# 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 Polic y 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. 3-05i 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 reco mmendation for use.ii Acknowledgements
We wish to acknowledge the contributions of the following i ndividuals to the success of this program:

• Michael Hartman and his staff at Air Tech LLC for fie ld 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 Gro up for proposed Method 202 preparation and analysis.

• Jennifer Colby and Tracey Footer at Eastern Research Gro up for Method 301 data analysis of the field test data.iii Abstract
This report presents results of a field evaluation of pro posed modifications to EPA Methods 201A and 202. These methods are used to quantify fine filt erable and condensable particulate matter (PM) emissions. The field tests eva luated the revised methods as proposed in the Federal Register on March 25, 2009 (74 FR 12970). The propose d methods were based on earlier laboratory experiments. The purpose of these f ield tests was to evaluate the performance of the methods in the field and to determine whether meth od precision and bias are acceptable based on the approach specified in EPA Method 301. The fiel d tests were completed on a hog fuel-fired boiler at a pulp and paper plant. This report cont ains 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 Re sults 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............................................

................................................... ................... 6-2v 

### 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 fr om Method 201A Evaluation ............. 4-2 Table 4-2. PM 10 Filterable Particulate Results from Method 201A Evaluati on......................... 4-4 Table 4-3. PM 2.5 Filterable Particulate Results from Method 201A Evaluati on........................ 4-5 Table 4-4. PM 2.5 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 ................

................................................... ....... 5-1vi 

### 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 PM 10 Particulate of Unspiked Trains....................... ............................... 4-4 Figure 4-4. Filterable PM 2.5 Particulate of Unspiked Trains...................... ............................... 4-6 Figure 4-5. PM 2.5 Filterable Mass....................................

................................................... ..... 4-7 Figure 4-6. Condensable Particulate Material Distribution in Unspiked Trains ........................ 4-9 Figure 4-7. Average Condensable Particulate Matter for Pai red 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/dsc m)....................................... 5-4 Table 6-1. Method Evaluation Objectives for the Dry Impinge r Condensable Particulate Method .............................................

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

Error! Bookmark not defined.1-1

1.0 INTRODUCTION Sampling and analytical methods for a particular air pol lutant 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 analyt es, methods have been developed and evaluated for sample analysis, but not for sample colle ction. Field validation for new or revised methods that have no comparable equivalent is accomplish ed by spiking known quantities of the pollutant or pollutant class into the collection apparat us in the field so that the precision and bias of the method can be demonstrated from sample collecti on through analysis. This report describes the execution and presents the results of a fi eld test to evaluate revisions to EPA Methods 201A and 202 that EPA proposed on March 25, 2009 (74 FR 12970). T hese methods are used to quantify fine filterable and condensable particulat e matter (CPM) emissions. Revisions to the methods were necessary to add the capabili ty to measure fine particulate matter and improve the measurement of CPM. The methods were ev aluated 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. Fil terable particulate collection performance was evaluated for precision and condensable par ticulate performance was evaluated for both precision and bias.

1.1 Background

Emission inventories for the National Emissions Inventor y (NEI), State Implementation Plans (SIPs), and the Consolidated Emissions Reporting Rule (CERR) require the reporting of primary PM emissions, including both the filterable and co ndensable components. The NEI, the SIP emissions inventories, and the periodic emissions inv entories required under the CERR must contain accurate data for government agencies to effecti vely manage ambient air quality. These
emission inventories are based on a combination of emissi on factors and site-specific test results, when test results are available. Site-specific test r esults provide a direct measurement of emissions and are conducted primarily to demonstrate com pliance with an existing emission limitation. Emission factors are based on the average s of several site-specific tests. Thus, both emission factor development and emissions inventory repo rting depend on site-specific tests. Results of site-specific compliance tests must be unbi ased and have known uncertainty.1-2

Since the promulgation of Method 202 in 1991, air emission t esting 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 (SO 2 ), nitrogen dioxide (NO 2 ), and/or soluble organic compound emissions. These gaseous contaminants can be partially absorbed in the impinger solutions and chemically oxidize to form materia l counted as CPM in Method 202. The “artifact” reaction products are not related to the primar y emission of CPM from the source. The artifacts formed in the Method 202 impingers translate i nto 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 undert ake laboratory studies in collaboration
with stakeholders to characterize the artifact formati on 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 t he laboratory test procedures, see “Laboratory Test Plan and Quality Assurance Project Pla n (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 Improv ement of Condensable Particulate Matter
Measurement” on the same Web site.

Based on results of the laboratory experiments, EPA pro posed revisions to Methods
201A and 202.

• Proposed amendments to Method 201A would add a particle-sizing cyclone to the sampling train to measure PM 2.5 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 micr ometers ( μ m)) and coarse PM1-3 (particles with mean aerodynamic diameters less than or equal to 10 μ m) 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 co nsistency between testing contractors in method application, improve the pre cision 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-fo rmed 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 301 1 requirements for replicate tests sufficient to evaluate the bias and precision of proposed methods

• Determine the precision associated with the measuremen t of filterable PM 10 and PM 2.5 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 t he (inorganic and organic components) condensable particulate matter using the sampl ing 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 sampl ing train glassware is reused in the field.

The precision data from blank trains in this field test w ere used to refine the laboratory estimates of the method detection limit (MDL) and provi de information on the usability of the method for compliance, emissions factor development, r ule development, and other fine particulate stack emission studies. The information on t he 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 rec overy 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 Im provement of Condensable Particulate Matter Measurement, which is included in Docket EPA-HQ-OA R-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 pr ecision in Method 202. There is currently no known in-situ spiking procedure for filterable PM 10 or PM 2.5 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 expe rimental 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

• PM 10 standard deviation of 0.85 mg/dscm

• PM 2.5 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 C PM
Measurement of filterable particulate matter collected during these tests showed precision that is consistent with Method 17 and the tests performe d to develop the multi-cyclone particle sizing sampling head that was used in this evaluation to co llect size fractionated particulate

matter.

The majority of the particulate matter collected in t hese evaluation tests was less than
PM 2.5 . The precision of the particulate matter greater than PM 10 and the particulate matter
between PM 10 and PM 2.5 was greater than the precision of PM 2.5 because these masses were near the sensitivity limit of the analytical balance used to det ermine mass. Therefore, the precision for the total particulate and the PM 10 particulate mass represents a worst case for the met hod.

The inorganic spike bias and precision meet Method 301 requireme nts for a new method without correction. Organic spike was not recovered indi cating the compound was too volatile for evaluation as an organic challenge for the sampling m ethod.

The field train recovery blank is a combination of vario us 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 recovere d from seven trains during this evaluation was 0.78 mg/dscm based on the average sample volu me collected during the field2-2

tests. The average inorganic field train blank recovered fr om seven trains in this evaluation was 2.48 mg/dscm based on the average sample volume collected duri ng the field tests.

The proof train recovery blank contained 0.32 mg/dscm and 2.23 mg/ds cm of organic and inorganic residue respectively based on the average samp le volume collected during the field

tests.

2.2 Method Recovery Method recovery is summarized below:

• Sulfuric acid recovered during 10 test runs collection avera ged 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 propose d 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 par ticulate can be determined based on the uncertainty in the data from the mass collecte d during the method evaluation tests. While these detection limits may be biased high because the ma ss may not be within a factor of five of the limits, they represent a best estimate of the det ection 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 Blanks3-1

3.0 EXPERIMENTAL APPROACH

3.1 Introduction This section describes the experimental approach to identi fy and conduct sampling at a representative site.

3.2 Field Test Site

EPA selected the field test site based on several crite ria. 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-fi red 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 compos ition is important to successfully challenge the proposed methods.

• Stack gases composition based on presite samples or rece nt stack tests - Organic CPM > 1 mg/dscm (compounds with vapor pressure les s than hexadecane) - Inorganic CPM > 2 mg/dscm (H 2 SO 4 , HNO 3 ) - SO 2 (25 - 150 ppmv) - NO x (> 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 trai ns. - Located within 250 miles of Research Triangle Park, NC

Based on stack gas composition and facility characterist ics, 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 blea ched kraft pulp and paper mill that produces uncoated freesheet, Xerographic, offset, opaque, and trade boo k 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 m g/dscm. CPM was found3-2

in both the inorganic and organic fractions. Approximately 70 m g/dscm of inorganic CPM and 3.0 mg/dscm of organic CPM were found during these tests. Base d 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 acceptabl e for the method validation tests. Testing of the No. 2 hog fuel-fired boiler (2HFB) was co mpleted 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 emi ssions from the boiler are controlled using a set of multi-cyclones and an electrost atic, gravel-bed filter (in series). The mill operates 24 hours a day, 7 days per week; however, the opera tion 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 i nsulated and the distance from the sampling port cover to the stack wall is 16 inches. Test p orts are located 576 inches, or 3.9 stack diameters downstream of the stack breaching, and approximate ly 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 pl atform. The walls of the platform are 82 inches (approximately 7 feet) from the st ack. Access panels in the walls (and two support hooks in the ceiling) across from each port provide su fficient space to maneuver the sampling trains.3-4

3.3 Field Test Procedures The field test and procedures followed the Category III QA PP/Site Specific Field Test Plan: Evaluation and Improvement of Condensable Particula te Matter Measurement, which is included in this report as Appendix A. Statistical methods f ollowed Method 301 to determine precision and bias.

3.3.1 Sampling and Analytical Methods Proposed Methods 201A and 202 served as the sampling and analyti cal 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. Pro be nozzle configuration was less than 2 percent of the stack area. The port location was a m inimum of eight stack diameters upstream from a flow perturbation and at least two stack diameter s downstream from flow perturbation including the stack exhaust.

The sampling procedure was followed except that no travers e of the emission source stack was necessary. Instead, the point of average veloc ity was determined across the stack diameter and single point, isokinetic sampling was perfo rmed at that location. The quadruplicate train sampling met the requirements in proposed EPA Meth od 201A for flow obstructions and isokinetic sampling.

3.3.2 Statistical Methods Data from the quadruplicate train results were statisti cally evaluated following Method 301 to determine the performance of the method relati ve to bias and precision. The respective method is considered to be a valid method if th e precision criteria is met (% RSD <50) and the bias is not significantly different from zero o r 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 fall s out of this range of recovery, bias will be determined according to Method 301 and reported with t he 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 particula te 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 e xperimental design chosen for this evaluation involved collecting approximately 1.5 cubic meters o f 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 e valuation of the performance of these
methods.

For the field test runs, the following sampling scheme wa s followed: two (2) complete quadruplicate sampling test runs were collected simultaneous ly. 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. Spik ing solutions were added to the first (dropout) impinger. Spiking was performed with a c ondensable inorganic compound, sulfuric acid, and a condensable organic compound, (heptadecane). The organic spiking material was selected based on thermodynamic calculations using t heoretical vapor pressure to estimate the expected recovery while still challenging the condensabl e sampling and analysis method. The inorganic spiking material, sulfuric acid was selected eve n though it exceeds the theoretical requirements for 100% retention in the proposed revision t o Method 202 because it is the most volatile common inorganic condensable available.

Five (5) milligrams of heptadecane were added to 20 mL of dioni zed 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 val id 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 resul ts. 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 sim ultaneously collected.4-1

4.0 RESULTS AND DISCUSSION A summary of the results from the field evaluation of pr oposed 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 e ach sampling train. Two sets of duplicate sampling trains were used to collect a total of fo ur simultaneous samples for each test run. Two of the sampling trains were spiked with known qua ntities of condensable particulate
material and two were used to measure the native amount of particulate from the source. Filterable particulate results are summarized in Sectio n 4.1. Condensable particulate results are
summarized in Section 4.2. Combined filterable and condensable particulate results are
summarized in Section 4.3.

H e a t e d B o x F i l t e r

O r i f i c e

M a n o m e t e r D r y G a s M e t e r B y
- P a s s V a l v e

P u m p

M a i n V a l v e V a c u u m

G a u g e V a c u u m L i n e W a t e r B a t h ( < 3 0 o C / 8 5 o F ) C o n d e n s

e r T h e r m o c o u p l e s

E m p t y S

i l i c a G e l ( 3 0 0 g r a m s ) R e c i r c u l a t i o n P u m p C h e c k V a l v e T e m p e r a t u r e S e n s o r

I c e B a t h

S t a c k W a l l M a n o m e t

e r S

- T y p e P i t o t T u b e

Figure 4-1. Configuration of Each Sampling Train
Statistical analysis of the filterable material coll ected 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 mete r basis. The average standard deviation of each quadruplicate sampling run was calculated to assess the precision of the method. Results4-2

are summarized for each reportable filterable particulat e fraction (i.e., PM-Total, PM 10 and
PM 2.5 ).

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 t he total filterable material collected in 40 test runs shows an average standard deviation of 1.63 milligrams pe r 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 amount s of particulate mass are captured in one size fraction compared to others the error in recov ery leads to higher uncertainty. The source emissions sampled in this method evaluation were dominate d by fine filterable (PM 2.5 ) particulate, which leads to more uncertainty in the PM 10 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) d i d i 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 d i 2 181.43 n 40 SD s 1.51 %RSD 6.664-3 0 5 10 15 20 25 30 35 40 45 50

1 2 3 4 5 6 7 8 9 10 10-Run Average Run NumberTotal 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 PM 10 filterable particulate results are shown in Tables 4-2. The average standard deviation of 40 test runs was 1.09 mg/dscm. P M 10 filterable results are the sum of the material caught in the PM 2.5 cyclone and on the final particulate filter. The PM 10 results are strongly influenced by the predominant PM 2.5 filterable particulate mass. Less uncertainty is
shown for the PM 10 filterable particulate results than the total particul ate mass as indicated by the smaller average standard deviation from the test runs fo r this particulate fraction.4-4

Table 4-2. PM 10 Filterable Particulate Results from Method 201A Evaluation

Run Number Train A Train B Train C Train D Average α (Standard Deviation) d i d i 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 d i 2 58.02 n 40 SD s 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 (PM 2.5 to PM 10 ) to the total in the PM 10 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 PM 10 Particulate of Unspiked Trains4-5

A summary of the PM 2.5 filterable particulate results are shown in Tables 4-3. The PM 2.5 filterable particulate results account for the major f raction of the particulate mass captured during these tests. These data provide a representative estima te of the anticipated performance of proposed Method 201A when source emissions are well above the detection limit for this
method.

Table 4-3. PM 2.5 Filterable Particulate Results from Method 201A Evaluation

Run Number Train A Train B Train C Train D Average α (Standard Deviation) d i d i 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 d i 2 51.70 n 40 SD s 0.80 RSD 3.94 DL 1.35

Figure 4-4 shows a bar graph of the filterable PM 2.5 mass normalized for the stack volume collected for each train in the 10 quadruplicate tes t 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 FilterableFilterable PM 2.5 (mg/dscm)

Figure 4-4. Filterable PM 2.5 Particulate of Unspiked Trains
Results for the recovery of filterable PM 2.5 from each of the individual 40 test runs are shown in Table 4-4 and graphically in Figure 4-5. The standard de viation 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 sam pling trains for all 40 tests, multiplied by Students t for 39 degrees of freedom, can be use d as a rough estimate the detection limit (DL) for this method for PM 2.5 . The limit of detection for this particulate matter f raction is 1.35 mg/dscm given the uncertainty at these concentrations

.4-7 Table 4-4. PM 2.5 Filterable Particulate Mass

Run Number Train A Train B Train C Train D Average α d i d i 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 d i 2 51.70 n 40 SD s 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 Average Run NumberPM (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. PM 2.5 Filterable Mass4-8

4.2 Condensable Particulate Results and Discussion Recovery and precision of the condensable particulate ma tter collection for the field evaluation tests are presented in this section. In add ition, results and discussion of the individual inorganic and organic spike recovery are presented. Test re sults from unspiked trains were used to determine the method precision.

Results of the unspiked condensable particulate matter col lected in the evaluation tests
are shown in Table 4-5. Table 4-5 includes the results of t he inorganic and organic fractions in addition to the combined condensable particulate matter mas s. 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 pr oof train or field train blank results.

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

Test Run Train A

Inorganic Train A

Organic Train C

Inorganic Train C

Organic Total

Train A Total

Train C Average Difference (d i ) d i 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 2.8 8 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 d i 2 365.67

n 20 Sd u 3.02 S m 14.7 RSD 20.524-9

Figure 4-6 shows the total M-202 CPM collected from the unspi ked trains in each of the ten test runs. The stacked bars show the inorganic and or ganic 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 t he 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 (Unspi ked)

0 5 10 15 20 25 30 35

1 2 3 4 5 6 7 8 9 10 10-run Average Run NumberCPM (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 i n 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 fract ion of the test samples is shown as a percent in the stacked bar for each test run. Inorganic C PM 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 coll ected 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 reason s; first to determine if the material was a satisfactory starting point for a stationary source met hod audit sample and second to evaluate the performance of the condensable particulate method to reta in material once it was collected.

4.3.1 Inorganic Condensable Recovery Results The average inorganic condensable material from each of t he test runs is shown in Figure 4-8. The stacked bars show the native condensable par ticulate 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 NumberCPM (mg/dscm)

Unspiked Trains Spiked Trains

Figure 4-8. Average Recovered CPM of Inorganic Particulate
The condensable particulate results of the spiked and unspi ked 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 F igure 4-9.4-12 Inorganic CPM Recovery of Spiked and Unspiked Train s

0 20 40 60 80 100 120

1 2 3 4 5 6 7 8 9 10 10-Run Average Run NumberCPM (mg/dscm)

Train A - Unspiked Train C - Unspiked Train B - Spiked Train D - Spiked Ave. FTB = 2.43 mg/dscm Spiked Amt.= 91.4 mg/dscm

Figure 4-9. Inorganic Mass for All Test Runs
To compare the results from sampling train to sampling tra in over the 40 test runs, the
native material from the source must be subtracted fr om the total recovered condensable material. The difference is the amount of spiking mat erial retained by the sampling train. Results from the unspiked sampling train were normalized based on t he 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 m ean for the simultaneous train runs. The diamond represents the average of the two simultane ous 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 Average Run NumberInorganic 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 H 2 SO 4 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 samplin g train meets the reference Method 301 criteria for a valid sampling method. The inorganic CPM r ecovery 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 t rains 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 sam pling 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 Average Run NumberCPM (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 Ru ns4-15

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 aver age 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 Resu lts and Discussion Figure 4-12 shows the average particulate collected from th e un-spiked trains for each fraction collected. All ten runs and a 10-run average are included. Filterable PM 2.5 accounts for 50 and 75% of the total particulate mass collected during samp ling runs. Inorganic CPM accounts for the second highest particulate catch rangi ng from 22 to 46% of the total particulate concentration. Organic CPM was approximately the same orde r of magnitude as the organic field train blank. Facility had little or no organic emissions upo n 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 Average Run NumberMass (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 Fraction5-1

5.0 QUALITY CONTROL AND QUALITY ASSURANCE This section provides information on the proof train blanks f or 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 s tack 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 r eported by the analysis laboratory for these tests. Horizontal lines have bee n added to show both the inorganic and organic field reagent blank values to demonstrate that field t rain 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 Blank s

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 NumberCPM (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 NumberInorganic 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 Fi gure 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 contam inant 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/d scm)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 t rain. Paired sampling trains with collocated probes collecting samples at similar s ampling rates were used during the field tests. Two sets of paired trains were used to collect quadr uplicate samples for each test run. For this field test, precision and bias was calculated accordi ng to EPA Method 301 (Appendix B) for the inorganic CPM. Evaluation objectives for these test s are shown in Table 6-1.

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

Method Bias (Percent Recovery) Precision (% RSD) Proposed Method 202 70 - 130 % 30 %

To meet Method 301 requirements, 10 quadruplicate sampling runs we re 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 wer e used in precision and bias calculations. Spiking solutions were added to the first (dro pout) 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, deioni zed 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 ea ch of the quadruplicate trains for each run was spiked with 1.0 mL of inorganic CPM (~150 mg/mL s ulfuric acid in water) and 1.0 mL of organic CPM (~5 mg/mL heptadecane in toluene). All sp ikes were added with a calibrated disposable tip repeating pipette accurate to 1.0 mL ±2%. In a ddition, seven field train blanks were collected. Data quality objectives for CPM are sho wn in Table 5-1. There is no audit method to spike filterable particulate into samples colle cted in these tests. Therefore, precision of the filterable particulate collection was determined an d reported.6-2

6.1 Precision The objective for precision for the proposed Method 202 is l ess than 30% relative
standard deviation. A mean and standard deviation of the con centrations of spiked samples will be calculated from 10 runs of quadruplet paired sampling trains

.

The precision (SD s ) of the measurements from the spiked samples is deter mined by calculating the difference, d i , between the pairs of spiked measurements for each quadr uplicate train. The pooled standard deviation of the spiked values, or the precision, SD s , 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 = S m – M m – CS (6-2)

where:
B = bias at the spiking level S m = mean of the measured concentrations of the spiked s amples M m = 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 de termine 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.