Draft Project Report: 

Field Evaluation of Condensable Particulate 

Matter Measurement 

Prepared for: 

Ron Myers 

U.S. Environmental Protection Agency 

Office of Air Quality Planning and Standards 

Sector Policy and Program Division Monitoring Policy Group 

Research Triangle Park, NC 27711 

Prepared by: 

Eastern Research Group, Inc. 

601 Keystone Park Dr. Suite 700 

Morrisville, NC 27560 

November 30, 2010 

EPA Contract No. EP-D-07-097 

Work Assignment No. 3-05 
i 

Disclaimer 

The information in this document has been funded wholly by the United States 

Environmental Protection Agency under EPA Contract Number EP-D-07-097 to Eastern 

Research Group. It has not been subjected to the Agency's peer and administrative review, and it 

has not been approved for publication as an EPA document. Mention of trade names or 

commercial products does not constitute endorsement or recommendation for use. 
ii 

Acknowledgements 

We wish to acknowledge the contributions of the following individuals to the success of 

this program: 

• Michael Hartman and his staff at Air Tech LLC for field sampling support to collect 

quadruplicate stack samples using proposed Method 201A and 202 and for filterable 

particulate fraction mass determinations. 

• Chris Kopp and Thomas McKenzie at Eastern Research Group for proposed Method 

202 preparation and analysis. 

• Jennifer Colby and Tracey Footer at Eastern Research Group for Method 301 data 

analysis of the field test data. 
iii 

Abstract 

This report presents results of a field evaluation of proposed modifications to EPA 

Methods 201A and 202. These methods are used to quantify fine filterable and condensable 

particulate matter (PM) emissions. The field tests evaluated the revised methods as proposed in 

the Federal Register on March 25, 2009 (74 FR 12970). The proposed methods were based on 

earlier laboratory experiments. The purpose of these field tests was to evaluate the performance 

of the methods in the field and to determine whether method precision and bias are acceptable 

based on the approach specified in EPA Method 301. The field tests were completed on a hog 

fuel-fired boiler at a pulp and paper plant. This report contains complete sampling and analytical 

results for both methods. 
iv 

Table of Contents 

1.0 INTRODUCTION....................................................................................................... 1-1 

1.1 Background...................................................................................................... 1-1 

1.2 Objective of this Field Test .............................................................................. 1-3 

1.3 Organization of This Report............................................................................. 1-4 

2.0 CONCLUSIONS AND RECOMMENDATIONS........................................................ 2-1 

2.1 Precision of the Methods.................................................................................. 2-1 

2.2 Method Recovery............................................................................................. 2-2 

2.3 Method Detection Estimate .............................................................................. 2-2 

3.0 EXPERIMENTAL APPROACH ................................................................................. 3-1 

3.1 Introduction ..................................................................................................... 3-1 

3.2 Field Test Site.................................................................................................. 3-1 

3.2.1 Process/Emission Unit Description....................................................... 3-2 

3.2.2 Sampling Locations .............................................................................. 3-2 

3.2.3 Sampling Platform................................................................................ 3-3 

3.3 Field Test Procedures....................................................................................... 3-4 

3.3.1 Sampling and Analytical Methods ........................................................ 3-4 

3.3.2 Statistical Methods ............................................................................... 3-4 

3.4 Experimental Design Matrix ............................................................................ 3-5 

4.0 RESULTS AND DISCUSSION .................................................................................. 4-1 

4.1 Filterable Particulate Results and Discussion.................................................... 4-2 

4.2 Condensable Particulate Results and Discussion .............................................. 4-8 

4.3 Spiked Condensable Field Train Results ........................................................ 4-10 

4.3.1 Inorganic Condensable Recovery Results ........................................... 4-10 

4.3.2 Organic Condensable Results ............................................................. 4-13 

4.4 Combined Filtered and Condensable Particulate Matter Results and Discussion. 4-

15 

5.0 QUALITY CONTROL AND QUALITY ASSURANCE............................................. 5-1 

5.1 Combined Inorganic and Organic Field Train Blank Results ............................ 5-1 

5.2 Inorganic Field Train Blank ............................................................................. 5-2 

5.3 Organic Field Train Blank................................................................................ 5-3 

6.0 METHOD EVALUATION PROCEDURES AND CALCULATIONS........................ 6-1 

6.1 Precision .......................................................................................................... 6-2 

6.2 Bias.................................................................................................................. 6-2 
v 

List of Tables 

Table 2-1. Estimated Method 201A/202 Detection Limits ....................................................... 2-2 

Table 3-1. Method 201A/202 Sampling Matrix ....................................................................... 3-6 

Table 4-1. Total Filterable Particulate Matter Results from Method 201A Evaluation ............. 4-2 

Table 4-2. PM10 Filterable Particulate Results from Method 201A Evaluation......................... 4-4 

Table 4-3. PM2.5 Filterable Particulate Results from Method 201A Evaluation........................ 4-5 

Table 4-4. PM2.5 Filterable Particulate Mass............................................................................ 4-7 

Table 4-5. Method 202 Average CPM (ug) of all Sample Trains by Fraction........................... 4-8 

Table 4-6. Percent Recovery of Inorganic CPM..................................................................... 4-11 

Table 4-7. Organic CPM Recovery Results ........................................................................... 4-14 

Table 5-1. Field Train Blank CPM Summary .......................................................................... 5-1 
vi 

List of Figures 

Figure 3-1. No. 2 HFB Stack Sampling Location..................................................................... 3-3 

Figure 4-1. Configuration of Each Sampling Train.................................................................. 4-1 

Figure 4-2. Average Total Particulate Collected by Method 201A........................................... 4-3 

Figure 4-3. Filterable PM10 Particulate of Unspiked Trains...................................................... 4-4 

Figure 4-4. Filterable PM2.5 Particulate of Unspiked Trains..................................................... 4-6 

Figure 4-5. PM2.5 Filterable Mass............................................................................................ 4-7 

Figure 4-6. Condensable Particulate Material Distribution in Unspiked Trains ........................ 4-9 

Figure 4-7. Average Condensable Particulate Matter for Paired Sampling Trains .................. 4-10 

Figure 4-8. Average Recovered CPM of Inorganic Particulate............................................... 4-11 

Figure 4-9. Inorganic Mass for All Test Runs........................................................................ 4-12 

Figure 4-10. Inorganic Spike Recovery for All Test Runs...................................................... 4-13 

Figure 4-11. Organic CPM Results from All Sampling Train Runs........................................ 4-14 

Figure 4-12. Total Particulate by Sampling Train Fraction .................................................... 4-15

Figure 5-1. Proof and Field Train Blank CPM Recovery ......................................................... 5-2 

Figure 5-2. Inorganic Proof and Field Train Blank Results (mg/dscm) .................................... 5-3 

Figure 5-3. Organic Proof and Field Train Blank Results (mg/dscm)....................................... 5-4 

Table 6-1. Method Evaluation Objectives for the Dry Impinger Condensable Particulate 

Method ................................................................................................................................... 6-1 

Error! Bookmark not defined.
1-1 

1.0 INTRODUCTION 

Sampling and analytical methods for a particular air pollutant group can be evaluated and 

validated by demonstrating their performance in field tests, thereby establishing the precision 

and bias of the methods experimentally. For some analytes, methods have been developed and 

evaluated for sample analysis, but not for sample collection. Field validation for new or revised 

methods that have no comparable equivalent is accomplished by spiking known quantities of the 

pollutant or pollutant class into the collection apparatus in the field so that the precision and bias 

of the method can be demonstrated from sample collection through analysis. This report 

describes the execution and presents the results of a field test to evaluate revisions to EPA 

Methods 201A and 202 that EPA proposed on March 25, 2009 (74 FR 12970). These methods 

are used to quantify fine filterable and condensable particulate matter (CPM) emissions. 

Revisions to the methods were necessary to add the capability to measure fine particulate matter 

and improve the measurement of CPM. The methods were evaluated by collecting flue gas 

samples for the measurement of filterable and condensable particulate matter at a hog fuel steam 

boiler and evaluating the data for bias and precision. Filterable particulate collection 

performance was evaluated for precision and condensable particulate performance was evaluated 

for both precision and bias. 

1.1 Background 

Emission inventories for the National Emissions Inventory (NEI), State Implementation 

Plans (SIPs), and the Consolidated Emissions Reporting Rule (CERR) require the reporting of 

primary PM emissions, including both the filterable and condensable components. The NEI, the 

SIP emissions inventories, and the periodic emissions inventories required under the CERR must 

contain accurate data for government agencies to effectively manage ambient air quality. These 

emission inventories are based on a combination of emission factors and site-specific test results, 

when test results are available. Site-specific test results provide a direct measurement of 

emissions and are conducted primarily to demonstrate compliance with an existing emission 

limitation. Emission factors are based on the averages of several site-specific tests. Thus, both 

emission factor development and emissions inventory reporting depend on site-specific tests. 

Results of site-specific compliance tests must be unbiased and have known uncertainty. 
1-2 

 Since the promulgation of Method 202 in 1991, air emission testing experience has 

shown that it is inappropriate to use water-filled impingers to cool the sample gas stream for 

CPM combustion sources having sulfur dioxide (SO2), nitrogen dioxide (NO2), and/or soluble 

organic compound emissions. These gaseous contaminants can be partially absorbed in the 

impinger solutions and chemically oxidize to form material counted as CPM in Method 202. The 

“artifact” reaction products are not related to the primary emission of CPM from the source. The 

artifacts formed in the Method 202 impingers translate into a bias in the inorganic condensable 

PM emissions reported in the compliance test reports. 

In Section II.L.c.1 of the preamble to the April 25, 2007 fine particulate matter 

implementation rule, EPA indicated that it would undertake laboratory studies in collaboration 

with stakeholders to characterize the artifact formation and other uncertainties associated with 

conducting Method 202. EPA would identify procedures to be used in applying methods to 

minimize uncertainties and EPA intended to propose revisions to the method to incorporate 

improvements and to clarify application. 

ERG completed laboratory tests to evaluate a dry impinger Method 202 designed to 

reduce artifact reaction products that are not related to the primary emission of CPM from the 

source. ERG also determined method precision and bias. For the laboratory test procedures, see 

“Laboratory Test Plan and Quality Assurance Project Plan (QAPP) for Method 202 Assessment 

& Evaluation for Bias and Other Uses” at 

(http://www.epa.gov/ttn/emc/methods/method202.html). For results of the laboratory 

experiments, see the test report “Evaluation and Improvement of Condensable Particulate Matter 

Measurement” on the same Web site. 

Based on results of the laboratory experiments, EPA proposed revisions to Methods 

201A and 202. 

• Proposed amendments to Method 201A would add a particle-sizing cyclone to the 

sampling train to measure PM2.5 using Method 201A and to provide for more accurate 

measurement of the filterable and condensable components of fine PM (particles with 

mean aerodynamic diameters less than or equal to micrometers (μm)) and coarse PM 
1-3 

(particles with mean aerodynamic diameters less than or equal to 10 μm) when using 

Method 202. 

• Proposed amendments to Method 202 would reduce the formation of sulfuric acid 

artifact by at least an additional 90 percent (compared to our recommended 

procedures for the existing Method 202), provide for greater consistency between 

testing contractors in method application, improve the precision of the method, and 

provide for more accurate quantification of direct (i.e., primary) PM emissions to the 

ambient air (the method will not measure secondarily-formed PM). 

1.2 Objective of this Field Test 

The objectives of the field test described in this report include the following: 

• Complete a field test that meets EPA Method 3011 requirements for replicate tests 

sufficient to evaluate the bias and precision of proposed methods 

• Determine the precision associated with the measurement of filterable PM10 and 

PM2.5 emissions using the twin cyclone sampling system using the hardware and 

procedures described in the proposed Method 201A. 

• Determine the precision and bias in the measurement of the (inorganic and organic 

components) condensable particulate matter using the sampling hardware and 

procedures described in the proposed Method 202. 

• Determine the achievable field blank levels associated with the procedures and 

reagents specified in the proposed Method 202 when the sampling train glassware is 

reused in the field. 

The precision data from blank trains in this field test were used to refine the laboratory 

estimates of the method detection limit (MDL) and provide information on the usability of the 

method for compliance, emissions factor development, rule development, and other fine 

particulate stack emission studies. The information on the field blank levels also provides 

information about the need to revise the allowable blank correction of the method due to normal 

variations of residue introduced in the preparation and recovery of the samples. 

For a complete description of the field test and procedures, see the Category III 

QAPP/Site Specific Field Test Plan: Evaluation and Improvement of Condensable Particulate 

Matter Measurement, which is included in Docket EPA-HQ-OAR-2008-0348. ERG evaluated a 

 

1

 EPA Method 301. Protocol for the Field Validation of Emission Concentrations from Stationary Sources. U.S.

Environmental Protection Agency. EPA 450/4-90-0015. April, 1991. (40 CFR Part 63, Appendix A) 
1-4 

spiking mixture that will be used to evaluate the bias and precision in Method 202. There is 

currently no known in-situ spiking procedure for filterable PM10 or PM2.5 particulate. Therefore, 

only precision of Method 201A is evaluated in this field test. 

1.3 Organization of This Report 

This report discusses the details of the field evaluation study of proposed revisions to 

Method 201A and 202. Section 2.0, Conclusions and Recommendations, summarizes the results 

and provides recommendations. Section 3.0 discusses the experimental approach for the field 

studies and Section 4.0 provides a discussion of the results. The analytical instrument 

performance and associated quality control data are provided in Section 5.0. Section 6.0 presents 

the method quality control. 
2-1 

2.0 CONCLUSIONS AND RECOMMENDATIONS 

2.1 Precision of the Methods 

The precision of the revised Methods 201A and 202 was evaluated and is summarized 

below. 

• Total Filterable PM standard deviation of 1.51 mg/dscm 

• PM10 standard deviation of 0.85 mg/dscm 

• PM2.5 standard deviation of 0.80 mg/dscm 

• Total CPM standard deviation for 8** tests was 2.0 mg/dscm 

− Organic CPM standard deviation for 9* tests was 0.43 mg/dscm 

− Inorganic CPM standard deviation for 8** tests was 1.9 mg/dscm 

* Test 10 was eliminated as an outlier for the organic CPM 

** Tests 1 and 2 were eliminated as outliers for inorganic CPM 

Measurement of filterable particulate matter collected during these tests showed precision 

that is consistent with Method 17 and the tests performed to develop the multi-cyclone particle 

sizing sampling head that was used in this evaluation to collect size fractionated particulate 

matter. 

The majority of the particulate matter collected in these evaluation tests was less than 

PM2.5. The precision of the particulate matter greater than PM10 and the particulate matter 

between PM10 and PM2.5 was greater than the precision of PM2.5 because these masses were near 

the sensitivity limit of the analytical balance used to determine mass. Therefore, the precision for 

the total particulate and the PM10 particulate mass represents a worst case for the method. 

The inorganic spike bias and precision meet Method 301 requirements for a new method 

without correction. Organic spike was not recovered indicating the compound was too volatile 

for evaluation as an organic challenge for the sampling method. 

The field train recovery blank is a combination of various contributions to mass including 

how well the train was recovered from the previous run and contamination from the field 

environment. The average organic field train blank recovered from seven trains during this 

evaluation was 0.78 mg/dscm based on the average sample volume collected during the field 
2-2 

tests. The average inorganic field train blank recovered from seven trains in this evaluation was 

2.48 mg/dscm based on the average sample volume collected during the field tests. 

The proof train recovery blank contained 0.32 mg/dscm and 2.23 mg/dscm of organic and 

inorganic residue respectively based on the average sample volume collected during the field 

tests. 

2.2 Method Recovery 

 Method recovery is summarized below: 

• Sulfuric acid recovered during 10 test runs collection averaged 87.4 % with a relative 

standard deviation of 15%. 

• The individual recoveries ranged from 82.5% to 95.7%. 

Once collected, sulfuric acid is retained in the proposed CPM method. Additional 

laboratory tests are underway to identify an appropriate organic CPM material for use as a static 

spike and a potential audit material. 

2.3 Method Detection Estimate 

The detection limit of the filterable and condensable particulate can be determined based 

on the uncertainty in the data from the mass collected during the method evaluation tests. While 

these detection limits may be biased high because the mass may not be within a factor of five of 

the limits, they represent a best estimate of the detection limit from this evaluation of 

Methods 201A and 202. Table 2-1 summarizes the data on detection limits based on this set of 

tests. 

Table 2-1. Estimated Method 201A/202 Detection Limits 

Parameter 

Average 

Mass 

(mg) 

Degrees of 

Freedom (n-1) 

(mg) 

Standard 

Deviation 

Estimated 

Detection (mg) 

Total Filterable PM* 22.61 39 1.51 2.54 

PM10* 21.21 39 0.85 1.44 

PM2.5* 20.41 39 0.8 1.35 

Inorganic CPM** 4.05 6 1.1 3.5 

Organic CPM** 1.28 6 0.63 2.0 

Total CPM** 5.33 6 1.7 4.1 

**Based on Field Recovery Train Blanks
3-1 

3.0 EXPERIMENTAL APPROACH 

3.1 Introduction 

This section describes the experimental approach to identify and conduct sampling at a 

representative site. 

3.2 Field Test Site 

EPA selected the field test site based on several criteria. Emphasis was placed on finding 

an industrial stationary source that generates both organic and inorganic condensable particulate 

matter emissions. Two sites were evaluated: a coal-fired steam boiler and a hog fuel-fired boiler. 

The following characteristics were assessed to determine if the sites were suitable for the 

evaluation tests for these methods. The stack gas composition is important to successfully 

challenge the proposed methods. 

• Stack gases composition based on presite samples or recent stack tests 

- Organic CPM > 1 mg/dscm (compounds with vapor pressure less than 

hexadecane) 

 - Inorganic CPM > 2 mg/dscm (H2SO4, HNO3) 

 - SO2 (25 - 150 ppmv) 

 - NOx (> 50 ppmv) 

 - Moisture content between 5% and 15% 

• Facility Characteristics 

 - Cooperation of facility and site personnel 

 - Industrial sector 

 - The facility has existing stack testing infrastructure (e.g., utilities, sampling 

ports). 

 - Ease of access and space for quadruplicate sampling trains. 

 - Located within 250 miles of Research Triangle Park, NC

Based on stack gas composition and facility characteristics, EPA selected the hog fuelfired boiler at a paper mill as a test site to evaluate the proposed Methods 201A and 202. The 

facility, located in eastern North Carolina, is a bleached kraft pulp and paper mill that produces 

uncoated freesheet, Xerographic, offset, opaque, and trade book papers. 

The mill conducted stack sampling using EPA Method 5 and OTM 28 the week of 

March 31, 2009. Total Method 5 particulate was approximately 740 mg/dscm. CPM was found 
3-2 

in both the inorganic and organic fractions. Approximately 70 mg/dscm of inorganic CPM and 

3.0 mg/dscm of organic CPM were found during these tests. Based on these preliminary results, 

EPA determined that it is necessary to collect between 1.5 and 3.0 cubic meters of stack gas to 

evaluate the proposed methods. Considering the preliminary CPM measurements and the 

sampling facilities, EPA determined this site was acceptable for the method validation tests. 

Testing of the No. 2 hog fuel-fired boiler (2HFB) was completed the week of June 8, 2009. 

3.2.1 Process/Emission Unit Description 

The emission unit for testing is a hog fuel-fired boiler (ID. No. 2HFB) that provides 

steam to the facility processes. The boiler also can co-fire dewatered sludge from the on-site 

wastewater treatment facility, waste oils, and coal. Normal operation process rate is 300 to 

500 thousand pounds per hour of steam. Particulate matter emissions from the boiler are 

controlled using a set of multi-cyclones and an electrostatic, gravel-bed filter (in series). The mill 

operates 24 hours a day, 7 days per week; however, the operation of the boiler varies (i.e., 

swings) based upon steam demands from mill processes. 

3.2.2 Sampling Locations 

The boiler stack has an internal diameter of 148 inches (approximately 12 feet). The stack 

is fitted with four 6-inch sampling ports. The stack is insulated and the distance from the 

sampling port cover to the stack wall is 16 inches. Test ports are located 576 inches, or 3.9 stack 

diameters downstream of the stack breaching, and approximately 100 feet, or 8.1 stack diameters 

upstream of the stack exit. A rough diagram of the stack and sampling configuration is shown in 

Figure 3-1. 
3-3 

100 feet

48 feet

From ESP

Breaching

Sampling Ports

Figure 3-1. No. 2 HFB Stack Sampling Location 

3.2.3 Sampling Platform 

The stack is equipped with a covered, circular sampling platform. The walls of the 

platform are 82 inches (approximately 7 feet) from the stack. Access panels in the walls (and two 

support hooks in the ceiling) across from each port provide sufficient space to maneuver the 

sampling trains. 
3-4 

3.3 Field Test Procedures 

The field test and procedures followed the Category III QAPP/Site Specific Field Test 

Plan: Evaluation and Improvement of Condensable Particulate Matter Measurement, which is 

included in this report as Appendix A. Statistical methods followed Method 301 to determine 

precision and bias. 

3.3.1 Sampling and Analytical Methods 

Proposed Methods 201A and 202 served as the sampling and analytical methods (74 FR 

12970). Sampling was performed in a stack of sufficient cross sectional area to meet EPA 

requirements for minimal obstruction of stack flow. Probe nozzle configuration was less than 

2 percent of the stack area. The port location was a minimum of eight stack diameters upstream 

from a flow perturbation and at least two stack diameters downstream from flow perturbation 

including the stack exhaust. 

The sampling procedure was followed except that no traverse of the emission source 

stack was necessary. Instead, the point of average velocity was determined across the stack 

diameter and single point, isokinetic sampling was performed at that location. The quadruplicate 

train sampling met the requirements in proposed EPA Method 201A for flow obstructions and 

isokinetic sampling. 

3.3.2 Statistical Methods 

Data from the quadruplicate train results were statistically evaluated following 

Method 301 to determine the performance of the method relative to bias and precision. The 

respective method is considered to be a valid method if the precision criteria is met (% RSD <50) 

and the bias is not significantly different from zero or can be corrected with a correction factor 

between 0.7 and 1.3. 

Spike recovery between 70 and 130% is considered valid without bias. If sample 

recovery meets Method 301 precision requirements and falls out of this range of recovery, bias 

will be determined according to Method 301 and reported with the results. 
3-5 

3.4 Experimental Design Matrix 

Each sampling train was configured to perform proposed Method 201A for filterable 

particulate and proposed Method 202 for condensable particulate as described in Appendix B. 

Based on the results of samples collected during a previous compliance test for total filterable 

and condensable particulate conducted by the facility the experimental design chosen for this 

evaluation involved collecting approximately 1.5 cubic meters of stack gas to ensure sufficient 

sample volume to yield enough mass to evaluate each of the test methods. The experimental 

matrix shown in Table 3.1 includes collecting 10 quadruplicate samples to yield a minimum of 

eight valid quadruplicate train tests for statistically evaluation of the performance of these 

methods. 

For the field test runs, the following sampling scheme was followed: two (2) complete 

quadruplicate sampling test runs were collected simultaneously. In each of the quadruplicate 

sampling train configurations two of the four trains were spiked and two of the four 

quadruplicate trains were unspiked in each sampling run. Spiking solutions were added to the 

first (dropout) impinger. Spiking was performed with a condensable inorganic compound, 

sulfuric acid, and a condensable organic compound, (heptadecane). The organic spiking material 

was selected based on thermodynamic calculations using theoretical vapor pressure to estimate 

the expected recovery while still challenging the condensable sampling and analysis method. The 

inorganic spiking material, sulfuric acid was selected even though it exceeds the theoretical 

requirements for 100% retention in the proposed revision to Method 202 because it is the most 

volatile common inorganic condensable available. 

Five (5) milligrams of heptadecane were added to 20 mL of dionized ultrafiltered water 

contained in the knockout impinger of each spiked train. One hundred fifty (150) milligrams of 

sulfuric acid were added to the same 20 mL of water in the knockout impinger of the spiked 

trains. Spike recovery between 70 and 130% is considered valid without bias. If sample recovery 

meets Method 301 precision requirements and falls out of this range of recovery, bias is 

determined according to Method 301 and reported with the results. If less than 70% of the 

organic spike is recovered the CPM bias of the method is based on the sulfuric acid recovery. 
3-6 

Table 3-1. Method 201A/202 Sampling Matrix 

Test Run 

Spiked 

Trains 

Unspiked 

Trains 

1,2 B,D A,C 

3.4 B,D A,C 

5,6 B,D A,C 

7 (simultaneous with 8) B,D A,C 

8 (simultaneous with 7) B,C A,D 

9,10 B,D A,C 

Proof Blank NA X 

Train Blank1 NA X 

Train Blank 2 NA X 

Train Blank 3 NA X 

Train Blank 4 NA X 

Train Blank 5 NA X 

Train Blank 6 NA X 

Train Blank 7 NA X 

A = Quadruplicate Train A 

B = Quadruplicate Train B 

C = Quadruplicate Train C 

D = Quadruplicate Train D 

NA = Not Applicable 

X = Single Train Recovery

 

Traversing the stack to obtain representative emissions results was not performed during 

validation tests. Instead, the point of average velocity was determined across the stack diameter 

and single point, isokinetic samples were collected at that location in the stack. Quadruplicate 

sampling runs were paired so that 8 sampling trains were simultaneously collected. 
4-1 

4.0 RESULTS AND DISCUSSION 

A summary of the results from the field evaluation of proposed method 201A and 

Method 202 is presented in this section. For this field test, 10 quadruplicate train samples were 

planned and completed. Figure 4-1 shows the configuration of each sampling train. Two sets of 

duplicate sampling trains were used to collect a total of four simultaneous samples for each test 

run. Two of the sampling trains were spiked with known quantities of condensable particulate 

material and two were used to measure the native amount of particulate from the source. 

Filterable particulate results are summarized in Section 4.1. Condensable particulate results are 

summarized in Section 4.2. Combined filterable and condensable particulate results are 

summarized in Section 4.3. 

Heated Box

Filter

Orifice

Manometer

Dry Gas

Meter

By-Pass

Valve

Pump

Main

Valve

Vacuum

Gauge

Vacuum

Line

Water Bath

(<30oC/ 85oF)

Condenser

Thermocouples

Empty

Silica Gel

Rec

(300 grams)

irculation

Pump

Check Valve

Temperature Sensor

Ice Bath

Stack

Wall

Manome ter

S-Type Pitot Tube

Figure 4-1. Configuration of Each Sampling Train 

Statistical analysis of the filterable material collected in each size fraction was performed 

based on the assumption that individual tests with the quadruplicate sampling train configuration 

collected identical samples on a milligram per cubic meter basis. The average standard deviation 

of each quadruplicate sampling run was calculated to assess the precision of the method. Results 
4-2 

are summarized for each reportable filterable particulate fraction (i.e., PM-Total, PM10 and 

PM2.5). 

4.1 Filterable Particulate Results and Discussion 

A summary of the total filterable particulate results from all 10 quadruplicate train tests is 

shown in Table 4-1. The average total particulate results from each of the 10 quadruplicate train 

tests is shown in Figure 4-2. Statistical analysis of the total filterable material collected in 40 test 

runs shows an average standard deviation of 1.63 milligrams per dry standard cubic meter 

(mg/DSCM). Uncertainty in the total particulate data is a function of the uncertainty of the 

individual cyclone and filter precision. When small amounts of particulate mass are captured in 

one size fraction compared to others the error in recovery leads to higher uncertainty. The source 

emissions sampled in this method evaluation were dominated by fine filterable (PM2.5) 

particulate, which leads to more uncertainty in the PM10 and total filterable particulate. 

Table 4-1. Total Filterable Particulate Matter Results from Method 201A Evaluation 

Run 

Number Train A Train B Train C Train D Average 

α

(Standard 

Deviation) di di

2

1 25.53 23.14 23.53 27.21 24.85 1.89 4.08 16.61 

2 17.98 18.15 17.38 21.44 18.74 1.83 4.06 16.49 

3 17.71 17.38 17.05 18.33 17.62 0.55 1.29 1.65 

4 22.14 18.97 21.58 23.29 21.49 1.83 4.32 18.69 

5 22.19 21.75 22.64 23.56 22.54 0.77 1.81 3.28 

6 22.08 22.00 22.38 24.04 22.62 0.96 2.04 4.17 

7 22.89 20.87 21.09 23.94 22.20 1.48 3.07 9.45 

8 25.41 22.57 22.74 32.36 25.77 4.58 9.79 95.84 

9 24.93 24.41 25.33 23.44 24.53 0.82 1.89 3.57 

10 25.34 24.88 24.67 28.09 25.75 1.59 3.42 11.67 

10-Run 

Average 22.62 21.41 21.84 24.57 22.61 1.63 NA NA 

 Σ di

2

 181.43

 n 40

 SDs

 1.51

 %RSD 6.66
4-3 

0

5

10

15

20

25

30

35

40

45

50

1 2 3 4 5 6 7 8 9 10 10-Run

Run Number Average

Total Particulate (mg)

> PM10 PM2.5 to PM10 < PM2.5 Filterable Inorganic Particulate Organic Particulate

47%

57%

47% 52%

60% 54% 55% 70% 59% 64%

56%

Figure 4-2. Average Total Particulate Collected by Method 201A 

A summary of the PM10 filterable particulate results are shown in Tables 4-2. The 

average standard deviation of 40 test runs was 1.09 mg/dscm. PM10 filterable results are the sum 

of the material caught in the PM2.5 cyclone and on the final particulate filter. The PM10 results 

are strongly influenced by the predominant PM2.5 filterable particulate mass. Less uncertainty is 

shown for the PM10 filterable particulate results than the total particulate mass as indicated by the 

smaller average standard deviation from the test runs for this particulate fraction. 
4-4 

Table 4-2. PM10 Filterable Particulate Results from Method 201A Evaluation 

Run 

Number Train A Train B Train C Train D Average 

α

(Standard 

Deviation) di di

2

1 25.16 22.33 22.48 25.14 23.78 1.59 2.83 8.01 

2 17.38 17.45 15.77 18.89 17.37 1.27 3.11 9.68 

3 17.23 16.79 16.24 17.18 16.86 0.46 0.99 0.98 

4 21.28 18.43 20.32 21.53 20.39 1.40 3.10 9.58 

5 21.64 20.80 20.18 22.59 21.30 1.04 2.40 5.77 

6 21.34 21.17 21.60 22.90 21.75 0.78 1.72 2.97 

7 20.89 19.04 18.06 20.85 19.71 1.40 2.83 7.98 

8 24.41 21.70 21.72 23.58 22.85 1.36 2.71 7.37 

9 24.13 22.90 24.20 22.87 23.52 0.74 1.32 1.75 

10 24.60 24.13 23.80 25.79 24.58 0.87 1.98 3.92 

10-Run 

Average 21.81 20.47 20.44 22.13 21.21 1.09 NA NA 

 Σ di

2

 58.02 

 n 40

 SDs

 0.85 

 %RSD 4.01 

The data in Table 4-2 is shown in bar graph from in Figure 4-3. The stacked bars clearly 

show the small contribution of coarse particulate (PM2.5 to PM10) to the total in the PM10 mass 

classification. 

0

5

10

15

20

25

30

35

40

45

50

1 2 3 4 5 6 7 8 9 10 10-Run

Average Test Run Number

< PM2.5 Filterable PM2.5 to PM10

Figure 4-3. Filterable PM10 Particulate of Unspiked Trains 
4-5 

A summary of the PM2.5 filterable particulate results are shown in Tables 4-3. The PM2.5

filterable particulate results account for the major fraction of the particulate mass captured during 

these tests. These data provide a representative estimate of the anticipated performance of 

proposed Method 201A when source emissions are well above the detection limit for this 

method. 

Table 4-3. PM2.5 Filterable Particulate Results from Method 201A Evaluation 

Run 

Number Train A Train B Train C Train D Average 

α

(Standard 

Deviation) di di

2

1 24.41 21.65 21.07 22.88 22.50 1.48 3.34 11.18 

2 16.90 16.91 15.16 17.36 16.58 0.97 2.20 4.84 

3 16.57 16.37 15.26 16.02 16.05 0.58 1.31 1.72 

4 20.60 17.90 19.23 20.86 19.64 1.37 2.96 8.77 

5 21.03 20.08 19.44 20.15 20.18 0.65 1.59 2.53 

6 21.07 20.98 20.69 22.16 21.23 0.64 1.47 2.15 

7 20.36 18.57 17.43 19.55 18.98 1.27 2.93 8.58 

8 23.73 20.82 20.87 22.84 22.07 1.45 2.90 8.43 

9 23.51 22.38 23.48 22.18 22.89 0.71 1.33 1.77 

10 24.29 23.83 23.23 24.54 23.97 0.58 1.31 1.73 

10-Run 

Average 21.25 19.95 19.58 20.86 20.41 0.77 NA NA 

 Σ di

2

 51.70 

 n 40

 SDs

 0.80 

 RSD 3.94 

DL 1.35 

Figure 4-4 shows a bar graph of the filterable PM2.5 mass normalized for the stack 

volume collected for each train in the 10 quadruplicate test runs. The 10-run average is also 

displayed in the last grouping. 
4-6 

0.00

5.00

10.00

15.00

20.00

25.00

30.00

1 2 3 4 5 6 7 8 9 10 10-Run

Average

Run Number

< PM2.5 Filterable

Filterable PM 2.5 (mg/dscm)

Figure 4-4. Filterable PM2.5 Particulate of Unspiked Trains 

Results for the recovery of filterable PM2.5 from each of the individual 40 test runs are 

shown in Table 4-4 and graphically in Figure 4-5. The standard deviation of each of the test runs 

are displayed and range from a low of 0.6 to a maximum of 1.5. The average standard deviation 

of the ten runs is 0.8. The 95% upper confidence limit of the standard deviation (precision) is 

1.6. The average standard deviation of the simultaneous sampling trains for all 40 tests, 

multiplied by Students t for 39 degrees of freedom, can be used as a rough estimate the detection 

limit (DL) for this method for PM2.5. The limit of detection for this particulate matter fraction is 

1.35 mg/dscm given the uncertainty at these concentrations. 
4-7 

Table 4-4. PM2.5 Filterable Particulate Mass 

Run 

Number Train A Train B Train C Train D Average α di di

2

1 24.41 21.65 21.07 22.88 22.50 1.48 3.34 11.18 

2 16.90 16.91 15.16 17.36 16.58 0.97 2.20 4.84 

3 16.57 16.37 15.26 16.02 16.05 0.58 1.31 1.72 

4 20.60 17.90 19.23 20.86 19.64 1.37 2.96 8.77 

5 21.03 20.08 19.44 20.15 20.18 0.65 1.59 2.53 

6 21.07 20.98 20.69 22.16 21.23 0.64 1.47 2.15 

7 20.36 18.57 17.43 19.55 18.98 1.27 2.93 8.58 

8 23.73 20.82 20.87 22.84 22.07 1.45 2.90 8.43 

9 23.51 22.38 23.48 22.18 22.89 0.71 1.33 1.77 

10 24.29 23.83 23.23 24.54 23.97 0.58 1.31 1.73 

10-Run 

Average 21.25 19.95 19.58 20.86 20.41 0.77 NA NA 

 Σ di

2

 51.70 

 n 40

 SDs 0.80 

 RSD 3.94 

 DL 1.35 

0.00

5.00

10.00

15.00

20.00

25.00

30.00

1 2 3 4 5 6 7 8 9 10 10-Run

Run Number Average

PM (mg/dscm)

Train A Train B Train C Train D

M301 Precision = 1.61mg/dscm

s = 1.5

s = 0.6

s = 1.0

s = 1.4 s = 0.7 s = 0.6

s = 1.3

s = 1.5 s = 0.7 s = 0.6

X= 0.8

Figure 4-5. PM2.5 Filterable Mass 
4-8 

4.2 Condensable Particulate Results and Discussion 

Recovery and precision of the condensable particulate matter collection for the field 

evaluation tests are presented in this section. In addition, results and discussion of the individual 

inorganic and organic spike recovery are presented. Test results from unspiked trains were used 

to determine the method precision. 

Results of the unspiked condensable particulate matter collected in the evaluation tests 

are shown in Table 4-5. Table 4-5 includes the results of the inorganic and organic fractions in 

addition to the combined condensable particulate matter mass. Sampling Trains A, B, C, and D 

were conducted simultaneously for each test run. Results for test runs 1 and 2 showed a higher 

standard deviation than subsequent test runs. However, all data was used in the statistical 

evaluation of the data. Results are not corrected for proof train or field train blank results. 

Table 4-5. Method 202 Average CPM (ug) of all Sample Trains by Fraction 

Test 

Run 

Train A 

Inorganic 

Train A 

Organic 

Train C 

Inorganic 

Train C 

Organic 

Total 

Train A 

Total 

Train C Average 

Difference 

(di) di

2

Standard 

Deviation 

1 26.28 3.70 16.17 2.67 29.98 18.83 24.4 11.14 124.17 7.88 

2 22.35 0.99 11.29 1.42 23.34 12.71 18.0 10.63 113.00 7.52 

3 9.32 1.06 15.85 0.97 10.38 16.81 13.6 6.43 41.32 4.55 

4 9.66 1.16 12.39 0.98 10.82 13.37 12.1 2.55 6.48 1.80 

5 16.03 1.35 12.19 1.02 17.38 13.21 15.3 4.17 17.35 2.95 

6 12.92 2.95 12.77 1.06 15.87 13.82 14.8 2.05 4.19 1.45 

7 12.43 1.21 12.26 0.94 13.64 13.20 13.4 0.44 0.19 0.31 

8 9.31 1.12 5.47 0.90 10.43 6.36 8.4 4.07 16.54 2.88 

9 11.28 1.11 15.59 1.10 12.39 16.68 14.5 4.30 18.46 3.04 

10 10.76 4.09 9.53 1.02 14.85 10.55 12.7 4.30 18.45 3.04 

10-run 

Ave 14.03 1.87 12.35 1.21 15.91 13.56 14.7 2.35 5.53 1.66 

 Σ di

2

365.67 

 n 20 

Sdu 3.02 

Sm 14.7 

RSD 20.52 
4-9 

Figure 4-6 shows the total M-202 CPM collected from the unspiked trains in each of the 

ten test runs. The stacked bars show the inorganic and organic contribution for each pair of 

unspiked trains in a run. The horizontal bars show the average of the total condensable 

particulate matter between the two trains. The standard deviation calculated according to the 

procedures in Reference Method 302 is shown above the paired bars as σ. The average standard 

deviation of all 10 test sets is 1.7 mg/dscm, shown above the 10-run average bars. The precision 

as defined by Method 301 is 4.28 mg/dscm which corresponds to a DL at 95% confidence level 

of 7.69 mg/dscm. 

Total CPM by Each Test Run on Trains A and C (Unspiked)

0

5

10

15

20

25

30

35

1 2 3 4 5 6 7 8 9 10 10-run

Run Number Average

CPM (mg/dscm)

Train A Inorganic Train A Organic Train C Inorganic Train C Organic Average CPM Per Run

M301 Precision = 4.24 mg/dscm

σ = 7.9

σ = 7.5

σ = 4.6

σ = 1.8

σ = 3.0

σ = 1.5

σ = 0.3

σ = 2.9

σ = 3.0

σ = 3.0

σ = 1.7

Figure 4-6. Condensable Particulate Material Distribution in Unspiked Trains 

Figure 4-7 shows the average of the unspiked condensable mass for the test set. The 

proportion of inorganic condensable material in each fraction of the test samples is shown as a 

percent in the stacked bar for each test run. Inorganic CPM accounts for 80 to 93% of the total 

CPM particulate mass from these tests. 
4-10 

0

5

10

15

20

25

1 2 3 4 5 6 7 8 9 10 10 Run 

Average

Run Number

Inorganic Particulate Organic Particulate

87%

93%

93% 91%

92% 86% 92%

88%

92%

80%

90%

Total Particulate (mg)

Figure 4-7. Average Condensable Particulate Matter for Paired Sampling Trains 

4.3 Spiked Condensable Field Train Results 

Two of each of the simultaneous quadruplicate trains collected for each test run were 

spiked with an inorganic recovery standard, sulfuric acid, and an organic recovery standard, 

heptadecane. These materials were spiked for two reasons; first to determine if the material was a 

satisfactory starting point for a stationary source method audit sample and second to evaluate the 

performance of the condensable particulate method to retain material once it was collected. 

4.3.1 Inorganic Condensable Recovery Results 

The average inorganic condensable material from each of the test runs is shown in 

Figure 4-8. The stacked bars show the native condensable particulate at the bottom and the 

spiked fraction at the top. 
4-11 

0

20

40

60

80

100

120

1 2 3 4 5 6 7 8 9 10 10-Run 

Average

Run Number

CPM (mg/dscm)

Unspiked Trains Spiked Trains

Figure 4-8. Average Recovered CPM of Inorganic Particulate 

The condensable particulate results of the spiked and unspiked train samples are shown in 

Table 4-6. 

Table 4-6. Percent Recovery of Inorganic CPM 

Run# 

Spiked Train 

Average 

(mg/dscm) 

Unspiked Train 

Average 

(mg/dscm) % Recovery 

1 99.29 21.22 85.44 

2 93.93 16.82 84.40 

3 90.61 12.58 85.39 

4 92.26 11.02 88.91 

5 89.52 14.11 82.54 

6 100.30 12.84 95.72 

7 89.51 12.35 84.45 

8 90.07 7.39 90.49 

9 91.15 13.43 85.06 

10 93.58 10.15 91.31 

10-Run Average 93.02 13.19 87.37 

Standard Deviation 3.90 3.76 4.09 

Figure 4-9 shows the inorganic mass recovered for spiked and unspiked test results. The 

average amount spiked in mg/dscm is shown as a doted line at 91.4 mg/dscm. For perspective the 

average field train blank of 2.43 mg/dscm is also shown in Figure 4-9. 
4-12 

Inorganic CPM Recovery of Spiked and Unspiked Trains

0

20

40

60

80

100

120

1 2 3 4 5 6 7 8 9 10 10-Run

Run Number Average

CPM (mg/dscm)

Train A - Unspiked Train C - Unspiked Train B - Spiked Train D - Spiked

Spiked Amt.= 91.4 mg/dscm Ave. FTB = 2.43 mg/dscm

Figure 4-9. Inorganic Mass for All Test Runs 

To compare the results from sampling train to sampling train over the 40 test runs, the 

native material from the source must be subtracted from the total recovered condensable 

material. The difference is the amount of spiking material retained by the sampling train. Results 

from the unspiked sampling train were normalized based on the amount of stack gas sampled. 

Figure 4-10 shows the inorganic spike recovery for all test runs. The ascending and descending 

whiskers represent the 98% confidence limits around the mean for the simultaneous train runs. 

The diamond represents the average of the two simultaneous train runs. 
4-13 

Inorganic Recovery by Spiked Train

0

10

20

30

40

50

60

70

80

90

100

1 2 3 4 5 6 7 8 9 10 10-Run

Run Number Average

Inorganic Recovery (mg/dscm)

Train B Train D Average Spike Level

Inorganic Spike = 91.4 mg/dscm

Figure 4-10. Inorganic Spike Recovery for All Test Runs 

Based upon this data, one can conclude that H2SO4 would be an acceptable audit material 

for use with Method 202 in either its present state or a future revision. Recovery of sulfuric acid 

spiked directly into the first impinger of the sampling train meets the reference Method 301 

criteria for a valid sampling method. The inorganic CPM recovery also reveals some loss in the 

sulfuric acid spike that may be due to recovery, handling, or analysis bias with the method. 

4.3.2 Organic Condensable Results 

The average organic recovery from spiked and unspiked sampling trains is shown in 

Table 4-7. 
4-14 

Table 4-7. Organic CPM Recovery Results 

Unspiked (mg/dscm) Spiked (mg/dscm) 

Run # Train A Train C Average Train B Train D Average

1 3.70 2.67 3.18 1.29 1.91 1.60 

2 0.99 1.42 1.21 1.69 1.52 1.61 

3 1.06 0.97 1.01 1.01 1.17 1.09 

4 1.16 0.98 1.07 1.36 1.50 1.43 

5 1.35 1.02 1.19 1.18 1.60 1.39 

6 2.95 1.06 2.01 1.15 1.43 1.29 

7 1.21 0.94 1.07 1.11 1.28 1.20 

8 1.12 0.90 1.01 0.73 1.06 0.90 

9 1.11 1.10 1.10 1.31 1.29 1.30 

10 4.09 1.02 2.55 1.03 1.58 1.30 

10-Run Average 1.87 1.21 1.54 1.19 1.43 1.31 

Standard Deviation 1.21 0.53 0.77 0.26 0.24 0.22 

The results from all organic CPM fractions for all sampling runs is shown graphically in 

Figure 4-11. 

Organic CPM Recovery of Unspiked and Spiked Trains

0

1

2

3

4

5

1 2 3 4 5 6 7 8 9 10 10-Run

Run Number Average

CPM (mg/dscm)

Train A - Unspiked Train C - Unspiked Train B - Spiked Train D - Spiked

Ave. FTB = 0.78 mg/dscm

Spiked Amt.= 3.05 mg/dscm

Figure 4-11. Organic CPM Results from All Sampling Train Runs 
4-15 

 In Figure 4-11 blue columns represent the unspiked trains while red represent the spiked 

trains. The recovered residual organic mass shown for the spiked trains are NOT normalized for 

the background present in the unspiked. Although the overall red (spiked) results are greater than 

the blue (unspiked) bars for selected run numbers, the average recovery of spiked trains is 

approximately the same as the unspiked trains. Many of the results are at or near the field train 

blank value for both the trains spiked with organic CPM and those not spiked. 

4.4 Combined Filtered and Condensable Particulate Matter Results and Discussion 

Figure 4-12 shows the average particulate collected from the un-spiked trains for each 

fraction collected. All ten runs and a 10-run average are included. Filterable PM2.5 accounts for 

50 and 75% of the total particulate mass collected during sampling runs. Inorganic CPM 

accounts for the second highest particulate catch ranging from 22 to 46% of the total particulate 

concentration. Organic CPM was approximately the same order of magnitude as the organic field 

train blank. Facility had little or no organic emissions upon which to base the precision of the 

organic CPM. 

0

5

10

15

20

25

30

35

40

45

50

1 2 3 4 5 6 7 8 9 10 10-Run

Run Number Average

Mass (mg/DSCM)

> PM10 PM2.5 to PM10 < PM2.5 Filterable Inorganic Particulate Organic Particulate

43%

57%

47% 52%

60% 54% 55% 70% 59% 64%

56%

46%

40%

32%

37%

34%

47%

34%

22%

35%

34%

26%

Figure 4-12. Total Particulate by Sampling Train Fraction 
5-1 

5.0 QUALITY CONTROL AND QUALITY ASSURANCE 

This section provides information on the proof train blanks for glassware and equipment 

prior to their use in field evaluation tests as well as field train blanks that demonstrate the 

cleanliness of the sampling trains between sampling runs. 

5.1 Combined Inorganic and Organic Field Train Blank Results 

The total CPM field train blank mass corrected for the average volume collected during 

the field tests field train blanks is shown in Table 5-1 and Figure 5-1. Blank results are reported 

in both total milligrams and normalized to the average stack gas volume (1.65 dscm) collected in 

the 40 sampling trains collected during field tests. 

Table 5-1. Field Train Blank CPM Summary 

 Inorganic Organic 

Run # mg mg/dscm mg mg/dscm 

PB-1 3.65 2.21 0.52 0.32 

FTB-1 4.46 2.71 1.08 0.66 

FTB-2 2.8 1.70 2.12 1.29 

FTB-3 4.21 2.55 1.29 0.78 

FTB-4 4.17 2.53 1.65 1.00 

FTB-5 6.15 3.73 0.07 0.04 

FTB-6 3.27 1.98 1.43 0.87 

FTB-7 3.29 2.00 1.31 0.79 

FTB Average 4.05 2.46 1.28 0.78 

 Figure 5-1 also shows the organic and inorganic train blank reported by the analysis 

laboratory for these tests. Horizontal lines have been added to show both the inorganic and 

organic field reagent blank values to demonstrate that field train blank residual CPM contributed 

to but was not entirely responsible for the field train blank results. The field blank results 

provides a screening method for revealing the potential source of contamination or recovery 

issues. 
5-2 

Concentration of CPM in Proof and Field Train Blanks

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

PB-1 FTB-1 FTB-2 FTB-3 FTB-4 FTB-5 FTB-6 FTB-7 FTB Average

Run Number

CPM (mg/dscm)

Inorganic Recovery Organic Recovery

PB = Proof Blank

FTB = Field Train Blank

Inorganic Field Reagant 

Blk = 1.24 mg/dscm

Organic Field Reagant 

Blk = 0.58 mg/dscm

Figure 5-1. Proof and Field Train Blank CPM Recovery 

5.2 Inorganic Field Train Blank 

The mass of inorganic field blank collected in each of the sampling trains corrected for 

the volume of gas sampled from the source is shown in Figure 5-2. The inorganic field blank 

recoveries are shown in dark blue and the proof blank PB-1 is shown in light blue. The field train 

blank average is also included (shadow blue). The average of seven field train blanks is 

approximately equal to the proof train blank. For comparison the inorganic field reagent blank 

was 1.24 mg/dscm. 
5-3 

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

PB-1 FTB-1 FTB-2 FTB-3 FTB-4 FTB-5 FTB-6 FTB-7 FTB

Average

Run Number

Inorganic Mass (mg/dscm)

PB = Proof Blank

FTB = Field Train Blank

Figure 5-2. Inorganic Proof and Field Train Blank Results (mg/dscm) 

5.3 Organic Field Train Blank 

Organic field and proof train blank results are shown in Figure 5-3. The organic field 

train blank data show low residual approximately twice the proof train blank. Laboratory reagent 

and field blank results were equivalent to the proof train blank demonstrating the reagents and 

glassware contained very low levels of organic blank at or near the detection limit of the 

analytical balance used to measure the residual weight. In comparison, the organic recoveries 

from the field train blanks for all but field train blank 5, there appears contain additional organic 

residue (0.8 mg/dscm) that is either an additional contaminant or that is not being recovered 

between sampling runs. 
5-4 

Mass of Organic CPM for Blanks 

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

PB-1 FTB-1 FTB-2 FTB-3 FTB-4 FTB-5 FTB-6 FTB-7 FTB Average

Run Number

PB = Proof Blank

FTB = Field Train Blank

Figure 5-3. Organic Proof and Field Train Blank Results (mg/dscm) 
6-1 

6.0 METHOD EVALUATION PROCEDURES AND CALCULATIONS 

The quality assurance objectives are given below for the measurements made in the field 

evaluation tests with the proposed Method 201A and 202 combined train. Paired sampling trains 

with collocated probes collecting samples at similar sampling rates were used during the field 

tests. Two sets of paired trains were used to collect quadruplicate samples for each test run. For 

this field test, precision and bias was calculated according to EPA Method 301 (Appendix B) for 

the inorganic CPM. Evaluation objectives for these tests are shown in Table 6-1. 

Table 6-1. Method Evaluation Objectives for the Dry Impinger Condensable 

Particulate Method 

Method

Bias 

(Percent Recovery)

Precision 

(% RSD)

Proposed Method 202 70 - 130 % 30 % 

To meet Method 301 requirements, 10 quadruplicate sampling runs were performed, with 

two of the four quadruplicate trains spiked and two of the four quadruplicate trains unspiked in 

each sampling run. All 10 quadruplicate train sampling runs were used in precision and bias 

calculations. Spiking solutions were added to the first (dropout) impinger in the proposed 

Method 202 sampling train used in this method evaluation. The dropout impinger in every train, 

spike or unspiked contained 20 mL of ultra-filtered, deionized water at the start of each test. This 

addition to the method was necessary to accommodate the Method 301 spikes used to evaluate 

CPM precision and bias. The dropout impinger in two of each of the quadruplicate trains for 

each run was spiked with 1.0 mL of inorganic CPM (~150 mg/mL sulfuric acid in water) and 1.0 

mL of organic CPM (~5 mg/mL heptadecane in toluene). All spikes were added with a calibrated 

disposable tip repeating pipette accurate to 1.0 mL ±2%. In addition, seven field train blanks 

were collected. Data quality objectives for CPM are shown in Table 5-1. There is no audit 

method to spike filterable particulate into samples collected in these tests. Therefore, precision of 

the filterable particulate collection was determined and reported. 
6-2 

6.1 Precision 

The objective for precision for the proposed Method 202 is less than 30% relative 

standard deviation. A mean and standard deviation of the concentrations of spiked samples will 

be calculated from 10 runs of quadruplet paired sampling trains. 

 The precision (SDs) of the measurements from the spiked samples is determined by 

calculating the difference, di, between the pairs of spiked measurements for each quadruplicate 

train. The pooled standard deviation of the spiked values, or the precision, SDs, is determined 

using Equation 6-1, where n equals the number of sampling runs (n = 10 in this study, if all runs 

are complete): 

n

d

SD i

S

2

2 ∑ = (6-1) 

6.2 Bias 

The bias (B) of the analyte spikes will be calculated from the recovery of the analyte 

from the spike, as follows: 

 B = Sm – Mm – CS (6-2) 

where: 

 B = bias at the spiking level 

 Sm = mean of the measured concentrations of the spiked samples 

Mm = mean of the concentrations of the unspiked samples 

 CS = calculated value of the concentration of the spike 

The bias for each spiked impinger set will be tested to determine if it is significantly 

different from zero at the 95% confidence level. If the significance test shows that the bias is 

significantly different from zero, a correction factor, CF, will be estimated for each analyte using 

Equation 6-3. 

CS

B

CF

+

=

1

1

 (6-3) 
6-3 

The objective for bias for this method is less than 30%, calculated according to EPA 

Method 301.