book 
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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 instrument is subjected to routine testing and 

maintenance. Table B.6.5 details the items to inspect, documentation 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 person performing the maintenance. 

Table B.6.5. Inspection Criteria for RTI EDXRF Laboratory 

Item 

Inspection 

Frequency Inspection Parameter 

Action 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/cm2

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 

notebook 
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Table B.6.6. RTI EDXRF Laboratory Maintenance 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 instrument 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 for CHESTER LabNet EDXRF Laboratory 

Item 

Inspection 

Frequency Inspection Parameter 

Action 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 Laboratory 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 filter samples. The list of elements analyzed by 

ICP/MS is shown in Table B.6.9. 
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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 Teflon 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 logbook. 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 tube. 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 removed for ICP-MS analysis. The 

ICP-MS is optimized daily with a tuning solution, and the samples are analyzed against a new 

calibration curve for each analytical sequence. 

Two Thermo X-Series Inductively Coupled Plasma Mass Spectrometers are used for this 

procedure. Both instruments are equipped with collision cell technology and the following major 

components: 

 Torch box, RF generator, lens stack, quadrapole, 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 range of calibration standards will be adjusted 

based on the indigenous concentration of individual elements in the samples. 

A check standard is prepared from a second 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 and near the midpoint of 

the calibration range. The check standard is analyzed following calibration and before the 

analysis of any samples at a frequency of one per 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 for the point to be valid. The initial calibration 

check, which is prepared from a separate standard source than the calibrants, must pass at +/– 
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10% of the expected concentration for each element. The initial calibration blank must be less 

than the reporting limit for each element. 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 frequency, and the measures of acceptable 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 samples n/a – flag LDU if > 20% 

The detection limit for each element is calculated by analyzing seven replicates of a 

known standard concentration and multiplying the standard deviation of the replicates by three. 

The uncertainty for the measurement is the percent relative standard deviation, which is 

calculated by the instrument operating software for 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 Sunset 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 and who will be responsible for performing the 

maintenance.

Table B.6.11. OC/EC Laboratory Maintenance 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.
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Table B.6.12. OC/EC Laboratory Maintenance 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 service dates and calibration 

results. NIST-traceable standards are tracked to determine if any bias is entering into the system. 

These standards are recertified annually. Control charts based on a standard weight are 

maintained to track long-term drift and other 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 concentrations typical of those found in the midrange of actual filter extract concentrations 

 QC sample containing anions/cations at concentrations typical of those 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 standard added to the calibration curve. 

B.7.3 EDXRF Laboratory 

RTI and CHESTER LabNet obtain their calibration standards 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 μg/cm2

. The multi-element standard is 

analyzed with each tray of samples. 
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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 energy. 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 Analyte Analyte 

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 Indium as In metal 

Sulfur as CuSx Copper as Cu metal Tin as Sn metal 

Potassium or Iodine as 

KI 

Zinc as ZnTe Antimony 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 performed 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 XRF thin film standard certified values are shown in Table 

B.7.2.
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Table B.7.2. Certified Values of Elements Present on NIST 

Standard Reference Material No. 1832 

Analyte 

Certified Value (μg/cm2) 

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 performed 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-energy line is measured at the Al K2 line (1.487 KeV) and a 

high-energy line is measured at the Cr K2 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 channel increment at 10 eV. 

Peak calibration is performed by analyzing the following thin-film standards: 

1. Micromatter, Inc., vapor deposit of single or two non-interfering elements onto 

thin mylar film 

2. EPA organo-metallic acetate film, usually 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 calculating peak location data, calibration factors, and interference 

factors correction for PM2.5 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 Verification Standards (NIST SRMs 1832 and 1833). Control limits are 

the uncertainties published with the NIST standards; 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 analyzer is checked daily using an 

external standard and during every analysis using an internal standard. The external standard is 

prepared by spiking a clean section of quartz filter with 10 μL of a standard sucrose solution, 

which corresponds to a filter loading of about 21 μgC. The internal NIST-traceable standard is 
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5% methane in helium. A set of three concentrations 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 internal standard and an external standard and during every analysis 

using an internal standard. The daily internal standard check consists of automated injections of 

the internal standard (5% CH4/He) in a non-oxidizing atmosphere (pure He), an oxidizing 

atmosphere (2% O2/He), and at the end of the run. The daily 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 injections (100 to 1500 μL, giving a range corresponding to 

about 2-36 μgC) each of NIST-traceable external CH4/He and CO2/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 initially 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% CH4/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% CH4/He and 5% CO2/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 CH4/He standard in He, He/O2, 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 injection 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% CH4/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 calibrated in three ways in this 

order: 

1. Semi-annual (or after instrument repair) full calibration using KHP, sucrose, 

CH4/He, and CO2/He standards; 

2. Daily calibration checks using injections of the two gas standards (CH4/He, and 

CO2/He); and 

3. Automatic injection of the CH4/H2 gas standard as an internal standard at the end 

of each analysis. 
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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% CH4/He, 5% CO2/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 (O2/He and He) between morning and afternoon 

injections (counts should be same) 

End-of-run calibration peak with 5% CH4/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 supervisor or laboratory 

technicians to determine if they are 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. The 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 monitoring. 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 specific analytical requirements, filters of all 

types must be examined individually prior to use to ensure that one or more of the following 

defects does not exist: 

 Pinholes. A small hole or tear in the filter matrix that appears when examined over a 

light table. 

 Loose material. Any extra loose material or particulate 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 discoloration that indicates problems 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 techniques that rely on the uniformity of aerosol 

deposition (e.g., XRF) are particularly sensitive to filter defects of this type.

 Other. Defined as any other defect (e.g., wrinkling, warping) that might prevent a 

filter from providing accurate measurement data. 
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The other acceptance criteria applicable to the different filter 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 filters and to satisfy all QA/QC needs (e.g., laboratory blanks and 

field blanks). Cassettes, if required, must be provided by the state sampling authority. The 

number of cassettes should be sufficient to allow for shipments to the sampling sites as well as 

preparation of upcoming shipments from RTI. Acceptance 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 potassium levels in each lot should be less than 

1μg/filter each based on 2% analysis 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 prefired 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 testing according to National Institute for 

Occupational Safety and Health (NIOSH) Method 5040. The results of the 

acceptance testing show evidence of inadequate cleaning or contamination that may 

have occurred during transport. 
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 If any filter analyzed gives, a measured blank total carbon level exceeding 1μg/cm2 

for the 47mm filters and 1.5μg/cm2 for the 25mm 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/cm2 total carbon) are assigned a Batch Number. Batches of acceptancetested filters are placed individually in petri slide 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. 

 Batches of the 47mm quartz filters that pass the acceptance-testing criterion 

(≤1 μg/cm2 total carbon) are assigned a Batch Number, which is used to associate the 

history of the filters with the batch and to track the batch until the filters are assigned 

individual identification numbers in the Sample Handling and Archiving Laboratory. 

Batches of acceptance-tested filters are placed 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 used for the IMPROVE_A OC/EC method requires a 

punch that has an area of about 0.5 cm2

, 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 cm2. RTI will store batches of 

prepared filters in a freezer until they are needed in preparation for field sampling. Before 

loading onto the cartridges or modules for field sampling, each quartz filter is carefully inspected 

for uniformity in size, shape, thickness, and appearance. 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, purified 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 historical databases, literature 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. 
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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 data 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 laboratory instrumentation systems. 

RTI created preset sampling configurations to ensure that samples were scheduled, 

prepared, and processed consistently. Each sampling event is scheduled for a specific sampling 

configuration. These configurations specify which 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, event, and sampling medium with a unique 

identification number (ID). To prevent data entry errors, barcode readers are used extensively 

and each ID contains a check digit to reduce errors in manual entry. 

Data reports are copied to a separate external Web server for review by the site data 

contacts. Data revisions are submitted via e-mail and 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 module 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 sampling 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, all identifiers have check digits 

to permit the data entry programs to immediately catch most manual data entry errors. Database 

referential integrity also prevents linkage of any sampling module, event, or sampling medium 

that has not been previously created in the database system. 

B.10.2.1 Sample Identifiers 

Each item that is tracked by the DMS is assigned 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 containers, and analysis aliquots in storage. ID 

numbers that are not automatically generated at the time of data entry (i.e., those that are entered 

from a local workstation) are obtained from preprinted barcode stickers. The stickers are 

generated with a unique leading character that specifies the type of item being generated and 

with a trailing checksum character. The leading character 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 sample) 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 common transposition and single character entries. 

Table B.10.1 shows the labels currently in use by the CSN Program. 
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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 the client workstation’s keyboard connection 

and provide a rapid and reliable means of entering 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 application-level programs. 

Referential integrity constraints prevent entry of a record in a dependent (child) record without a 

corresponding record in the independent (parent) table. This prevents entry of records that are 

not linked to other database items. Similarly, an independent (parent) record cannot be deleted 

while records that depend on that record exist. This prevents the creation of orphaned records. 

As an example of referential integrity, laboratory results for a laboratory sample (aliquot) 

cannot be entered unless the laboratory sample number was previously 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 analytical data would also be prevented, as this would 

orphan the analytical results (i.e., leave results that have no corresponding sample information). 

B.10.2.4 Double Entry 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 program. 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 laboratory to the DMS as an electronic file via email. The laboratory data are obtained directly from instrument data system outputs that contain 
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the sample identifier and the measured value. 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 transfer prevents data 

entry errors that could result from manually retyping data into the DMS. 

B.10.2.6 Training and Development Databases 

Separate training and development databases have been established for operator training 

and program development purposes, respectively. This permits us to train operators and develop 

new software without risk of modifying the actual 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 accidental 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 indicate specific problems and or conditions that might affect data 

quality. Flags may be added to entire sampling 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 entire sampling event apply to all results in that 

event, flags affecting a sampler flow channel apply to all results using that channel, etc. 

A number of automated range checks are currently in place. Outlier checks, also known 

as “Level 1 checks,” are done based on mass balance, anion-cation balance ratios, and other 

metrics. Assigning the limits for these outlier checks required the development of sufficient 

historical data to establish a baseline to set appropriate QC limits. Tables B.10.2 and B.10.3

show the statistical QC limits that have been developed for PM2.5 based on experience during the 

mini-trends pilot program. The upper and lower limits were based on the 2nd and 98th percentile 

points on the distributions of the mini-trends data. For blanks, the concentrations were flagged at 

the upper 95th percentile. Similar validation limits will be developed for speciated PM10 and 

PMcoarse when sufficient data has been gathered. 

Additional strategies for establishing acceptance limits should be discussed between RTI 

and EPA. 
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Table B.10.2. Statistical Validation Limits for Routine Data 

Percentile Tail Validation Test Sample Type 

Limit, 

μg Analyte(s) 

Outlier 

Flag 

2.0 LOWER PM2.5 Mass Conc. ROUTINE 2.98 PM2.5 Mass Conc. QL1 

 

2.0 LOWER Anion/Cation Ratio ROUTINE 0.86 All ions QAC 

98.0 UPPER Anion/Cation Ratio ROUTINE 2.82 All ions QAC 

2.0 LOWER Mass Ratio ROUTINE 0.60 All analytes QMB 

98.0 UPPER Mass Ratio ROUTINE 1.32 All analytes QMB 

2.0 LOWER Sulfur/Sulfate Ratio ROUTINE 0.25 Sulfate ion, XRF QCR 

98.0 UPPER Sulfur/Sulfate Ratio ROUTINE 0.45 Sulfate ion, XRF QCR 

Table B.10.3. Statistical Validation Limits for Blanks 

Tail Analyte(s) Sample Type 

Limit

μg Analyte 

Outlier 

Flag 

UPPER PM2.5 Mass FIELD BLANK 50.00 PM2.5 Mass QL1 

UPPER PM2.5 Mass TRIP BLANK 50.00 PM2.5 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 monthly data reports; however, these are not 

accepted by AQS and must be converted into valid 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-to-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 careful review of the available documentation, “generic” AQS codes 

must be used in these cases, as shown in the table. 
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Table B.10.4. Mapping of Outlier Flags onto AQS Codes 

Objective Cause Found for Level 1 Outlier 

AQS 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 Malfunction (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 criteria 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 

Parameter Limits AQS Null Value Code 

Exposure Duration, texp 23 < texp < 25 hrs AN – Machine malfunction 

AQ – Collection error 

AV – Power failure 

Other code as appropriate 

Holding Time before removal from 

sampler, tpick-up

tpick-up < 48 hrs None – As per EPA direction 

Average Flow Rate, Favg 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 following sections prior to 

delivery to the state monitoring 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 completeness and integrity of data 

assignments. Missing or anomalous results are investigated and corrected by the data processing 

staff with the assistance of SHAL 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 rectangular table. Missing 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. 
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2. Total counts of AQS-deliverable records – Each sampler type should generate a 

specific number of AQS record counts. Exceptions typically are the result of missing 

analytical results or of processing records. RTI tries to hold reporting on events until 

all analysis results have been received. If no additional analysis 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 necessary. If a sample was actually run on the 

wrong date, the data are transmitted to AQS with 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 generated. This is checked for integrity using crosstab tables and other 

simple reporting methods. Record counts per event and sampling date checks are particularly 

helpful in detecting problems with the record set. After any anomalies 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-Hour Blank data are currently sent to AQS. 

Table B.10.6 summarizes all of the AQS parameter codes applicable to the PM2.5 Chemical 

Speciation analytes. Table B.10.7 presents the AQS parameter codes for field data parameters. 

Units for all analytes are micrograms per cubic meter under ambient conditions (i.e., not 

corrected to standard temperature and pressure). The nominal sampling period is 24 hours. 

Similar tables for PM10 and PMcoarse 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 Validity 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 current AQS system, the Null Value Code overwrites 

the data value such that the AQS user cannot access the data. The Null Value Codes applicable to 

the CSN Program are shown in Table B.10.9. 
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Table B.10.6. Analytes and AQS Parameter Codes (PM2.5 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) 
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AQS Parameter 

Codes: PM2.5 

(LC) 

Analyte Symbol Analysis 

88184 Sodium Na EDXRF (trace elements) 

88185 Zirconium Zr EDXRF (trace elements) 

88301 Ammonium NH4

+ 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 NO3- 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_A 
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Table B.10.7. Field Data and AQS Parameter Codes 

AQS Parameter Code Property Units 

68103 Min Ambient Temp EC 

68104 Max Ambient Temp EC 

68105 Avg Ambient Temp EC 

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 Eruptions 
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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 Rate 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) 
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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 laboratories are responsible for managing their data prior to its 

entry into the CSN Program’s database. The procedures for data management vary significantly 

between laboratories and are described in the respective SOPs. 

B.10.7 Management and Reporting 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 reporting 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. 
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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 laboratory certification required for the program. 

 The QA Manager for this project, Dr. James Flanagan or his designee, will perform 

periodic technical systems audits of the RTI activities. These audits will cover all aspects of 

RTI's work, including sample receipt, custody, conditioning, weighing, shipping, data reduction 

and reporting. These audits are scheduled 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 summarize 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 serious problems are identified that require 

immediate action, such as a large, systematic analytical bias, the QA Manager will convey these 

to Dr. Jayanty verbally or through electronic mail 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 project 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 corrective action system for 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 informal surveillance of project activities. If 

new staff members eventually perform some of the activities that others are initially responsible 

for, the experienced personnel and/or technical supervisors will perform ongoing surveillance of 

the new persons’ work to ensure that 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. The on-site audits and assessments as of this 

writing are listed below. The most current assessments and reports are available at the PM2.5 

Speciation Quality Assurance section of EPA's AMTIC website, 

http://www.epa.gov/ttn/amtic/pmspec.html. 

 EPA/NAREL: 

‐ Experimental Inter-comparison of Speciation Laboratories (June 15, 2011), 

(accessed 5/7/2012). 

‐ 2010 DRI laboratory Technical Systems audit (June 1, 2011), (accessed 5/7/2012). 
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‐ UC Davis Laboratory Audit (January 11, 2011), 

http://www.epa.gov/ttn/amtic/pmspec.html accessed 8/10/2010). 

‐ Experimental Inter-comparison of Speciation 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 Inter-comparison of Speciation Laboratories 

(September 9, 2009), (http://www.epa.gov/ttn/amtic/pmspec.html accessed 

8/10/2010). 

‐ Multilab Speciation PE Report (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 Chemical Speciation Lab Operations 

 - October 2003 PM2.5 Chemical Speciation Trends Network Lab Audit Report 

 12/05/03, www.epa.gov/ttn/amtic/files/ambient/pm25/spec/audit03.pdf

 – EPA audit of RTI Chemical Speciation Laboratory Operations 03/20/02, 

 www.epa.gov/ttn/amtic/files/ambient/pm25/spec/rtiaudit2.pdf

 – A report on the study to evaluate specific 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 Laboratory Audit Report", 02/02/01, 

www.epa.gov/ttn/amtic/files/ambient/pm25/spec/audit.pdf

– "Performance Evaluation Samples for PM2.5 Chemical Speciation Network", 

02/02/01, www.epa.gov/ttn/amtic/files/ambient/pm25/spec/pesreport.pdf

– "PM2.5 Chemical Speciation Laboratory Audit Report", 09/01/00, 

www.epa.gov/ttn/amtic/files/ambient/pm25/spec/pereport.pdf
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– "Performance Evaluation Samples for 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 and 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 composite annual data summary reports are issued by 

RTI to the EPA Project Officer. 

 

 The SPM or designee approves the monthly data postings and the annual reports. The 

SPM and the QA Manager are notified whenever there is a QA problem and will be apprised of 

corrective actions taken to solve the problem. The QA Manager will 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 performed 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 described in items 3 and 4, below. 

2. Level 1 Validation Report (Checklist). Cation/anion balance, sulfur/sulfate balance, 

and reconstructed mass balance reports (spreadsheets) are generated from the DBMS. 

Other statistical reports are done using data from the DBMS during monthly 

validation to assist validation personnel in identifying problems. Additional statistical 

reports are being developed as needed based on experience with the chemical 

speciation data. Data flags generated during the Level 1 validation process are 

attached to each data record and are reported 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 filters, analytical results, etc., 
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to the correct event. Electronic copies of this report are prepared and made available 

to each of the following: the state agencies submitting the delivery orders, the 

DOPOs, and the EPA Regional QA Laboratory. The information for the monthly 

traceability report is included as part of the Monthly Analytical 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 field and analytical data and the flags 

produced during Level 0 and Level 1 validation. RTI has developed SQL queries to 

produce the reports and spreadsheets. Electronic copies of these reports are made 

available to the DOPOs, the state agencies submitting the delivery orders, and 

EPA/OAQPS through RTI's password-protected website. These data users are 

notified by e-mail of the availability of new 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 changes 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 operation), 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 electronic 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 

PM2.5 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 finalized annual report is posted 

to AMTIC after EPA approval. 
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D.1 Data Review, Validation, and Verification Requirements 

The following describes RTI’s approach to data review, validation, and verification for 

PM2.5 filter analysis. Similar procedures will be developed for the other forms of PM as the new 

program progresses. The QC criteria given elsewhere in this QAPP will be used as the data 

validation requirements. Any data that fails routine validation checks will be flagged for review 

by the monitoring agencies. Large or systematic exceedance criteria may also 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 to, 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 PM2.5 data in AQS. RTI will implement any additional or 

alternative flags that may be defined for PM2.5 chemical speciation data. 

D.2 Validation and Verification 

RTI is responsible for validating analytical 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, final data review, validation, and verification and for 

data reporting. 

D.2.1 Level 0 Validation 

Level 0 data sets contain all available ambient data and may contain nonambient data in 

the form of QC checks and/or flags 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 these 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 Level 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 power failures, temperature flags, and insufficient 

data for the averaging period generated by the speciation sampler in the field. 

Occasionally, RTI personnel may become aware of an excessive rate of problematic 

samples from a particular monitoring organization. Such problems might include inadequate 

packing, excessive numbers of damaged filter media, and incorrectly or inadequately completed 

forms. RTI will work with the monitoring organization to bring about corrective action. Also, the 

RTI PM will contact the DOPOs (or the appropriate contact designated by the DOPOs) to inform 

him/her of the problem. 
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D.2.2 Level 1 Validation 

Level 1 data are reviewed more fully for technical acceptability and reasonableness based 

on information such as routine QC sample results, data quality indicator (DQI) calculations, 

performance evaluation (PE) samples, internal and external audits, statistical screening, internal 

consistency checks, and range checks. Unacceptable long-term performance of the analytical 

system can also be uncovered in the process of documenting the DQIs of completeness, 

precision, accuracy, and detection limits, and comparing those indicators with the program’s 

goals or DQOs. 

In response to major or systematic problems 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 include, for example, the following: 

 Investigating the specific conditions 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 transcription errors and evidence 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 are transmitted to the state agencies for review. 

Initial screening of data is performed by data management personnel using screening criteria 

developed by the QA Manager and the laboratory 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 Area Supervisors to address the problem. Data 

problems that originate outside the scope of RTI’s operations are reported to the appropriate 

DOPO. 

RTI will take any necessary corrective actions on problems identified during Level 0 and 

Level 1 data review activities and input from the state monitoring 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 issues. 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 agencies during their review. 

D.2.3 Screening of Subcontractor Data 

Although CHESTER LabNet will conduct their own Level 0 and Level 1 screening of the 

EDXRF data, RTI must further validate its results at Level 0 to ensure a consistent data set. In 

doing so, RTI will ensure that the sample identifications and COC information from the 

subcontractor are consistent with RTI’s records. This process will consist primarily of comparing 
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the original sample numbers, dates, types, and so on, with the data received from the 

subcontractor. Of particular importance is ensuring that sample results from the subcontractor 

match up exactly with data from the other analyses 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 screenings on the subcontractor’s EDXRF data 

because this would duplicate efforts already expended. However, data from EDXRF are included 

in certain Level 1 checks such as reconstructed mass balance and sulfur/sulfate ratio. 

RTI's screening of DRI's OC/EC includes assignment checks based on date, site, and the 

various ID numbers assigned to filters, aliquots and sampling events. Monthly validation queries 

are run that incorporate the DRI data, including reconstructed mass balance, invalid data counts 

by site and date. Data from DRI are also scanned 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 information. Questionable data will be flagged 

appropriately. The following paragraphs briefly discuss 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 encountered with Teflon filters with rings in which 

the manufacturer used an adhesive to attach the 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 artifacts 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 factors differ by particulate size fraction (PM2.5, 

PM10, or PM10-2.5), and XRF instrumental conditions. 

 Filter lot-specific background levels will be accounted for in the instrumental method. 
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D.2.4.3 Ions 

RTI’s experience has indicated that artifacts and interferences pose no problem to the 

analysis of PM2.5 ions using state-of-the-art IC systems. High-resolution columns and excellent 

chromatographic data processing software provide 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 potential interferences. RTI will use its best 

judgment in applying corrections, will fully document 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 artifact; however, if EPA provides the equations to 

be used for making such a correction, RTI will process 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 CO2) and takes carbonate carbon as the 

difference between the pre- and post-acidification results. The second approach estimates 

carbonate carbon by integrating separately the carbonate peak in the thermogram and using the 

instrument’s software to calculate the mass of carbonate carbon volatilized. Carbonate carbon is 

not generally present in PM2.5 on quartz filters at loadings above the absolute error of the 

measurement; therefore, carbonate carbon 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 ensure that artifacts such as 

analyte loss and poor recovery do not pose a significant risk to achieving acceptable analysis 

results: 

 Field blanks 

 Method blanks 

 Field controls or matrix spikes 

 Laboratory controls (spiked sample matrices) 

 Method controls (spiked extraction solvent) 

 Replicate extract analyses. 
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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 performance characteristics are met. RTI will do the 

following to ensure that our performance meets contract requirements and client expectations: 

 Regular communications between the Program Manager and the DOPOs, the EPA 

Project Officer, and EPA technical leader. Communications will include conference 

calls scheduled biweekly or as needed, e-mail and written correspondence, and 

meeting with EPA/OAQPS personnel in the Research Triangle Park, NC, area. 

 An organized system of corrective action notification 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 including 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 define data delivery formats for AQS) and contacts 

between shipping/receiving personnel at RTI and the state agencies for the purpose of expediting 

or locating specific shipments. No one at RTI other than the Program Manager is authorized to 

alter schedules, increase or decrease the number of samples to be analyzed, or change the 

schedule of shipments to/from a state agency. All such requests must go through the RTI 

Program Manager. 

 
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Appendix 1: 

Uncertainty Calculations 

Uncertainty values reported to AQS with each concentration record will include 

components of both the analytical and the volumetric uncertainty. The reported uncertainties are 

estimated “1-sigma” values (one standard deviation). No blank corrections are assumed other 

than laboratories’ instrumental baseline corrections, which are an integral part of each analysis. 

The equations below describe how RTI will calculate the total uncertainty for the CSN analytes. 

A list of symbols is given at the end of this section. Uncertainties for PM10 are likely to be 

determined in the same manner as for PM2.5. Uncertainties for PMcoarse will initially be 

determined by statistically combining the uncertainties of the two filters (PM10 and PM2.5) used 

to calculate the PM10–PM2.5 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) will 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 than the average uncertainty for blanks. In most 

cases, the first term should be the larger. 

σ σσ σ M i j , = +⋅ max( Ai Vk M , Bi) 222

 (1) 

The mass uncertainty is converted to concentration units (micrograms per cubic meter) 

according to equation (2). 

σC i j σ 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 Teflon filter used in the STN program weighs 

145,000 micrograms, while the deposits on the filter are typically on the order of a few hundred 

micrograms. The total mass of loaded and clean filters is thus approximately the same (i.e., on 

the order of 145,000 micrograms). RTI has conducted experiments demonstrating that loaded 

filters have approximately the same repeatability as blank filters. Therefore, a constant value is 

assumed for the analytical uncertainty, σAi, used in equation 1, independent of filter loading. 

Data obtained from filter lot acceptance blanks have provided a good data set on which to 

calculate uncertainties for clean filters. The standard deviation of a large population of replicate 

filter weighings from 2002 and 2003 was determined in order to set the baseline parameters σAi

and σBi in equation 1. These are multiplied by a factor of the square root of 2 to account for the 

fact that two weighings are involved for each reportable mass concentration value. 
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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 must 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 posted 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 Fluorescence Measurement Uncertainties – Detailed 

Discussion – http://www.epa.gov/ttn/amtic/files/ambient/pm25/spec/xrfdet.pdf 

For the RTI XRF Lab, the XRF software does not calculate an uncertainty for an analyte 

when the peak and concentration values are 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 linear function of concentration, as 

shown. The intercept at low concentrations, σB, is determined from a replicate set of reanalyses 

of a low-level standard. We attempted to base our initial analytical uncertainty values (σAi) on 

replicate analysis of an up-scale QC standard; however, large and difficult-to-reproduce 

variability was found, so that we assumed a multiplier, σREL, of 5% for all analytes and all 

instruments. Equation 3 is used to calculate the analytical uncertainty, σAi, 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 measurements, provides the formulas used by their 

software to calculate uncertainties, which include constant uncertainty components of 

±0.20μgC/cm2 for OC and EC and ±0.30μgC/cm2 for TC, and a proportional uncertainty 

component of 5% for all three species. Assuming a filter area of 11.76 cm2

, the constant loadings 

are 2.35μgC/filter for OC and EC, and ±3.53μgC/filter for TC. See Appendix 2 to this QAPP for 

more details. Equation 4 is used for calculating analytical uncertainty for OC/EC. 

δ Ai CONST PROP = ( )/ δ + M M •δ (4) 

 
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where: 

δ Ai = estimated uncertainty of measurement1

 (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 Laboratory uncertainty estimates to include the 

OC Peaks. For all reported carbon fractions, the constant and proportional components of 

uncertainty defined for each fraction below include at least 95% of replicate measurements 

across three analyzers for 127 filters 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 section will be updated when that 

guidance becomes available. 

1.6 Determination of Volume Uncertainty 

The relative uncertainty associated with sampled volume and other shipping and handling 

components of sampling error is often the predominant part of the total measurement uncertainty. 

However, RTI has no way to determine these, based on any of the field data that we routinely 

receive. A nominal value of 5%, which is used by the IMPROVE program (see IMPROVE SOP 

351, Data Processing and Validation), is probably in the right order of magnitude for most of the 

CSN samplers. More accurate values for relative volume uncertainty would require statistical 

assessment of field audit results, which have not been consistently available for the CSN in 

previous years. Studies using data from collocated samplers and other means for assessing whole 

system variability for both the CSN and IMPROVE networks have shown that the value of 5% is 

probably an underestimate for the majority of chemical species, though it is reasonably accurate 

for high-level species that are relatively 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. Expanded Uncertainty section. Available at 

http://physics.nist.gov/Document/tn1297.pdf (accessed April 2008). 
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1.7 Definitions 

 I = Index for analytes 

 j = Index for individual 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) 

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

σCi,j = Relative standard deviation for analyte I from lab QC samples (dimensionless) 

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

σG = Std. dev. for replicate gravimetric analyses (micrograms per filter) 

σVk = Relative std. dev. of sampler volume (dimensionless) [typically 5%] 
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Appendix 2: Method Detection Limits 

Laboratory method detection limits (MDLs) are reported annually and are subject to 

periodic updates by each of the analytical laboratories. The MDLs shown in this Appendix are 

from the 2010 CSN Annual Data Report. Laboratory MDLs are converted to concentration 

units by dividing the sampled volume for the respective sampler type and channel. Note that the 

resulting MDL in concentration units will not include any allowance for uncertainties related to 

field operations, including uncertainty in the measurement of volume, contamination, or other 

field-related issues. Because AQS does not distinguish the instrument used to analyze a 

particular filter sample, the tables in the sections below only include 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 instruments that have been approved for used on 

the CSN program. Chester Labnet operates two 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 the 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 shown in the table is the maximum reported MDL over 

all balances for calendar 2010. The MDLs shown in the table apply to 47 mm Teflon filters. 

2.3 Anion and Cation Analysis 

 RTI operates the anion and cation analysis laboratory. MDLs 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 corrections for the IMPROVE_A data as of this 
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writing. The MDLs listed below are "typical" since MDLs can vary between instruments and 

over time. In addition, the MDLs in concentration 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 have 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