United States Office of Air Quality Environmental Protection Planning and Standards Agency Research Triangle Park, NC 27711 EPA 454/ R 00 035s September 2001 AIR Final Report  Volume I of II Testing of a 4 Stroke Diesel Cycle Oil fired Reciprocating Internal Combustion Engine to Determine the Effectiveness of an Oxidation Reduction Catalyst System for Reduction of Hazardous Air Pollutant Emissions FINAL REPORT TESTING OF A 4 STROKE DIESEL CYCLE OIL FIRED RECIPROCATING INTERNAL COMBUSTION ENGINE TO DETERMINE THE EFFECTIVENESS OF AN OXIDATION CATALYST SYSTEM FOR REDUCTION OF HAZARDOUS AIR POLLUTANT EMISSIONS VOLUME I OF II Prepared for:

Terry Harrison ( MD l 9) Work Assignment Manager SMTG, EMC, EMAD, OAQPS U. S. Environmental Protection Agency Research Triangle Park, NC 27711 September 200 1 Submitted by:

PACIFIC ENVIRONMENTAL SERVICES, INC. 5001 S. Miami Blvd., Suite 300 Research Triangle Park, NC 27709 2077 ( 919) 941 0333 FAX ( 919) 941 0234 DISCLAIMER Pacific Environmental Services, Inc. ( PES) prepared this document under EPA Contract No. 68 D 01  003, Work Assignment No. l 04. PES reviewed this document in accordance with its internal quality assurance procedures and approved it for distribution. The contents of this document do not necessarily reflect the views and policies of the U. S. EPA. Mention of trade names does not constitute endorsement by the EPA or PES. TABLE OF CONTENTS VOLUME I 1.0 INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . l l 2.0 SUMMARY OF RESULTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 1 2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 EMISSIONS TEST LOG. ...................................... 2 l ENGINE PARAMETERS AND ................................. 2 3 FTIRS AND CEMS MEASUREMENTS .......................... 2 3 GCMS MEASUREMENTS .................................... 2 6 POLYNUCLEAR AROMATIC HYDROCARBON ( PAH) MEASUREMENTS.. ......................................... 2 9 DESTRUCTION OF ORGANIC COMPOUNDS BY THE CATALYST 2 l 1 PARTICULATE MATTER MEASUREMENTS ................... 2 15 FUEL OIL ANALYSIS ....................................... 2.15 .

3.0 SOURCE DESCRIPTION AND OPERATION . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 1 3.1 ENGINE DESCRIPTION ...................................... 3  1 3.2 ENGINE OPERATION DURING TESTING ....................... 3 4 4.0 SAMPLING LOCATIONS . . . . . . . . . . . . . . . . . . . . . . . . . . . u . . . . . . . . . . . . . . . 4 1 5.0 SAMPLING AND ANALYSIS METHODS. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 l 5.1 5.2 5.3 5.4 5.5 5.6 5.7 5.8 LOCATION OF MEASUREMENT SITES AND SAMPLE/ VELOCITY TRAVERSE POINTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 l DETERMINATION OF STACK GAS VOLUMETRIC FLOW RATE. . . 5 3 DETERMINATION OF STACK GAS OXYGEN AND CARBON DIOXIDE CONTENT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 4 DETERMINATION OF STACK GAS MOISTURE CONTENT . . . . . . . 5 4 DETERMINATION OF NITROGEN OXIDES . . . . . . . . . . . . . . . . . . . . . 5 6 DETERMINATION OF CARBON MONOXIDE . . . . . . . . . . . . . . . . . . . 5 6 DETERMINATION OF TOTAL HYDROCARBONS . . . . . . . . . . . . . . . 5 7 DETERMINATION OF METHANE AND NON METHANE HYDROCARBONS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 7 ii TABLE OF CONTENTS ( Concluded)

Pane 5.9 DETERMINATION OF GASEOUS ORGANIC HAP USING FTIRS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 8 5.10 DETERMINATION OF ORGANIC HAPS BY DIRECT INTERFACE GCMS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 9 5.11 DETERMINATION OF POLYCYCLIC AROMATIC HYDROCARBONS BY CARB 429 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 12 5.12 DETERMINATION OF PARTICULATE MATER . . . . . . . . . . . . . . . . . 5 14 5.13 DETERMINATION OF FUEL OIL COMPOSITION . . . . . . . . . . . . . . . 5 14 6.0 QUALITY ASSURANCE/ QUALITY CONTROL PROCEDURES ANDRESULTS.................................................... 6 l 6.1 FTIRS QA/ QC PROCEDURES ................................. 6 l 6.2 CEMS QA/ QC PROCEDURES ................................. 6 5 6.3 GCMS QA/ QC PROCEDURES ................................ 6 12 6.4 CARB 429 QA/ QC PROCEDURES ............................. 6 19 6.5 DATA QUALITY ASSESSMENT .............................. 6 29 APPENDIX A APPENDIX B VOLUME II APPENDIX C APPENDIX D SUBCONTRACTOR TEST REPORT  COLORADO STATE UNIVERSITY ENGINES AND ENERGY CONVERSION LABORATORY, " EMISSIONS TESTING OF CONTROL DEVICES FOR RECIPROCATING INTERNAL COMBUSTION ENGINES IN SUPPORT OF REGULATORY DEVELOPMENT BY THE U. S. ENVIRONMENTAL PROTECTION AGENCY ( EPA) PHASE 3: FOUR STROKE, DIESEL INTERNAL COMBUSTION ENGINES"

SUBCONTRACTOR TEST REPORT  EMISSION MONITORING, INC. " RESULTS OF DIRECT INTERFACE GCMS TESTING CONDUCTED ON A 2 STROKE LEAD BURN ENGINE"

SUBCONTRACTOR TEST REPORT  EASTERN RESEARCH GROUP, INC. " CARB METHOD 429: SAMPLE ANALYSIS"

CARB METHOD 429 FIELD DATA . . . 111 LIST OF TABLES Table 2.1 Table 2.2 Table 2.3 Table 2.4 Table 2.5 Table 2.6 Table 2.7 Table 2.8 Table 2.9 Table 2.10 Table 2.11 Emissions Test Log ........................................... 2 2 Summary of Engine and Exhaust Gas Parameters ................... 2 4 Stack Concentrations of Detected FTIRS and CEMS Compounds ....... 2 5 Stack Concentrations of Detected GCMS Compounds ................ 2 7 Summary of Stack Gas and Sampling Parameters CARB 429 Catalyst Inlet and Outlet. ...................................... 2 10 Emission Rates of Detected PAHS at Catalyst Inlet ................. 2 12 Emission Rates of Detected PAHS at Catalyst Outlet ................ 2 17 Mass Flow Scenarios ......................................... 2 13 Removal Efficiencies of Detected Organic Compounds ............. 2 l 5 Method IS0 8 178 l Particulate Matter Mass Flow Data .............. 2 l 6 Summary of Fuel Oil Analysis .................................. 2 17 Table 3.1 Table 3.2 Table 3.3 Table 3.4 Table 3.5 Engine and Catalyst Specifications Caterpillar 3508 EUI ( 4 stroke, diesel cycle, oil fired). ..................................... I ... 3 2 Summary of Nominal Engine Parameters .......................... 3 3 Target Engine Operating Conditions During Testing ................. 3 5 Summary of Engine Parameters  Caterpillar 3508 EUI ............... 3 6 Summary of Engine Parameters During Baseline Runs. ............... 3 7 Table 5.1 Summary of Sampling and Analysis Methods ....................... 5 2 Table 5.2 FTIRS Analyzer Specifications .................................. 5 8 Table 5.3 Summary of Fuel Oil Analysis Methods .......................... 5 l 5 Table 6.1 Table 6.2 Table 6.3 Table 6.4 Table 6.5 Table 6.6 Table 6.7 Table 6.8 Table 6.8 Table 6.10 Table 6.11 Detection Limits of FTIRS and CEMS Compounds .................. 6 6 Types and Frequencies of CEMS Analyzer Calibrations. .............. 6 8 Summary of Fuel Factor Values ................................ 6 l 1 Summary of CEMS Analytical Detection Limits ................... 6 12 Summary of GCMS Continuing Calibrations ...................... 6 14 GCMS Analyte Spike Recoveries ............................... 6 15 Detection Limits of GCMS Compounds at Catalyst Inlet ............. 6 17 Detection Limits of GCMS Compounds at Catalyst Outlet ............ 6 l 8 CARB 429 Sample Train  Summary of Temperature Sensor Calibration Data ............................................. 6 20 CARB 429 Sample Train Summary of Pitot Tube Calibration Data ..... 6 21 CARB 429 Sample Train Summary of Dry Gas Meter and Orifice Calibration Data ............................................. 6 22 Page iv LIST OF TABLES ( Concluded)

Page Table 6.12 Surnmary of CARB 429 Blank Results ........................... 6 25 Table 6.13 Summary of CARB 429 Surrogate Recoveries ..................... 6 26 Table 6.14 Detection Limits of PAH Compounds at Catalyst Inlet ............... 6 27 Table 6.15 Detection Limits of PAH Compounds at Catalyst Outlet ............. 6 28 Table 6.16 Summary of Engine and Method Performance ..................... 6 3 1 LIST OF FIGURES Figure 1.1 Test Program Organization and Major Lines of Communication . . . . . . . . l 3 Figure 4.1 Figure 4.2 Figure 4.3 Figure 4.4 Figure 5.1 Figure 5.2 Figure 5.3 Page Inlet Sample Port Locations for Velocity, CARB 429, FTIRS, CEMS, and GCMS Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 2 Inlet Traverse Point Locations for Velocity and CARB 429 Sampling . . . . 4 3 Outlet Sample Port Locations for Velocity, CARB 429, FTIRS, CEMS, and GCMS Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 4 Outlet Traverse Point Locations for Velocity and CARB 429 Sampling . . 4 5 Schematic Diagram of EECL FTIRWEMS Sampling and Analysis System .............................................. 5 6 Schematic of GCMS Sampling and Analysis System ................ 5 l 1 Schematic Diagram of CARB 429 PAH Sampling Train ............. 5 13 1.0 INTRODUCTION The United States Environmental Protection Agency ( EPA) is investigating Reciprocating Internal Combustion Engines ( RICE) to characterize engine emissions and catalyst control efficiencies of hazardous air pollutants ( HAP). This document describes the results of HAP and particulate matter ( PM) emissions testing conducted on a Caterpillar 3508 EUI diesel cycle, oil fired, 4 stroke engine. Early in 1998, several industry and EPA representatives agreed that the Caterpillar 3508 EUI engine at the Colorado State University's ( CSU) Engine and Energy Conversion Laboratory ( EECL) is adequately representative of existing and new diesel cycle engines. The group agreed that a matrix of test results from testing conducted at the EECL could be used to develop Maximum Achievable Control Technology ( MACT) standards for RICE. The group further agreed that an oxidation catalyst installed on the Caterpillar 3508 EUI could be used to determine the effectiveness of oxidation catalysts for these engines, and that the EPA could use the results from testing at CSU as the basis for developing the MACT standard for diesel cycle oil fired engines.

PES conducted emission testing to measure pollutant concentrations in the exhaust gas both up and downstream of an oxidation catalyst. Englehard Corporation manufactured the catalyst and CSU personnel installed it on the engine. Several sampling and analysis methods measured HAP emissions before and after the oxidation catalyst. Fourier transform infrared spectroscopy ( FTIRS) measured formaldehyde, acetaldehyde, and acrolein. Benzene, toluene, ethyl benzene, ( o, m, p) xylenes, styrene, hexane, and 1,3 butadiene, were measured using a direct interface gas chromatograph with a mass spectrometer detector ( GCMS). Continuous emission monitors ( CEMS) measured oxygen, ( O,), carbon dioxide ( CO,), nitrogen oxides ( NO,), carbon monoxide ( CO), total hydrocarbons ( THC), methane ( CH,) j and non methane hydrocarbons ( NMHC). Naphthalene and polycyclic aromatic hydrocarbons ( PAHs) [ acenaphthene, acenapthylene, anthracene, benzo( a) anthracene, benzo( a) pyrene, benzo( b) fluoranthene, benzo( e) pyrene, benzo( k) fluoranthene, benzo( g, h, i) perylene, chrysene, dibenzo( a, h) anthracene, fluoranthene, fluorene, indeno( 1,2,3 cd) pyrene, 2 methylnapthalene, perylene, phenanthrene, and pyrene] were measured by California Air Resources Board ( CARB) Method 429.

PM testing was conducted using a dilution sampling system. A sample of the exhaust gas was extracted from the stack, and diluted with clean, dry air then passed through a series of filters. Particle mass was determined gravimetrically. Fuel oil samples were collected and analyzed to determine the concentrations of target metals ( beryllium, cadmium, chromium, lead, maganese, mercury, nickel, and selenium).

PES employed four subcontractors for this effort. The CSU EECL provided the Final Report  Caterpillar 3508 EUI l l September 200 1 facility and the engine for the test program, operated the engine at predefined conditions, and recorded engine operational data during the testing. In addition, CSU EECL personnel operated two FTIRS sampling and analysis systems and two CEMS systems that measured pollutants and diluents in the exhaust gas. Emissions Monitoring, Inc., ( EMI) of Raleigh, North Carolina provided emissions testing services and two direct interface GCMS sample extraction and analysis systems. Eastern Research Group ( ERG) of Morrisville, North Carolina, prepared filter media and XAD 2@ sorbent resin traps and analyzed the CARB Method 429 samples for PAHs using Low Resolution Mass Spectrometry ( LRMS). Galbraith Laboratories, Inc. of Knoxville, Tennessee provided ultimate, proximate, and metals analysis of the fuel oil samples collected by PES.

Under a separate work EPA assignment, ERG personnel operated an EPA owned dynamic spiking system for the validation of the FTIRS systems for formaldehyde, acetaldehyde, and acrolein. Sierra Instruments, Inc., of Monterey, California conducted the PM testing on the engine in conjunction with the testing conducted by PES.

The test program organization and major lines of communication employed during this project are presented in Figure 1.1. The balance of this report contains the following Sections:

Section 2.0 Summary of Results Section 3 . O Source Description and Operation Section 4.0 Sampling Locations Section 5 . O Sampling and Analysis Methods Section 6.0 Quality Assurance/ Quality Control Procedures and Results The appendices of this report contain the engine test report submitted to PES by CSU, the test report outlining the results of the testing for the GCMS compounds submitted to PES by EMI, and the analytical report for PAH compounds submitted to PES by ERG. Also included are PES field data sheets and calibration data associated with the PAH sampling.

Final Report  Caterpillar 3508 EUI l 2 September 200 1 PES Project Manager Dennis A. Falgout ( 703) 471 8383 Test Plan PES Testing PES Analysis PES Subcontractor CSU EECL Subcontractor Eastern Research Group, Inc. I Subcontractor Eastern Research Subcontractor Eastern Research Group, Inc.

Figure 1.1. Test Program Organization and Major Lines of Communication Draft Final Reports PES I Subcontractor CSU EECL I i Subcontractor Emissions Monitoring, Inc. I Final Report  Caterpillar 3508 EUI l 3 September 200 1 2.0 SUMMARY OF REXULTS This section provides summaries of the stack gas parameters and HAP emissions measured during the test program. Testing of the Caterpillar 3508 EUI engine was conducted August 3 1 through September 2, 1999 at CSU's Engines and Energy Conversion Laboratory in Fort Collins, Colorado. The following sub sections present the test times and durations, engine and stack gas parameters, HAP concentrations before and after the oxidation catalyst, PM concentrations and metal content in the fuel oil.

The measurements that were made of fuel flow consumption during each test run were determined by EECL personnel to be inaccurate. Pollutant emission data is presented on a concentration basis, corrected to a reference oxygen concentration of 15%. The removal efficiency of HAP by the catalyst is calculated using pre and post catalyst concentrations of each compound, corrected to 15% oxygen.

2.1 EMISSIONS TEST LOG During the test period, the test team conducted twenty five test runs. These test runs consisted of ten 5 minute Quality Control ( QC) runs, ten 33  minute sampling runs for collection of FTIRS, CEMS and GCMS data, three CARB Method 429 runs, and two 5 minute baseline runs. PM sampling runs were conducted just before and just after each 33 minute FTIRS/ CEMS/ GCMS sampling run. Table 2.1 presents the emissions test log. The test log summarizes the date and time of each run and the sampling methods used during that particular run. Additional discussions of the engine operating parameters may be found in Section 3.0 of this document.

In Table 2.1, the sampling runs are presented in the order of their conduct. In the tables that follow Table 2.1, the sampling runs are presented in numerical order. The test team decided to arrange the test order so that making small changes in engine operation could accomplish changes from condition to condition rather than large changes. The approach reduced both the time between test runs needed to effect the change and the time the engine needed to stabilize after the change. The effect on the test program was that we did not conduct the engine load tests in the order in which the Quality Assurance Project Plan ( QAPP) presents them. To maintain consistency with the QAPP, we did not change the numbers denoting the engine test conditions. The reader should note that no Runs designated 5,6,7, and 8 were conducted on this engine. These run designations describe conditions that were applicable to the other two engines tested during the HAP characterization project.

Final Report  Caterpillar 3508 EUI 2 l September 200 1 TABLE 2.1 EMISSIONS TEST LOG Date 813 l/ 99 Run Time 1006 1011 Run ID Run 1 QC Sampling Methodology 813 l/ 99 1 1047 1120 1 Run 1 I FTIRS/ CEMS/ GCMS/ PM 813 1 I99 1 1335 1340 1 Run 14 QC 2 I 813 1 I99 I 1358 143 1 I Run 14 I FTIRWEMWGCMZYPM 813 l/ 99 1 1645 1650 1 Run 13 QC I 813 1 I99 1 1659 1732 1 Run 13 I FTIRS/ CEMS/ GCMS/ PM 813 1 I99 1 1831 1836 1 Run 10 QC I 813 1 I99 1 1859 1932 1 Run 10 I FTIRWEMWGCMWM 813 1 I99 1 1859 2059 1 PAH 1 ( Run 10) I CARB Method 429 813 l/ 99 1 2220 2225 1 Run 9 QC I 813 1 I99 1 2243 2316 1 Run 9 I FTIRS/ CEMS/ GCMS/ PM 9/ I/ 99 1 1055 1100 1 Run 4 QC I 9/ l/ 99 1 1116 1149 1 Run 4 I FTIRS/ CEMS/ GCMS/ PM 9/ l/ 99 1 1309 1314 1 Baseline No. 1 I 9/ l/ 99 1 1340 1345 I Run 11 QC I 9/ l/ 99 I 1517 1550 I Run 11 I FTIRS/ CEMS/ GCMS/ PM 9/ l/ 99 1 1624 1629 1 Run 12 QC I 9/ l/ 99 1 1637 1710 1 Run 12 I FTIRS/ CEMS/ GCMS/ PM 9/ l/ 99 I 1830 1835 I Run 2 QC I

9/ l/ 99 1 1845 1918 1 Run 2 I FTIRWCEMWGCMW'M 911199 1 1912 2124 1 PAH 2 ( Run 2) CARB Method 429 912199 1 0949 0954 1 Run 3 QC I 912199 1 1005 1038 1 Run 3 I FTIRS/ CEMS/ GCMS/ PM 912199 I 1038 1218 I PAH 3 ( Run 3) I CARB Method 429 912199 I 1250 1255 I Baseline No. 2 I Final Report  Caterpillar 3508 EUI 2 2 September 200 1 2.2 ENGINE PARAMETERS Table 2.2 summarizes some engine and exhaust gas parameters measured and/ or calculated during the test program. The EECL's Data Acquisition System ( DAS), monitored and recorded approximately 200 engine operating parameters, and gas temperatures, and concentrations of 02, CO,, and moisture at the catalyst inlet and exhaust. ( The test report generated by CSU EECL is presented in Appendix A).

2.3 FTIRS AND CEMS MEASUREMENTS Table 2.3 summarizes the in stack and corrected concentrations of the FTIRS target compounds ( formaldehyde, acetaldehyde, and acrolein) and the CEMS target compounds ( carbon monoxide, nitrogen oxides, THC, methane, and NMHC).

EECL operated two FTIRS sampling and analysis systems to quantify concentrations of the target compounds. Exhaust gas samples were extracted from locations upstream and downstream of the oxidation catalyst, conditioned, and transported to a Nicolet Rega 7000 FTIRS ( upstream location) and a Nicolet Magna 560 FTIRS ( downstream location). The upstream FTIRS also measured the moisture content in the exhaust gas. Moisture measurements by the downstream FTIRS were determined by EECL personnel to be inaccurate. A carbon balance method calculated the moisture concentration at the downstream sampling location.

EECL reported formaldehyde, acetaldehyde, and acrolein values upstream of the catalyst during every run. Inspection of EECL's FTIRS detection limit ( DL) data for these compounds showed that reported formaldehyde concentrations were approximately 10 times the formaldehyde DLs, acetaldehyde concentrations were between 1 and 2 times the acetaldehyde DLs, and acrolein concentrations were less than the acrolein DLs. PES changed a reported value to " Not Detected" ( ND) if the reported value was less than the DL value reported by EECL. Run by run detection limit values of the FTIRS compounds are presented in Table 6.1.

Downstream of the catalyst, EECL reported formaldehyde values for ten of the thirteen runs. Concentrations for the other three runs were all reported as zeros. At the downstream location, only one ( Run 1) of the ten runs where formaldehyde values were reported was greater than the formaldehyde DL. PES changed the reported formaldehyde values downstream of the catalyst to ND for every run except for Run 1. EECL reported acetaldehyde values for every run downstream of the catalyst. The reported downstream Final Report  Caterpillar 3508 EUI 2 3 September 200 1 TABLE 2.2 SUMMARY OFENGINEAND EXHAUST GAS PARAMETERS rptn  revolutions per rrinute t#~  reciprocal of % Excess Air f t lb  foot pounds " F  degrees Fahrenheit bhp  brake horsepower % vd d. b.  % volume dry basis Final Report  Caterpillar 3508 EUI 2 4 September 200 1 TABLE 2.3 STACK CONCENTRATIONS OF DETECTED FllRS AND CEMS COMPOUNDS ppmvd  parts per Milton by volume, dry basis ppnwd Q 15% 02  parts per rrittii by voluma, dry basis, normaitzed to 15% oxygen ppnww  parts per niitiin by volume, wet basis Final Report  Caterpillar 3508 EUI 2 5 September 200 1 concentrations were between one and three times the values of the DLs. These values were approximately twice the acetaldehyde concentrations reported upstream of the catalyst. EECL reported zeros for acrolein for all runs downstream of the catalyst. PES changed the reported acrolein concentrations for all runs downstream of the catalyst to ND.

Table 2.3 also shows in stack and corrected concentrations of the CEMS compounds. EECL personnel operated two CEMS sampling and analysis systems. Engine exhaust gas samples were extracted from locations upstream and downstream of the catalyst. These samples were filtered and dried ( except that the methane/ non methane sample was not dried), then transported to the CEMS analyzer racks. The CEMS detected all target compounds at both the inlet and the outlet locations. Table 6.1 presents the CEMS detection limits for each run.

2.4 GCMS MEASUREMENTS Table 2.4 presents the in stack concentrations and concentrations corrected to 15% oxygen of the GCMS compounds ( 1,3 butadiene, hexane benzene, toluene, ethyl benzene, ( o, m, p) xylenes, and styrene). EM1 personnel operated two Inficon Portable Gas Chromatographs with Mass Spectrometer Detectors. Gas samples for GCMS analysis were extracted from the up and downstream locations through a heated probe and quartz fiber filter, then transported via a heated Teflon@ sample line to a Peltier condenser that continuously removed moisture. The sample was then co mixed with an internal standard mixture ( in a constant ratio of 10: 1) in the GC sampling loop for 1 minute before injection into the GCMS. After purging the sample loop for 1 minute, the GCMS injected the sample onto the separatory column to resolve the target compounds for quantization. A PC based DAS supported each GCMS to calculate peak areas of the target compounds.

The large quantity of small, highly adsorptive soot particles found at both the inlet and outlet sampling locations caused analytical problems. The soot adsorbed a portion of the target analytes ( i. e., benzene and toluene). This effect was documented by analyte spiking ( See Section 6). EM1 took special precautions including modification of the sampling equipment and modification of sampling procedures to minimize the effects of the soot on the measurement results. ( See detailed discussion in Section 5) In spite of these efforts to minimize collection of particulate matter, concentration results for benzene and toluene are consistently biased low.

Benzene and toluene were the only compounds detected upstream of the catalyst. Their concentrations varied from 30 to 140 ppb. These are near, or below the lowest GCMS calibration point of 100 ppb. Benzene was the only compound detected at the catalyst outlet at concentration levels ranging from 30 to 150 ppb. These concentration levels are near, orB below the lowest GCMS calibration point of 100 ppb.

Final Report  Caterpillar 3508 EUI 2 6 September 200 1 TABLE 2.4 STACK CONCENTRATIONS OF DETECTED GCMS COMPOUNDS Pun ID Run1 Run2 Run3 Run4 Run9 Run10 Run11 Run12 Run13 Run14 PAH 1 PAH 2 PAH 3 Catalyst Inlet PPbd ND ND ND ND ND ND ND ND ND ND ND ND N/ A I, 3 Butadiene iexane ppbd @ 15% 02 ND ND ND ND ND ND ND ND ND ND ND ND iwbd ND ND ND ND ND ND ND ND ND ND ND ND N/ A N/ A ppbti @ 15% 02 ND ND ND ND ND ND ND ND ND ND ND ND N/ A ppbd 40 50 120 90 33 35 53 58 33 40 35 50 N/ A jenzene ppbut @ 15% 02 22 30 66 46 19 20 30 33 19 23 20 30 N/ A PPbd 140 loo 0 loo loo 100 loo IO0 loo loo loo loo N/ A  0luene ppb\ rd@ 15% 02 79 100 0 loo loo loo loo loo loo loo loo loo N/ A ppbd ND ND ND ND ND ND ND ND ND ND ND ND N/ A Ithyl Benzene n/ p Xylene Zyrene ppbti @ 15% 02 ND ND ND ND ND ND ND ND ND ND ND ND N/ A ppbd ND ND ND ND ND ND ND ND ND ND ND ND N/ A  Xy lene ppkd @ 15% 02 ND ND ND ND ND ND ND ND ND ND ND ND N/ A PPbd ND ND ND ND ND ND ND ND ND ND ND ND N/ A ppbuj @ 15% 02 ND ND ND ND ND ND ND ND ND ND ND ND PPbd ND ND ND ND ND ND ND ND ND ND ND ND N/ A N/ A ppbuj @ 15% 02 ND ND ND ND ND ND ND ND ND ND ND ND N/ A ppbvd parts perbilliinbyvolume, drybasis ppbvd@ 15% 02 parts perbilliin byvokrme, drybask, noralizedto lS% ox) gen ND  Referto Table6.7forIxm bywndetection limits atthecatatystinlet, andTable68forrun by rundetection limits atthecatalptoutkt.

N/ A  Notavailable. GCMS dataws notcollectedduringthis samplingrun.

Final Report  Caterpillar 3508 EUI 2 7 September 200 1 TABLE 2.4 ( Concluded)

STACK CONCENTRATIONS OF DETECTED GCMS COMPOUNDS Run LD Run1 Run2 Run3 Run4 Run9 Run10 Run11 Run12 Run13 Run14 PAH 1 PAH 2 PAH 3 Catalyst Outlet ppbd ND ND ND ND ND ND ND ND ND ND ND ND N/ A I, 3 Butadiene ppbuj @ 15% 02 ND ND ND ND ND ND ND ND ND ND ND ND N/ A Hexane PPbd ND ND ND ND ND ND ND ND ND ND ND ND N/ A ppb\ rd @ 15% 02 ND ND ND ND ND ND ND ND ND ND ND ND N/ A Benzene Toluene PPbd 0 100 100 100 IO0 100 ND ND 100 0 100 100 N/ A ppbti@ l5% 02 0 0 loo loo loo 0 ND ND 0 0 0 100 N/ A ppbd ND ND ND ND ND ND ND ND ND ND ND ND N/ A ppbul@ 15% 02 ND ND ND ND ND ND ND ND ND ND ND ND N/ A ppbd ND ND ND ND ND ND ND ND ND ND ND ND N/ A Ethyl Benzene ppbui @ 15% 02 ND ND ND ND ND ND ND ND ND ND ND ND N/ A m/ pXylene ND ND ND ND ND ND ND ND ND ND ND ND N/ A ppb\ rd @ 15% 02 ND ND ND ND ND ND ND ND ND ND ND ND N/ A Styrene ND ND ND ND ND ND ND ND ND ND ND ND N/ A ppbu4 @ 15% 02 ND ND ND ND ND ND ND ND ND ND ND ND N/ A PXylene PPbd ND ND ND ND ND ND ND ND ND ND ND ND N/ A ppbui @ 15% 02 ND ND ND ND ND ND ND ND ND ND ND ND N/ A ppbvd park perbillbnbyvolume, dtybasis ppbvd @ I 15% 02 parts perbillbn byvolume, d~ basis, nortnallzed to lS% oxygen ND  Referto Table6.7forrun by rundetectbn limits atthecatalyst lnlet, andTable6.8forrun byiundetectbn limits atthecatalystoutlet.

N/ A  Not available. GC M S data was not collected during this sampling run.

Final Report  Caterpillar 3508 EUI 2 8 September 200 1 2.5 POLYNUCLEAR AROMATIC HYDROCARBON ( PAH) MEASUREMENTS PES used CARB Method 429 to collect samples of the engine exhaust for determination of PAHs up and downstream of the catalyst. A sample of the exhaust gas was extracted through a glass nozzle, heated glass lined probe, a heated quartz filter, and a chilled sorbent trap containing XAD 2 sorbent resin. The resin was extracted and combined with the front half train rinses and the filter and analyzed for PAH content by ERG using Low Resolution Mass Spectrometry. PES did three CARB 429 sampling runs. Each run consisted of simultaneous sampling at both the upstream and downstream locations. The first PAH run was conducted at Run Condition No. 10, and the second PAH run was conducted at Run Condition No. 2. The last PAH run was conducted at Run Condition No. 3. Table 2.5 presents stack gas and sample train parameters for the CARB 429 testing.

The dangerous characteristics ( 5 inches Hg static pressure, 800 " F stack temperature, 2,000 ppm NO, concentration) of the exhaust gas and inadequate access to one of the sample ports mandated that sampling be conducted through only one sampling port upstream of the catalyst. The first sampling run at the inlet was aborted after 50 minutes of sampling. The static pressure of the engine exhaust pushed the glass liner from the heated probe. PES modified the sample probe by replacing the glass liner with a stainless steel liner. The technicians tightened the compression nuts and ferrules on the stainless steel liner more than was possible on the glass liner. This modification enabled collection of samples for the remaining CARB 429 sampling runs. Both of the remaining runs were 120 minutes in duration. PES could not conduct velocity traverses upstream of the catalyst. When the pitot tube was inserted into the duct for velocity traverses, the reading on the manometer was greater than 10 inches H, O. This phenomenon was likely due to the high static pressure. PES did a velocity traverse downstream of the catalyst. This traverse was used to calculate gas velocities upstream of the catalyst, to set sampling rates, and to estimate isokinetic sampling ratios at the inlet. The estimated isokinetic sampling ratios for the CARB 429 runs upstream of the catalyst were 68.4, 104.5, and 92.5 percent for PAH Runs 1,2, and 3.

Downstream of the catalyst, PES conducted three CARB 429 sampling runs. Each sampling run was 120 minutes in duration. Velocity traverses were conducted before and after each run, and the results used to set sampling rates and calculate isokinetic sampling ratios. The isokinetic sampling ratios were 97.1,96.2, and 101.7 for PAH Runs 1,2, and 3, respectively.

Table 2.6 presents the mass emission rates of detected PAH target compounds upstream of the catalyst. Since velocity traverses were conducted in conjunction with the PAH sampling, mass flow rates for the PAH compounds could be calculated. Several of the PAH target compounds ( acenapthylene, benzo( b) fluoranthene, benzo( k) fluoranthene, chrysene, fluoranthene, fluorene, napthalene, phenanthrene, and pyrene) were detected during all three runs. Benzo( a) anthracene was detected during Runs PAH 2 and PAH 3. Acenapthene, anthracene, benzo( g, h, i) perylene, benzo( a) pyrene, dibenzo( a, h) anthracene,

Final Report  Caterpillar 3508 EUI 2 9 September 200 1 TABLE 2.5 SUMMARY OF STACK GAS AND SAMPLING PARAMETERS CARB 429 CATALYST INLET AND OUTLET Run ID PAH 1 PAH 2 PAH 3 Date 8131 I99 9/ l / 99 g/ 2/ 99 Average Catalyst Inlet Sampling Duration, minutes Average Sampling Rate, dscfm a Sample Volume, dscf b Exhaust Gas Temperature, " F Stack Pressure, inches Hg O2 Concentration, % by Volume CO2 Concentration, % by Volume Moisture, % by Volume Exhaust Gas Volumetric Flow Rate:

acfm ` Id dscfm ` ld Stack Gas Velcocity, ft/ s d lsokinetic Sampling Ratio, %

Sampling Duration, minutes Average Sampling Rate, dscfm a Sample Volume, dscf b Exhaust Gas Temperature, " F Stack Pressure, inches Hg O2 Concentration, % by Volume CO2 Concentration, % by Volume Moisture, % by Volume Exhaust Gas Volumetric Flow Rate:

acfm '

dscfm a Stack Gas Velcocity, ft/ s lsokinetic Sampling Ratio, % 50 120 120 0.755 0.621 0.555 37.745 74.575 66.598 800 800 800 29.84 29.84 29.84 10.7 11.1 10.1 7.5 6.8 7.8 8.4 9.3 9.3 0.644 59.639 800 29.84 10.6 7.4 9.0 2979 3035 3061 3025 1,140 1,150 1,160 1150 142 145 146 144 68.4 104.5 92.5 80.4 Catalyst C rttet 120 120 120 0.504 0.503 0.539 60.470 60.399 64.685 761 760 762 25.30 25.38 25.38 10.70 11.20 10.06 7.65 6.87 7.74 8.1 8.2 6.9 0.515 61.851 761 25.38 10.65 7.42 7.7 3,380 3,410 3,410 3400 1,140 1,150 1,160 1150 71.9 72.4 72.5 72.3 97.1 96.2 101.7 98.3 a Dry standard cubic feet per minute at 68" F ( 20" C) and 1 atm.

b Dry standard cubic feet at 68" F ( 20" C) and 1 atm.

' Actual cubic feet per minute at exhaust gas conditions.

d Calculated from standard flow conditions observed at catalyst outlet ( SEE text) C Final Report  Caterpillar 3508 EUI 2 10 September 200 1 TABLE 2.6 EMISSION RATES OF DETECTED PAHS AT CATALYST INLET Run ID PAH 1 PAH 2 PAH 3 Date 8131 I99 9/ l / 99 g/ 2/ 99 Average a Acenaphthene pg/ bhp hr NDb ND ND < 0.15 plb/ hr ND ND ND < 0.22 Acenaphthylene pg/ bhp hr 13 20 35 28 plb/ hr 28 31 48 39 Anthracene pg/ bhp hr ND 6.3 ND < 3.2 plb/ hr ND 9.6 ND < 4.9 Benzo( a) anthracene pg/ bhp hr ND 1.0 1.2 < 1.1 plb/ hr ND 1.6 1.6 < 1.6 Benzo( b) fluoranthene pg/ bhp hr 0.34 1.6 1.7 1.6 plblhr 0.75 2.4 2.3 2.3 Benzo( k) fluoranthene pg/ bhp hr 0.14 0.43 0.41 0.42 plb/ hr 0.31 0.66 0.55 0.61 Benzo( g, h, i) perylene pg/ bhp hr ND ND ND < 0.15 plb/ hr ND ND ND c 0.22 Benzo( a) pyrene pg/ bhp hr ND ND ND < 0.15 plb/ hr ND ND ND C 0.22 Chrysene pg/ bhp hr 1.4 2.8 3.3 3.0 plb/ hr 3.0 4.2 4.5 4.4 Dibenz( a, h) anthracene pg/ bhp hr ND ND ND c 0.15 plb/ hr ND ND ND < 0.22 Fluoranthene pg/ bhp hr 3.5 16 25 21 plb/ hr 7.7 24 34 29 Fluorene pg/ bhp hr 41 43 56 49 @ b/ hr 90 65 75 70 Indeno( l, 2,3 cd) pyrene pg/ bhp hr ND ND ND < 0.15 plb/ hr ND ND ND < 0.22 Naphthalene pg/ bhp hr 179 215 381 298 plb/ hr 390 328 517 422 Phenanthrene pg/ bhp hr 57 71 118 94 plb/ hr 124 107 160 134 Pyrene pg/ bhp hr 14 25 35 30 vlb/ hr 30 38 48 43 * Average of Runs PAH 2 and PAH 3; Run PAH 1 was aborted after 50 minutes because the glass liner separated from the nozzle. PAH 1 data are presented for information only.

b ND indicates that the compound was not detected. Averages include detection limits.

Table 6.14 presents detection limits of PAHs at the catalyst inlet.

Final Report  Caterpillar 3508 EUI 2 11 September 200 1 TABLE 2.7 EMISSION RATES OF DETECTED PAHS AT CATALYST OUTLET Run ID Date Acenapt hene pg/ bhp hr pi b/ hr PAH 1 PAH 2 8131199 9/ l/ 99 ND ND ND ND PAH 3 912199 Average ND < 0.15 ND < 0.25 Benzo( a) anthracene ND indicates that the compound was not detected. Averages include detection limits.

Table 6.15 presents detection linits of PAHs at the catalyst inlet.

Final Report  Caterpillar 3508 EUI 2 12 September 200 1 and indeno( 1,2,3 cd) pyrene were not detected during any of the sampling runs upstream of the catalyst. The table presents the results of each sampling run. Run PAH 1 was aborted, so the averages reported are the averages of the results for the second and the third run. For those compounds that were not detected, the average is the average of the in stack mass flow rate using analytical detection limits reported by ERG. Table 6.14 presents the in stack detection limits at the catalyst inlet for each compound on a run by run basis.

Table 2.7 presents the mass emission rates of detected PAH target compounds at the catalyst outlet. Napthalene and phenanthrene were detected during all three runs, and acenapthylene and fluorene were detected during two of the three runs. Fluoranthene was detected during the third run only. None of the remaining PAH compounds were detected downstream of the catalyst. For these compounds, the ( 3 r@ average detection limit is presented in the average column. Table 6.15 presents the in stack detection limits at the catalyst outlet for each compound on a run by run basis.

2.6 DESTRUCTION OF HAP BY THE CATALYST There are five possible HAP concentration ( or in the case of PAH compounds, mass flow rate) combinations that can occur across the oxidation catalyst. Table 2.8 presents these combinations, and notes whether a destruction efficiency is reported. Out of the five possible combinations, there are two instances where the destruction efficiency of the target pollutant is reported. If pollutant emissions into the catalyst ( Qin) is greater than pollutant emissions exiting the catalyst ( QOJ, % DE is calculated. If the pollutant is detected entering the catalyst, but is not detected exiting the catalyst, % DE is estimated using the concentration of PAH mass flow rate at the inlet, and the concentration or PAH mass flow rate corresponding to the analytical detection limit at the outlet.

TABLE 2.8 MASS FLOW SCENARIOS Scenario No. Result DE Reported?

1 Qin > 0; Qout ' 0; Qin ' Qmt YES II 2 I Qin ' 0; Qout = ND I YES II 3 I Qin < Qout I NO II 4 I Qin = ND; Qwt ' 0 I NO I 5 Qin = ND; Q,", = ND NO Final Report  Caterpillar 3508 EUI 2 13 September 200 1 _ . lll  _" ll._ PES calculated the catalyst destruction efficiency of several target compounds. These data are presented in Table 2.9. Formaldehyde is the only FTIRS compound for which catalyst removal efficiencies are calculated. Since formaldehyde was detected downstream of the catalyst during Run 1, the formaldehyde removal efficiency for Run 1 is calculated with quantified mass emissions rates. For all other runs, the removal efficiency of formaldehdye is estimated using the value of detection limit values at the catalyst outlet. Acetaldehyde removal efficiencies are not calculated, since the mass flow rate of acetaldehyde downstream of the catalyst exceeds the upstream mass flow for every run. Acrolein removal was not calculated because acrolein was detected neither upstream nor downstream of the catalyst.

PES calculated the removal of carbon monoxide and total hydrocarbons, but none of the remaining CEMS compounds. The mass flow rates of NOx into and out of the catalyst were essentially the same. Toluene was the only GCMS compounds for which removal efficiencies were calculated. Since toluene was not detected downstream of the catalyst, toluene detection limits values were used to estimate toluene removal efficiency. Removal efficiencies for benzene were not calculated, since the calculated mass flow rates downstream of the catalyst usually exceeded the flow rates upstream of the catalyst.

PES calculated removal efficiencies for most of the PAH compounds using the data from Runs PAH 2 and PAH 3. Since the Run PAH 1 was aborted at the inlet, no PAH removal efficiencies have been calculated for this run. On the remaining two runs, fluorene, napthalene, and phenanthrene were detected both upstream and downstream. of the catalyst. Acenaphthylene and flouranthene were detected at both locations during Run PAH 3.

2.7 PARTICULATE MATTER MEASUREMENTS Under contract to the Engine Manufacturer's Association, Sierra Instruments conducted testing to determine the mass flow rates of total condensible particulate matter upstream and downstream of the catalyst. EECL included the results of these tests in its test report to PES. PES has reproduced those data in Table 2.9. At the time that this report was written, PES had not received a test report describing the testing or test procedures. Sierra used a BG 1 Micro Dilution Test Stand ( which they manufacture) to extract, dilute, and collect entrained particulate matter up and downstream of the catalyst.

2.8 FUEL OIL ANALYSES PES collected three samples of the fuel oil that was used to fire the Caterpillar engine. One sample was collected each day. Galbraith Laboratories, Inc. in Knoxville, Tennessee did ultimate and proximate analysis of each sample, and analyzed each sample for the target metals. Table 2.10 presents the results of these analyses.

Final Report  Caterpillar 3508 EUI 2 14 September 200 1 TABLE 2.9 REMOVAL EFFICIENCIES OF DETECTED ORGANIC COMPOUNDS I' I Values preceeded by " 9' indicate that the value of the Detectii Limit at the catalyst outlet was used to estimate removal efficiency. "" indicates that the compound was not detected at the catalyst inlet, therfore removal effiiiency was not calculated.

Final Report  Caterpillar 3508 EUI 2 15 September 200 1 TABLE 2.10 METHOD IS0 8178 l PARTICULATE MAITER MASS FLOW DATA Run ID Run 1 Run 2 Run 3 Run 4 Run 9 Run 10 Run 11 Run 12 Run 13 Run 14 Engine Load, bhp 988 692 615 878 988 989 988 988 989 989 Catalyst Inlet Test Aa, g/ bhp hr 0.05 0.07 0.06 0.07 0.05 0.10 0.04 0.10 0.05 0.09 Test Bb, g/ bhp hr 0.05 0.08 0.06 0.05 0.06 0.08 0.04 0.05 0.05 0.09 Awrage 0.05 0.08 0.06 0.06 0.06 0.09 0.04 0.08 0.05 0.09 Catalyst Outlet Test Aa, g/ bhphr 0.08 0.10 0.10 0.08 0.10 0.12 0.08 0.09 0.07 0.17 Test Bb, g/ bhphr 0.07 0.05 0.10 0.08 0.12 0.12 0.08 0.11 0.08 0.15 AIRrage 0.08 0.08 0.10 0.08 0.11 0.12 0.08 0.10 0.08 0.16 a Test Run A was conducted prior to the 33 minute FTIRSICEMSIGCMS run b Test Run B was conducted atier the 33 minute FTlRS/ CEMS/ GCMS run Final Report  Caterpillar 3508 EUI 2 16 September 200 1 TABLE 2.11 SUMMARY OF FUEL OIL ANALYSES C FO 1 C FO 2 C FO 3 S/ 31/ 99 9/ l/ 99 912199 2005 2135 1545 Average Carbon, % w/ w I 87.03 I 87.17 I 87.14 I 87.11 Hydrogen, % w/ w I 13.19 I 13.33 I 13.44 I 13.32 Nitrogen, % w/ w ~~ I < 0.5 I < 0.5 I < 0.5 I < 0.5 Oxygen, % w/ w I < 0.5 I < 0.5 I < 0.5 I < 0.5 Sulfur, % w/ w I 0.04 I 0.04 I 0.06 I 0.05 Water, % w/ w I 0.0073 I 0.0078 I 0.0065 I 0.0072 Ash, % w/ w I < 0.009 I < 0.009 I < 0.008 I < 0.009 Heat of Combustion, Btu/ ib I 19347 I 18,668 I 18,888 I  18,968 Beryllium, ppmw I < l I cl I < l I cl Cadmium, ppmw I < l I < l I < l I ~ Cl Chromium, ppmw I co. 1 I co. 1 I < 0.1 I co. 1 Lead, ppmw I < l I 0.4 I 0.54 I ~ < 0.6 Manganese, ppmw I < l I < l I < l I < I Mercury, ppmw I < 0.57 I < 0.61 I < 0.62 I < 0.60 Nickel, ppmw ~ Selenium, ppmw < l < l  cl < l < 0.6 < 0.6 < 0.6 < 0.6 Final Report  Caterpillar 3508 EUI 2 17 September 200 1 3.0 SOURCE DESCRIPTION AND OPERATION This section presents discussions of the candidate engine and the catalyst that EPA selected for the test program. The sections that follow describe the engine and the operation of the engine during testing.

3.1 ENGINE DESCRIPTION The Caterpillar 3508 EUI stationary internal combustion engine is an eight cylinder, 4 stroke, diesel cycle, internal combustion engine with a manufacturer's sea level rating of 775 brake horsepower ( bhp) at 1800 rpm. The pistons are 6.7 inches in diameter with a 7.5 inch stroke. Air is delivered to the engine via a pressurized air delivery system; air manifold pressures are controlled by the EECL process control system. Engine loading is controlled by a computer controlled water brake dynamometer. Before the test program EECL installed an oxidation catalyst, manufactured by Engelhard, on the engine. EECL aged the catalyst under its normal operating condition ( i. e., burned in the catalyst) before the test program. This procedure ensured that the catalyst's HAP destruction efficiency approximated the HAP destruction efficiency of mature catalysts installed on 4 stroke diesel engines in industry. Table 3.1 presents specifications of the engine and the catalyst. Table 3.2 presents nominal engine operating parameters.

The compression ignition ( Diesel' cycle) engine is similar to the spark ignition ( Otto* cycle) engine, except that the compression ratio is higher, and air alone, rather than a combustible mixture, is admitted into the cylinder chamber on the intake stroke. The rapid compression of the air during the compression stroke raises its temperature higher than the ignition temperature of the fuel. During the first part of the expansion stroke, the fuel is injected into the cylinder chamber at a rate such that the combustion maintains constant pressure in the cylinder. The exhaust stroke pushes the combustion products from the chamber.

' Named for Rudolf Diesel, who began design of the compression ignition engine in 1892.

* Named for Nikolaus A. Otto, who built a highly successful four stroke spark ignited engine in 1876. The name of the cycle of events during the operation of the engine gradually came to be known as the Otto cycle.

Final Report  Caterpillar 3508 EUI 3 l September 200 1 TABLE 3.1 ENGINE AND CATALYST SPECIFICATIONS Caterpillar 3508 EUI ( 4 stroke, diesel cycle, oil fired)

Engine Classification I Four Stroke, Diesel Cycle I Caterpillar 3508 EUI Manufacturer and Type:

Number of Cylinders: I 8 Bore and Stroke: I 6.7 in. x 7.5 in.

Nominal Engine Speed: I 1800 rpm Catalyst Classification I CO/ Odor Control Manufacturer: I Engelhard Date of Manufacture: . Model Number: Serial Number: Item Number: unknown unknown unknown unknown '

Catalyst Material:

Element Size:

Number of Elements: unknown 12 in. x 16 in. x 3.5 in.

4 Final Report  Caterpillar 3508 EUI 3 2 September 200 1 TABLE 3.2 SUMMARY OF NOMINAL ENGINE PARAMETERS Parameter Nominal Value Acceptable Range Designation Torque, & lb 2880 f 2% of value Primary Speed, rpm I 1800 I f 2% of value I Primary Jacket Water Temperature Outlet, " F I 196 I f 5% of value I Primary Oil Temperature Outlet, " F I 215 I f 5% of value I Primary Air Manifold Temperature, " F I 150 I f 5% of value I Primary Air Manifold Pressure, in. Hg I 5" above atm. I f 5% of value I Primary Exhaust Manifold Pressure, in. Hg Varies with AMP f 5% of value Primary Injection Timing I 21' BTDC I f 5% of value I Primary Overall Air/ Fuel Ratio I 3O: l I f 5% of value I Primary Inlet Air Humidity Absolute, lb H, O/ lb Air Fuel Flow, gal/ hr ( lb/ lx) 0.015 42 ( 310) f 10% of value f 5% of value Primary Primary Oil Pressure Inlet, psi I 67 I f 5% of value I Secondary Air Flow, scfm Average Exhaust Temperature, " F 2150 f 5% of value 1000 f 5% of value Secondary Secondary ft lb  foot pounds rpm  revolutions per minute " F  degrees Fahrenheit in. Hg  inches mercury column BTDC  Before Top Dead Center lb H, O/ lb Air  pounds water vapor per pound of air gal/ hr  gallons per hour lb/ hr  pounds per hour psi  pounds per square inch scfm  standard cubic feet per minute Final Report  Caterpillar 3508 EUI 3 3 September 200 1 3.2 ENGINE OPERATION DURING TESTING As stated in Section 2 of this document, four types of test runs were conducted during the test program: quality assurance runs, sampling runs for FTIRS/ CEMS/ GCMS/ PM, CARB 429 sampling runs, and daily baseline runs. The operation of the engine during these various runs is discussed on the following pages and in the following tables.

Table 3.3 presents the test matrix for the Caterpillar engine. The test matrix originally presented in the Quality Assurance Project Plan was estimated based upon the manufacturer's data. When the engine was installed and operated at the EECL, the estimates were found to be inaccurate. Therefore, the test matrix was revised to represent nominal engine operating conditions. Run Conditions 5,6,7, and 8 are conditions which call for changes in the air/ fuel ratio. These conditions are not applicable to the Caterpillar engine, since there is no mixture of air and fuel. These conditions were applicable during testing of the 2 stroke and 4 stroke spark ignition engines.

During the test program, the five engine operating parameters expected to have the greatest impact on pollutant formation were varied. These parameters were: engine speed ( measured in revolutions per minute or r pm), engine torque ( measured in foot pounds or ft lb), injection timing ( the location of the cylinder, relative to top dead center, at the time of fuel injection), intercooler air temperature ( measured in degrees Fahrenheit), and jacket water outlet temperature ( also measured in degrees Fahrenheit). Table 3.4 presents engine parameters that were recorded during each test run and their percent deviation from the target values. The target engine operating parameters were met for every run, except for the engine equivalence ratio. Actual equivalence ratios were less than the target equivalence ratios for every run, which means that engine excess air was greater than the target for every run.

Table 3.5 presents engine parameters during baseline test points, and the deviation of the parameters from the nominal engine parameters. The testing was conducted over a period of three days. During that period the engine did not run continuously, but was shut down each night. Test accuracy required that the overall engine operation did not change over the three day period. The stability of the engine over this period was shown by operating the engine at the baseline condition for one 5 minute period on the second and third day of testing. Changes to the baseline parameters would have indicated a change in the overall operating characteristics of the engine. Distinguishing between emission rate changes attributable to changes in the independent variables and emission rate changes attributable to random changes in the performance of the engine would have been impossible.

Final Report  Caterpillar 3508 EUI 3 4 September 200 1 TABLE 3.3 TARGET ENGINE OPERATING CONDITIONS DURING TESTING Operating Conditions Tested:

Condition 1 Condition 2 Condition 3 Condition 4 Condition 5 Condition 6 Torque Air/ Fuel Injection Intercooler Speed Jacket Water (" A of Equivalence Timing Air Temperature @ pm) maximum) Ratio Temperature ( 9) (" BTDC) ( em 09 H H N S S S H L N S S S L L N S S S L H N S S S Operating Condition Not Applicable For This Engine Operating Condition Not Applicable For This Engine Condition 7 I Operating Condition Not Applicable For This Engine Condition 8 Operating Condition Not Applicable For This Engine Condition 9 H H N S L S Condition 10 H H N S H S Condition 11 H H N S S L Condition 12 H H N S S H Condition 13 H H N L S S Condition 14 H H N H S S H = 1800 H = 100 H = 23 H = 160 H= 206 L = 1600 L= 70 1 N = 0.58 s= 21 s= 150 S= 196 I I I L= 19 I L= 120 I L= 186 Final Report  Caterpillar 3508 EUI 3 5 September 200 1 lABIE3.4 suMMARYmmGlNEP~ 3508m  F& m 10  lam 13   PAJi2 PAH3 1799 1600 1800 16tJl 0% 0%

2018 2019 2016 2016 0.1% 0.2%

21.0 21.0 21.0 21.0 0.0% 0.0%

150 149 130 130 3.4% 3.3%

195 195 196 196 4.7% 4.6%

691 615 0.49 0.54 Fan1 FaRl2 Rm3 fam4 Iam9 Rm II lam 12 lam 14 PAHI 1800 1800 0% 1800 1800 0%

2019 2019 2016 2016 0.1% 0.1% 0.2% 0.2% 0.1%

21.0 21.0 O. O? h 21.0 21.0 0.0% 21.0 21.0 O. C% 21.0 21.0 O. O? h 21.0 21.0 O. U?! 21.0 21.0 O. oD! 19.0 19.0 O. U?~ 23.0 23.0 0.0% 21.0 21.0 0.0% 21.0 21.0 O. oo/ o 150 150 4.1% Mud InjectionTining, " BTDC Target 151 150 0.2% 151 150 0.1% 140 140 0.0% 257 160  0.5% 150 150  0.1% 151 150 0.2% 149 150  0.2% 150 150 0.0% 159 140 3.2%

194 1%

 1.1% 195 196 4.5% 195 196 4.5% 195 196  0.7% 194 196  0.9% 185 186  0.7% 2cE 206 0.1% 194 196  1.0% 194 196 4.9% 194 196  l. u? h 988 692 615 878 988 989 988 988 989 989 Ec+ i& me Ratio, Q 0.52 0.49 0.53 0.57 0.49 0.51 0.51 0.51 0.51 0.52 0.51 rpn rmh.& ims per minute It lb W pods Final Report  Caterpillar 3508 EUI 3 6 September 200 1 TABLE 3.5 SUMMARY OF ENGINE PARAMETERS DURING BASELINE RUNS un ID Baseline 1 ngine Speed, rpm Actual Target Detiation 1799 1800  0.05%

ngine Torque, ft lb Actual Target Deviation 2884 2880 0.14%

Actual jection Timing, " BTDC Target Detiation Actual ltercooler Air Outlet Temperature, ' Target Detiation acket Water Temperature, " F Actual Target Detiation 194 196  0.30%

Gl Temperature, " F Actual Target Detiation 231 215 2.37%

, ir Manifold Pressure, in. Hg rlet Air Humidity, lb H, O/ lb air Actual Target Dedation Actual Target Detiation 29.6C 29.6C 0.01%

O. OlE 0.015 6.67%

) il Pressure, psig Actual Target Deviation 66.4f 67.0(

 0.82%

ixhaust Temperature, " F Actual Target Detiation 230 215 2.27%

rpm  rewlutions per minute ft lb  foot pounds " BTDC  degrees Before Top Dead Center lb H20 / lb air  pounds water Mpor per pound of air in. Hg  inches of mercury psig  pounds per square inch, gauge " F  degrees Fahrenheit Final Report  Caterpillar 3508 EUI 3 7 September 2001 4.0 SAMPLING LOCATIONS Figures 4.1 and 4.2 present schematic drawings of the pre catalyst exhaust gas piping and CARB 429 traverse point locations for the Caterpillar 3508 EUI engine. Figures 4.3 and 4.4 present a schematic drawing of the 12 inch ( ID) post catalyst exhaust gas piping and traverse point locations for the 3508 EUI engine. Sample locations for the testing of this engine are also shown.

The exhaust piping upstream of the catalyst consisted of an 8 inch internal diameter ( ID) pipe that connected the engine exhaust to the catalyst. The sampling location before the catalyst consisted of several sets of sampling ports used for isokinetic sampling and extraction of sample gas for the FTIRS, CEMS and GCMS systems. CAR$ 429 sampling before the catalyst was conducted using one 3 inch ID sample port. The sample port was located 36 inches ( 4.5 diameters) downstream of the turbo charger exhausts. The port was located 26 inches ( 3.25 diameters) upstream of the the nearest disturbance, which was a 90" bend. The sample port was fitted with a ball valve and high pressure couplings to enable sample traveres. Sampling was conducted through one port using a three point sample matrix, as shown in Figure 4.2. Lack of safe access to the second port precluded a traverse at this location.

Multiple ports for sample gas extraction were installed on an exhaust header after the catalyst. The common header was 12 inches in diameter and directed exhaust gases from the engines tested to the atmosphere. CARB 429 sampling and velocity traverses were conducted through two 3 inch ID ports. The ports were on perpendicular diameters and located 8 1 inches ( 6.75 diameters) downstream of the nearest flow disturbance, which was a " tee" union. Exhaust gases from the outlet of the catalyst made a 90" turn into the exhaust header. The third leg of the tee was disconnected and capped off. The ports were located 225 inches ( 18.75 diameters) upstream of the nearest flow disturbance, which was a 90" bend in the header. Velocity and sample traverses were conducted using a 12 point sample matrix, as shown in Figure 4.4.

Final Report  Caterpillar 3508 EUI 4 l September 200 1 Oxidation Catalyst FTIRS Port GC/ MS Port Expansion Joint ( typ.)

I I t Hydraulic Back Pressure Valve A Frame ___)

Note: Drawing is not to scale Sampling Platform PM Port r1 v 0 b Caterpillar 3508 EUI Diesel Engine 8"

f 26 '

c PAH Sampling Location Dynomometer Figure 4.1 Inlet Sample Port Locations for Velocity, CARB 429, FTIRS, CEMS, AND GCMS Sampling 1 Final Report  Caterpillar 3508 EUI 4 2 September 200 1 8 "

Traverse Point Number : 3 Distance from Inside wall ( inches )

15116 4 7 l/ 16 Figure 4.2 Inlet Traverse Point Locations for Velocity and CARB 429 Sampling Final Report  Caterpillar 3508 EUI 4 3 September 200 1 p 8+ 4 1 225"

l l t FTIRS Hydraulic Back Pressure + Valve Oxidation Catalyst + Ll Ll t t t Port PAH Sampling PM Port Ports Note: Top View GUMS Port Ll Flow from Engine Figure 4.3 Outlet Sample Port Locations for Velocity, CARB 429, FTIRS, CEMS and GCMS Sampling Final Report  Caterpillar 3508 EUI 4 4 September 200 1 12 " 6 5 `:

Traverse Point Distance from Number Inside wall ( inches )

1 II2 2 1 314 3 3 I/ 2 4 8 7116 5 10 l/ 4 6 11 I/ 2 Figure 4.4 Outlet Traverse Point Locations for Velocity and CARB 429 Sampling Final Report  Caterpillar 3508 EUI 4 5 September 200 1 5.0 SAMPLING AND ANALYSIS METHODS This section discusses the various sampling and analysis methods employed by PES, EMI, EECL, ERG and Sierra Instruments to quantify the HAP emissions before and after the oxidation catalyst. PES selected the sampling and analysis procedures that would provide the information required during the planning stages of the project. The methods were selected to provide the required data in the most economical fashion, while providing the quality required by the Emissions Standards Division ( ESD).

PES divided these methods into two categories based upon quality control procedures employed. Type I methods were typical source test methods, designed by EPA to be portable, field test procedures. PES and the subcontractors followed QA and calibration procedures described in 40 CFR 60, Appendix A ( or other references as appropriate) for these methods.

Type II methods were those that used permanently installed instruments housed in a temperature controlled environment and operated in the same fashion as continuous monitors used by industry to show compliance with emission regulations. Because these instruments are maintained in a laboratory type environment ( the control room at EECL), fewer QA activities and calibrations adequately show their continuing accuracy. The only significant change to the quality assurance activities was that fewer instrument calibrations were done to quantify instrument drift. Historical calibration data for the instruments shows their stable operation over extended, e. g., 24 hour, periods. Multipoint calibrations were conducted ( including the sampling system bias checks) on these instruments once at the beginning of each engine test.

Table 5.1 summarizes the parameters measured, the sampling methods, the classification, and measurement principle. The text that follows presents brief descriptions of the sampling and analysis procedures used.

5.1 LOCATION OF MEASUREMENT SITES AND SAMPLE/ VELOCITY TRAVERSE POINTS PES used EPA Method 1, " Sample and Velocity Traverses for Stationary Sources," to select the measurement sites for velocity traverses and CARB 429 sampling up and Final Report  Caterpillar 3508 EUI 5 l September 200 1 TABLE 5.1 SUMMARY OF SAMPLING AND ANALYSIS METHODS Parameter sample Point Location Velocity and Volumetric Flow Oxygen and Carbon Dioxide Moisture Nitrogen Oxides Carbon Monoxide Formaldehyde, Acetaldehyde, Acrolein 1,3 Butadiene, Hexane, Benzene, Toluene, Ethyl benzene, Xylenes, Styrene Methane Non& Methane Hydrocarbons Total Hydrocarbons Polycyclic Aromatic Hydrocarbons Measurement Test Method QA Category Principle EPA Method 1 Type I Linear Measurement EPA Method 2 Type I Differential Pressure Paramagnetic and EPA Method 3A Type II Non dispersive Infrared Analyzers EPA Method 4 Type I Gravimetric GRI Protocol' Type I FTIRS Analyzer Carbon Balance* Type I Stoichiometry Chemiluminescent EPA Method 7E Type II Analyzer EPA Method 10 Type II GFC/ NDIR Analyzer GRI Protocol Type II FTIRS Analyzer Gas Chromatograph Alternate Method 17 Type I w/ Mass Spectrometer Detector EPA Method 25A ( modified) Type II GC FID Analyzer EPA Method 25A ( modified) Type II GC FID Analyzer EPA Method 25A Type II FID Analyzer CARB 429 Type I Low Resolution GCMS Particulate Matter IS0 8178 1 Type I Micro Dilution Gravimetric ' Measurement of Select Hazardous Air Pollutants, Criteria Pollutants, and Moisture Using Fourier Transform Infrared ( FTIR) Spectroscopy. Presented as an Appendix to Fourier Transform Infrared Spectroscopy ( FTIRS) Method Validation at a Natural Gas Fired Internal Combustion Engine ( G& 95/ 027 l), Gas Research Institute, December 1995.

2 Derivation of General Equation for Obtaining Engine Exhaust Emissions on a Mass Basis Using the " Total Carbon" Method.

Final Report  Caterpillar 3508 EUI 5 2 September 200 1 TABLE 5.1 ( Concluded)

SUMMARY OF SAMPLING AND ANALYSIS METHODS Parameter Test Method QA Category Measurement Principle Fuel Oil Composition ( Ultimate Analysis) ASTM D 5291 ( C, H, N) ASTM 4239 ( S) ASTM D 1744 ( Moisture) ASTM D482 Ash Type I ( See Text)

Fuel Oil Metals Analysis SW 846 3051 ( Prep) SW 846 6010B SW 846 7000 SW 846 7470A SW 846 7471A Type I ( See Text)

downstream of the catalyst. PES used the cyclonic flow check procedure outlined in Method 1 to evaluate the suitability of the inlet location for isokinetic sampling. The measurement sites are discussed in Section 4.0.

5.2 DETERMINATION OF STACK GAS VOLUMETRIC FLOW RATE ,

During the PAH runs, Method 2 was used in direct support of the CAIXB 429 sampling. The mass flow rates of the PAH compounds and the run by run detection limits are calculated using the results of these velocity traverses. PES used EPA Method 2, ` Determination of Stack Gas Velocity and Volumetric Flow Rate ( Type S Pitot Tube)," to determine stack gas velocity during CARB 429 sampling. The test crew used a Type S pitot tube, constructed according to specifications of Section 2.1 of Method 2 and having a coefficient ( C,) of 0.84. The pitot tube was connected to an inclined/ vertical manometer and the Ap measured at each traverse point. Stack gas temperature was measured using a Type K thermocouple. The average stack gas velocity was calculated from the average of the square roots of the Ap values, the average stack gas temperature, the stack gas molecular weight, and the absolute stack pressure. The volumetric flow rate is the product of velocity and the stack cross sectional area of the duct at the sampling location. PES conducted a velocity traverse using the standard pitot tube before each run and adjusted the sampling rate of the CARB 429 train based upon these data. PES employed this approach with the approval of the WAM. Access to the sampling locations was severely restricted due to the short runs of exhaust piping and the profusion of sampling probes required during each sampling run.

Final Report  Caterpillar 3508 EUI 5 3 September 200 1 5.3 DETERMINATION OF STACK GAS OXYGEN AND CARBON DIOXIDE CONTENT EECL used EPA Method 3A, " Determination of Oxygen and Carbon Dioxide Concentrations in Emissions from Stationary Sources ( Instrumental Analyzer Procedure)," to measure oxygen and carbon dioxide content of the exhaust gas during testing. EECL's sample gas extraction and transport system extracted a gas sample from the exhaust gas stream. The sample was conditioned to remove moisture and entrained particulate matter and directed the Rosemount NGA 2000 gas analysis system. Oxygen was measured using the paramagnetic detection principle. Carbon dioxide was measured using a non dispersive infrared ( NDIR) analyzer. The oxygen and carbon dioxide monitors were calibrated with a pre purified zero gas and three upscale gas standards corresponding to approximately 30,55, and 85 percent of the instruments' analytical ranges. EECL used only EPA Protocol gas standards certified by the gas manufacturer. The calibration gases that were used and the calibration responses of the instruments are discussed in Section 6.0 of this document. A schematic diagram of the FTIRWEMS sampling and analysis system is presented in Figure 5.1.

5.4 DETERMINATION OF STACK GAS MOISTURE CONTENT PES and EECL used three methods to determine the moisture concentration in the exhaust gas before and after the catalyst. Method 4 was used in direct support of the CARB 429 sampling during the PAH runs. During the CEMS/ GCMS/ FTIRS runs, moisture was measured using the FTIRS upstream of the catalyst, and by a carbon balance calculation downstream of the catalyst. During the testing, EECL personnel determined that the moisture concentrations after the catalyst, as measured by the Nicolet Magna 560 FTIRS analyzer, were about 6 percent higher that actual. EECL calculated the moisture concentration after the catalyst using a carbon balance method.

PES used EPA Method 4, " Determination of Moisture Content in Stack Gases," to measure the flue gas moisture content during the CARB 429 sampling. The gas sample was extracted from the exhaust pipe and pulled through an impinger train chilled by an ice bath. The field technicians weighed the impinger train ( including the XAD@ 2 sorbent trap) before and after sampling. PES then calculated the quantity of water collected in the train and the moisture content of the stack gas.

EECL used methodology described in the document " Measurement of Select Hazardous Air Pollutants, Criteria Pollutants, and Moisture Using Fourier Transform Infiared ( FTIRS) Spectroscopy" to measure moisture concentrations upstream of the catalyst. This document is called the GRI Protocol in this report, and is presented as Appendix B of a report published by the Gas Research Institute: " Fourier Transform Inpared Spectroscopy ( FTIRS) Method Validation at a Natural Gas Fired Internal Combustion Engine." A sample Final Report  Caterpillar 3508 EUI 5 4 September 200 1 . CHjNMHC Analyzer    I I Heated Sample Line I I t I I I . _ _. . . . .  . . ..   . . ti Miratech Oxidation I I I I .

88 ( Acq& if$ m 1 I I Calibration Gas Cylinders : Catalyst I c . .._..._........... i Exhaust Flow Heated Sample Line  1 I  THC Analyzer I I { CHjNMHC Analyzer I  i Figure 5.1 Schematic Diagram of EECL FTIRWCEMS Sampling and Analysis System Final Report  Caterpillar 3508 EUI 5 5 September 200 1 of the gas was extracted from the exhaust and directed to a Nicolet Rega 7000 FTIRS analyzer to measure the moisture concentration in the exhaust gas. The gas sample was filtered to remove entrained particulate matter and transported to the analyzer via a heated Teflon@ sampling line. Further discussion of the FTIRS sampling and analysis method may be found in the report generated by the EECL and the GRI protocol.

Because the FTIRS analyzer downstream of the catalyst did not measure the moisture concentration accurately, EECL used a carbon balance method to calculate the moisture present in the gas stream downstream of the catalyst. The method used is discussed in the EECL report in Appendix A.

5.5 DETERMINATION OF NITROGEN OXIDES EPA Method 7E, " Determination of Nitrogen Oxide Emissions from Stationary Sources ( Instrumental Analyzer Procedure)," determined nitrogen oxide content of the exhaust gases. These tests also provided the data needed to do the EPA Method 301 validation of the FTIRS for NO, emissions from this source. A gas sample was extracted from the exhaust gas stream, conditioned to remove moisture, and the nitrogen oxide concentration determined by an instrumental analyzer. The measurement principle for oxides of nitrogen is chemiluminescence. The NO, monitor was calibrated with a pre purified zero gas, and three upscale gas standards corresponding to approximately 30,55, and 85 percent of the instruments analytical ranges. EECL used EPA Protocol gas standards certified by the gas manufacturer. The calibration gases that were used and the calibration responses of the instruments are discussed in Section 6.0 of this document. A schematic diagram of the FTIRSKEMS sampling and analysis system is presented in Figure 5.1.

5.6 DETERMINATION OF CARBON MONOXIDE EPA Method 10, " Determination of Carbon Monoxide Emissionsfiom Stationary Sources," measured the CO concentration of the exhaust gas during the testing. These tests also provided the data needed to do the EPA Method 30 1 validation of the FTIRS sampling and analysis system for CO emissions from this source. A gas sample was extracted from the exhaust gas stream, conditioned to remove moisture, and the carbon monoxide concentration determined by an instrumental analyzer. The measurement principle for carbon monoxide is GFUNDIR. The CO monitor was calibrated using a pre purified zero gas and three upscale gas standards corresponding to approximately 30,55 and 85 percent of the instrument's analytical range. All gas standards used for calibrations were prepared according to EPA Protocol and certified by the gas manufacturer. The calibration gases that were used and the calibration responses of the instruments are discussed in Section 6.0 of this document. A schematic diagram of the FTIRSKEMS sampling and analysis system is presented in Figure 5.1.

Final Report  Caterpillar 3508 EUI 5 6 September 200 1 5.7 DETERMINATION OF TOTAL HYDROCARBONS EPA Method 25A, Determination of Total Gaseous Organic Concentration Using a Flame Ionization Analyzer, determined the total hydrocarbon concentrations at the inlet and the outlet of the catalyst. At the catalyst inlet, EECL used a Therm0 Environmental Instruments ( TECO) Model 5 1 Total Hydrocarbon Analyzer. The analyzer consisted of a heated compartment to prevent condensation of organic compounds, and a Flame Ionization Detector ( FID) to measure THC concentrations. At the catalyst outlet, EECL used a Rosemount Analytical NGA 2000 FID Hydrocarbon Analyzer. This analyzer also used an FID to measure the concentrations of THC in the gas stream. The FID detector consists of a burner in which a regulated flow of a sample gas passes through a flame sustained by regulated flows of a fuel gas and air. The hydrocarbon components of the sample stream ionize in the flame. The positive ions that are produced are collected by an electrode causing current to flow through a measuring circuit. The ionization current is proportional to the rate at which carbon atoms enter the burner, and is therefore a measure of the concentration of hydrocarbons in the sample.

5.8 DETERMINATION OF METHANE AND NON METHANE HYDROCARBONS A modification of EPA Method 25A, " Determination of Total Gaseous Organic Concentration Using a Flame Ionization Analyzer," determined the methane and non methane concentrations at the inlet and the outlet of the catalyst. Gas samples extracted from each gas stream were transported to MSA 1030H Methane/ Non Methane Analyzers. These analyzers are single purpose gas chromatographs that separate methane from the other organic compounds in the sample by passing the sample through a separation column. The methane elutes from the column first and is directed to the flame ionization detector. Then, the analyzer reverses the flow through the column and the remaining organic compounds are back flushed to the same detector. The analyzer sums the two fractions to yield the concentration of total organic compounds. Because this unit is a gas chromatograph, it cannot measure methane and non methane concentrations continuously. During testing, each analyzer determined concentrations once every five minutes. This frequency is sufficient for testing on RICE because the operating conditions were maintained within close constraints. Each analyzer was calibrated before each week of testing using methane and propane calibration standards corresponding to approximately 30,50, and 85 percent of the instrument span. The calibration gases that were used and the calibration responses of the instruments are discussed in Section 6.0 of this document. A schematic diagram of the FTIRWEMS sampling and analysis system is presented in Figure 5.1.

Final Report  Caterpillar 3508 EUI 5 7 September 200 1 5.9 DETERMINATION OF GASEOUS ORGANIC HAP USING FTIRS EECL used two FTIRS systems that met the sampling and analysis requirements set forth in the GRI Protocol. GRI validated extractive FTIRS systems successfully for an analysis of emissions from natural gas fired RICE. The extractive FTIRS continuously extracts a sample gas from the stack, transports the sample to the FTIRS system, and does spectral analysis of the sample gas. The computer system analyzes sample gas spectra for target analytes continuously and archives them for possible later reanalysis. Table 5.2 presents specifications of the FTIRS analyzers.

TABLE 5.2 FTIRS ANALYZER SPECIFICATIONS Parameter Pre catalyst Manufacturer and Type Nicolet Rega 7000 Post catalyst Nicolet Magna 560 Spectral Resolution Detector Type Cell Type Cell Temperature Cell Pressure 0.5 cm  I 0.5 cm"

MCT A MCT A 4.2 Meter  Fixed Path Length 2.0 Meter  Fixed Path Length 185 " C 165 " C 600 Torr 600 Torr Cell Window Material Zinc Cellinide KE3r The sampling and measurement system consists of the following components:

l heated probe;

l heated filter;

l heat traced Teflon@ sample line;

l Teflon@ coated, heated head sample pump;

l FTIRS spectrometer; and l QA/ QC apparatus.

EECL validated each sample extraction and analysis system for formaldehyde, acetaldehyde, and acrolein before testing. The results of the FTIRS validation are discussed in Section 6.0. The basic sampling procedure consisted of EECL taking an initial Final Report  Caterpillar 3508 EUI 5 8 September 200 1 interferogram of the stack gas with the FTIRS measurement and analysis system before each test to describe the sample matrix. This measured the concentrations of moisture and the target pollutants and allowed for adjustments to the cell pathlength and the spectral analysis regions if the concentrations differed from expectations. Sample conditioning was not necessary at the EECL test site.

After QA/ QC procedures and initial adjustments were completed for a given test day, a gas sample was drawn continuously through the heated FTIRS cell while the system collected spectral data. The FTIRS systems collected data simultaneously with the other continuous monitors and with the manual train sampling for PAHs during CARB 429 runs. The spectrometer collected one complete spectrum of the sample, as an interferogram, per second and averaged interferograms over l minute periods. The FTIRS computer converted these time integrated interferogram into conventional wave number spectra, analyzed for the target compounds, and archived the data. Sample collection was 33 minutes in duration, coinciding with the test runs.

5.10 DETERMINATION OF ORGANIC HAP BY DIRECT INTERFACE GCMS The sampling and analytical procedures used during this testing program followed those detailed in EPA Alternate Method 17 " Determination of Gaseous Organic Compounds by Direct Interface GUMS". The instrument was calibrated on site using a lo ppm manufacturer's certified compressed gas mixture consisting of nine target analytes ( benzene, toluene, o, m, p xylenes, styrene, ethyl benzene, 1,3 butadiene, and hexane) in nitrogen balance. Calibrations were conducted at 10 ppm, 3 ppm, 1 ppm and 100 ppb to provide enough calibration points for all of the target analytes. The 10 ppm standard was diluted with VOC free nitrogen using an EM1 calibration gas manifold with three mass flow meters. The mass flow meters were calibrated in the field on the day of use by comparison to a digital bubble meter with a NIST traceable calibration. Also, an independent 1 ppm standard was used to verify the calibration validity and calibration gas dilution technique as required by the method.

Effluent gas samples were withdrawn at a constant flow rate ( 1.5 liters/ minute, dry basis) from a single point located approximately at the midpoint of the exhaust pipe. The estimated gas residence time through the sampling system at this flow rate is less than 1 minute. The response time required to equilibrate a step change in sample concentration was approximately 6 minutes. During this test program, the catalyst inlet and outlet GCMS measurement systems collected effluent simultaneously from each location for a period not less than 10 minutes before acquisition by the GCMS instrumentation. A test run consisted of collection of four lo minute samples from each location.

Figure 5.2 presents a schematic of the GCMS measurement system( s) used during the test program. Each sampling system consisted of a heated probe, heated 0.3 micron quartz Final Report  Caterpillar 3508 EUI 5 9 September 200 1 fiber filters, heated head sample pump, and a heated Teflon@ sampling line to transport the gas to the control units. The control units included flow measurement and flow control capabilities and Peltier cooled condensers with continuous condensate removal to dry the sample gas. All of the sample gases were directed through the condensers ( i. e., the condenser bypass was not used) and the condensers were operated at 36 39 " F. This resulted in a sample moisture content of less than 2%. The control units also included provisions to ensure that the sample gas at the GCMS inlet probe was at atmospheric pressure so that the quantity of internal standards co injected with the sample was unaffected.

Several equipment modifications were made for the test on the Caterpillar engine. High soot loading was expected at the inlet sampling location. Therefore, two 0.3 micron quartz fiber filters were installed in series on the sampling system upstream of the catalyst to prevent breakthrough of the particulate matter and subsequent coating of the internal surfaces of the measurement system. A single 0.3 micron quartz fiber filter was used in the downstream of the catalyst. A short length of unheated stainless steel tubing was installed at the inlet sampling location to cool the exhaust stream from 1100 " F to about 300 400 " F. A three way valve with an atmospheric vent was installed at the upstream location sampling probe because of the elevated static pressure at this sampling location and concerns that this could adversely affect system calibration checks. The three way valve was very useful because it also allowed sampling of ambient air between test runs during the extended periods required to achieve stable engine operation and during other test delays. Finally, a cooling system comprised of a fan and metal foil flexible duct was used to convey relatively cool ambient air from the floor of the engine room to the electronic control sections of the inlet and outlet sampling system probe boxes. This prevented overheating of electronics and pump motors caused by the elevated ambient temperatures and infrared radiation at the sampling locations during the tests.

Final Report  Caterpillar 3508 EUI 5 10 September 200 1 Heated Probe 250'

.5 lpm constant rate sampling)

___ ___ _.

Excess Samnle Atmosnheric Vent ____   By Mass Flow Meter Mass Flow Meter I Condenser _ Flow Control l 71 Flow r l Flow Condenser System ondensate Drain \ Contr 1 Box Heated to 125 ° F ( or at least 5 ° F above saturation temperature of sample gas ) Connection Line 50 cc/ min during GC MS sample acquisition)

GC MS Analyzer Figure 5.2 Schematic of GCMS Sampling and Analysis System Final Report Caterpillar 3508 EUI 5 l 1 September 2001 . 5.11 DETERMINATION OF POLYCYCLIC AROMATIC HYDROCARBONS BY CARB 429 PES used CARB Method 429, " Determination of Polycyclic Aromatic Hydrocarbon ( PAH) Emissions porn Stationary Sources," to quantify PAH concentrations and emission rates before and after the catalyst. Sample run times were 120 minutes in duration. Runs PAH 1, PAH 2, and PAH 3 were conducted with the engine and test conditions 10,2, and 3, respectively. Figure 5.3 presents a simplified schematic diagram of the CARB 429 sample train. The CARB 429 sampling train was modified to enable sampling under difficult test conditions. At the inlet location a ball valve was placed inclined at the end of the probe. The valve was used to restrict the static pressure and to ensure that the sampling train was not over pressurized. The outlet of the ball valve was connected to the inlet of the condenser with a heated Teflon@ sample line. A heated sample line between the sample probe and the condenser was also used downstream of the catalyst. The sample line was used to facilitate sample traverses in the horizontal duct.

PES field technicians recovered the CARB Method 429 sample train as described by CARB Method 429. Method 429 specifies that sample recovery rinses be done with acetone, hexane, and methylene chloride. PES collected blank samples of reagent grade water, acetone, hexane, methylene chloride, unused filters, and XAD@ 2 resin cartridges used during the test program. The sample recovery apparatus consisted of pre cleaned Teflon@' or glass. Field technicians did three acetone rinses, three hexane rinses, and three methylene chloride rinses of each sample train component from the nozzle to the front half of the filter. They also rinsed the back half of the filter holder, the connector, and the condenser three times with acetone. They soaked the back half of the filter holder, connector, and condenser three times with acetone, hexane, and methylene chloride, for five minutes each time. PES provided pre cleaned amber glass sample bottles with Teflon@ seals for the recovery of solvent rinses.

After sampling and recovery, the CARB 429 sample fractions were stored on ice and transported by PES personnel from Fort Collins, Colorado, to PES' laboratory facilities in Research Triangle Park, North Carolina. The sample bottles were examined for breakage and sample loss. The samples were then transferred by PES personnel to ERG laboratory facilities in Morrisville, North Carolina, for sample extraction and analysis. ERG extracted the sample fractions for each PAH sampling run with methylene chloride, then combined the extracts. The 6 extracts ( 3 inlet samples and 3 outlet samples) were concentrated to a volume of about 15 ml using a Kuderna Danish flask, then evaporated to dryness using a nitrogen blowdown apparatus. The extracts were each reconstituted with 1 ml hexane before analysis using a gas chromatograph with a low resolution mass spectrometer.

Final Report Caterpillar 3508 EUI 5 12 September 200 1 / bygone ( Optional)

Heated Probe, S type Pitot & Temp. Sensor t Temp. Readout Pitot Manometer Filter Assembly  Transfer Line Thermocou Sorbent Module ( water cooled)

Impingers in Ice Bath:

Thermocouple Main Valve Orifice Dr Gas 9 eter Pump Figure 5.3. Schematic Diagram of CARB 429 PAH Sampling Train Final Report Caterpillar 3508 EUI 5 13 September 200 1 5.12 DETERMINATION OF PARTICULATE MATTER Particulate sampling was conducted simultaneously with the FTIRS/ CEMS/ GCMS and CARB 429 testing both upstream and downstream of the catalyst. PM sampling was conducted by Sierra Instruments using a BG 1 Micro dilution test stand. Sierra employed procedures outlined in International Organization for Standardization ( ISO) Method 8 178 1 " Reciprocating Internal Combustion Engine  Exhaust Emission Measurement  Part 1: Test bed Measurement of Gaseous and Particulate Exhaust Emissions ".

5.13 DETERMINATION OF FUEL OIL COMPOSITION PES personnel collected one sample of the fuel oil used to fire the engine on each day of sampling. These samples were analyzed by Galbraith Laboratories, Inc. The sample analysis consisted of ultimate and proximate analyses and an analysis to measure the concentrations of the target metals. Table 5.3 summarizes the analytical methods used for these determinations.

Galbraith Laboratories used methods from the American Society for Testing and Materials ( ASTM) to determine the carbon, hydrogen, nitrogen, sulfur, moisture, and ash content of the fuel oil. Galbraith Laboratories also determined the heat content of the fuel oil. From this information, PES calculated a fuel factor, F,, and the heating rate of the engine during each of the test runs.

Galbraith Laboratories used analysis methods published by EPA's Office of Solid Waste ( OSW) to measure the content of the target metals. An aliquot of the fuel oil was acid digested, and the digestate analyzed to determine metals content.

Final Report Caterpillar 3508 EUI 5 14 September 200 1 TABLE 5.3 SUMMARY OF FUEL OIL ANALYSIS METHODS Parameter Analysis Method Carbon, Hydrogen, Nitrogen ASTM D529 l 96 Sulfur Moisture Ash ASTM D4239 ASTM D1744 ASTM D482 I Sample Preparation ( Metals) SW 846 305 1 I Cadmium, Chromium, Lead, Manganese, Nickel, SW 846 6010B ( ICP AES)'

II Mercury I SW 846 7470A ( CVAAS) 4 SW 846 7471A ( CVAAS) ( I 3 Inductively coupled plasma atomic emission spectrometry.

4 Cold vapor atomic absorption spectrophotometry.

Final Report Caterpillar 3508 EUI 5 15 September 200 1 6.0 QUALITY ASSURANCE/ QUALITY CONTROL PROCEDURES AND RESULTS This section summarizes the specific QA/ QC procedures that PES, EECL, EMI, and ERG personnel employed during the performance of this source testing program. PES' quality assurance program was based upon the procedures and guidelines contained in the " Quality Assurance Handbook for Air Pollution Measurement Systems, Volume III, Stationary Source Specific Methods," EPA/ 600/ R 94/ 038c, and in the test methods. These procedures ensure the collection, analysis, and reporting of reliable source test data.

6.1 FTIRS QA/ QC PROCEDURES EECL calibrated the FTIRS instruments before each engine test series and at the beginning and end of each test day. The calibration procedures employed were consistent with procedures found in the following documents:

Gas Research Institute Report Number GRI 95/ 027 1 entitled, " Fourier Transform Infrared ( FTIRS) Method Validation at a Natural Gas Fired Internal Combustion Engine"

This report was prepared for the Gas Research Institute by Radian Corporation. Included as appendices are two additional documents, which also have relevance in the test program:

" Measurement of Select Hazardous Air Pollutants, Criteria Pollutants, and Moisture Using Fourier Transform Infrared ( FTIRS) Spectroscopy"  Prepared by Radian Corporation for the Gas Research Institute.

" Protocol for Performing Extractive FTIRS Measurements to Characterize Various Gas Industry Sources for Air Toxics"  Prepared by Radian Corporation for the Gas Research Institute.

Final Report  Caterpillar 3508 EUI 6 l September 200 1 6.1.1 FTIRS Svstem PreDaration Both FTIRS sampling systems ( before and after the catalyst) were subjected to an EPA Method 301 validation process for formaldehyde, acetaldehyde, and acrolein. The validation process quantified the precision and accuracy of each FTIRS analyzer for these compounds. Besides the validation program, EECL personnel did the following calibration procedures before each engine test series.

1. Source Evaluation  Initial source data were acquired to verify concentration ' ranges of target compounds and possible interferences. This was completed before and during the Method 301 validation process for formaldehyde, acetaldehyde, and acrolein, and during the test program for moisture.

2. Sample System Leak Check  A leak check was done on the portions of the system between the sample filter and the pump outlet. A rotameter was connected to the discharge side of the sample pump. The indicated sample flow rate was recorded while the sample system was operating at typical temperatures and pressures ( the sample pump pulled a slight vacuum on the suction side). The inlet was closed off just downstream of the sample probe. A rotameter monitored the flow rate. A leak rate of 4% or less of the standard sampling rate of 500 ml/ min indicated an acceptable leak check.

3. Analyzer Leak Check  Both FTIRS analyzers were checked to ensure that they were operating at normal operating temperatures and pressures. The operating pressures were recorded. The automatic pressure control device was disabled and the inlet to the FTIRS was closed. The cell was evacuated to 20% or less of the normal operating pressure. After the cell was evacuated, it was isolated and the cell pressure was monitored with a dedicated pressure sensor. The leak rate of the measurement cell must be less than 10 Torr per minute for 1 minute for the analyzer leak to be considered acceptable.

4. Cell Pathlength Determination  The FTIRS cell pathlengths were to be determined using the procedure outlined in the Field Procedure Section the document entitled " Protocol for Performing Extractive FTIRS Measurements to Characterize Various Gas Industry Sources for Air Toxics." Because each FTIRS was a fixed pathlength unit ( i. e., the pathlengths were not adjustable) measurements of the cell pathlengths were, deemed unnecessary. The cell pathlengths specified by the manufacturer were used in the measurement algorithms.

Final Report  Caterpillar 3508 EUI 6 2 September 200 1 6.1.2 FTIRS Daily Calibrations and OA Procedures Before each day of testing, EECL personnel calibrated each FTIRS system following the procedures outlined below.

1. Instrument Stabilization  Each of the following components were checked for proper operation to ensure the stability of the operation of the FTIRS instruments:

4 Instrument heaters and temperature controllers.

W Pressure sensors and pressure controllers.

C> Sample system ( pump, filters, flow meters, and water knockouts).

2. The FTIRS analyzers were purged with conditioned air for a minimum of 30 minutes before conducting and analysis of the background spectrum. During periods when the instruments were in stand by mode ( i. e., between sampling runs or between test days), they were maintained at normal operating temperatures and purged with conditioned air.

3. Background Spectrum Procedures  Each instrument was allowed to stabilize while being purged with Ultrahigh Purity ( UHP) nitrogen for 10 minutes. The FTIRS spectra were monitored during this time, until CO and HZ0 concentrations reached a steady state. The following procedures were then done:

a> The interferogram signal was checked using signal alignment software.

b) A single beam spectrum was collected and inspected for irregularities.

C> Using the single beam spectrum, the detector was checked for non linearity, and corrected if necessary.

d) The instrument alignment procedure was done.

9 A background spectrum consisting of 256 scans was collected.

4. Analyzer Diagnostics  Analyzer diagnostics were done by analyzing a diagnostic cylinder containing 109 ppm CO. The standard was an EPA Protocol gas. EECL used CO because it has distinct spectral features that are sensitive to variations in system operation and performance. The standard was introduced directly into each instrument, and instrument readings were allowed to stabilize for five minutes. The accuracy and precision of each instrument were calculated. The pass/ fail criterion for accuracy and precision was 10% of the concentration of the Final Report  Caterpillar 3508 EUI 6 3 September 200 1 standard gas. A second diagnostic standard consisting of a blend of CO*, CO, CH4, and NOx was analyzed using the same procedure. Each instrument met the precision and accuracy requirements. Analyzer diagnostic data are presented in the report generated by EECL 5. Indicator Check & Sample Integrity Check  An indicator check was done by analyzing an indicator standard. A 10.66 ppm formaldehyde standard was introduced directly into each instrument. The instrument readings were allowed to stabilize and a 5 minute data set was collected. The indicator standard was then introduced into the sample system at the sample probe, just upstream of the filter. The instrument readings were allowed to stabilize and a 5 minute set of data was collected. The accuracy, precision, and recovery were calculated based on equations in the document entitled " Protocol for Performing Extractive FTIRS Measurements to Characterize Various Gas Industry Sources for Air Toxics", prepared by Radian International for the Gas Research Institute. The pass/ fail criterion for accuracy, precision, and recovery is 100 f 10% of the known standard ( recovery shall be 100 f 10% of the instrument reading when the indicator gas was introduced directly into the instrument.) Each instrument met these criteria. Indicator check and sample integrity data sheets are included with the EECL report.

6.1.3 Backeround Assessment During data acquisition procedures, the baseline absorbance was continually monitored. If at any time the baseline spectrum changed by more than 0.1 absorbance units, the instrument's interferometer was realigned and a new background spectrum collected.

6.1.4 Post Test Checks Upon completion of the daily test program steps 4 and 5 of the pre test calibration procedures were repeated. Both of the FTIRS analyzers met all of the acceptance criteria for the calibration and QA procedures. Post test calibration data sheets are included in the EECL report.

6.1.5 FTIRS Validation Before the initiation of testing of the engine, both FTIRS sampling and analysis systems were validated for formaldehyde, acrolein, and acetaldehyde. The validation was conducted by personnel from ERG, using procedures outlined in EPA Method 301 " Field Validation of Pollutant Measurement Methods from Various Waste Media." The validation was conducted using a dynamic spiking the sample gas with known concentrations of formaldehyde, acrolein, and acetaldehyde. The spike gas consisted of a compressed gas cylinder containing a mixture of acrolein and acetaldehyde. Formaldehyde was added to the Final Report  Caterpillar 3508 EUI 6 4 September 200 1 mixture by injecting a stock formalin solution onto a heated block at a fixed rate. The acrolein/ acetaldehyde gas standard was used as a carrier gas for the vaporized formaldehyde. The three component mixture was injected into each FTIRS sampling system at a point upstream of each system's filter. Further discussions of the validation procedures employed may be found in the report generated by EECL.

6.1.6 FTIRS Detection Limits Table 6.1 presents the in stack detection limits for formaldehyde, acetaldehyde, and acrolein as reported by CSU EECL. These detection limits have been used to calculate the run by run mass detection limits for each of the target pollutants.

6.2 CEMS QA/ QC PROCEDURES The following paragraphs describe the CEMS quality assurance procedures that EECL personnel used during the test program. The calibration and QC frequencies far exceeded those required for permanently installed, compliance analyzers, but are less than those specified for compliance tests by EPA ( 40 CFR 60, Appendix A). EECL operates their CEMS in a way that is more similar to permanently installed analyzers.

6.2.1 Analvzer Calibration Gases EECL used EPA Protocol calibration gases. The calibration gases were manufactured by Scott Specialty Gases. For this program, EPA Protocol 1 calibration gases ( RATA Class) were used. Formaldehyde and acetaldehyde/ acrolein standards with concentration ranges between 5  20 ppm were obtained for FTIRS calibrations. These gases are not available as EPA Protocol Gases, so EECL specified the highest quality available. Scott supplied certification sheets, which may be found in the Appendices of EECL's test report.

6.2.2 Resaonse Time Tests Response time tests were done on each sample system before initiation of the engine test program. The response time tests were done before the FTIRS validation process for each sampling system. The response time of the slowest responding analyzer ( Questar Baseline) was determined. Response time tests conducted at the EECL indicated sampling system response times of 1: 10 minutes. This is the time for the Rosemount Oxygen Analyzer ( the slowest responding continuous analyzer) to stabilize to response output of the analyzer. The Questar Baseline Industries CH4/ Non CH4 analyzers have a minimum cycle time of 4: 50 minutes. The overall response time for these analyzers when their cycle is started 1: 10 minutes after a sample source change is 550 minutes. When the methane/ non methane analyzer cycle time was initiated at a sample source change, the, overall response time was Final Report  Caterpillar 3508 EUI 6 5 September 200 1 TABLE 6.1 DETECTION LIMITS OF FI'IRS AND CEMS COMPOUNDS ppmev partsper~ byvdume, wetbasis parts per million by volum?. dry basis ppnwd Q 15% 02  parts per niBion by vohnm, dry basis, corrected to 15% oxygen F& al Report  Ckerpillar 3508 EUI 6 6 September 200 1 9: 00 minutes. The response time was tested to assure that the analyzers' response was for exhaust gas entering the sample system from each of the test point conditions.

6.2.3 Analvzer Calibrations Zero and mid level span calibration procedures were done on the CO, CO*, OS, NOx, and THC analyzers before each test day. Zero and span drift checks were performed upon completion of each data point and upon completion of each test day. A zero and mid level gas was introduced individually directly to the back of the analyzers before testing for carbon monoxide, carbon dioxide, oxygen, total hydrocarbons, Methane/ Non Methane, and oxides of nitrogen. The analyzers output response was set to the appropriate levels. Each analyzer's stable response was recorded. From this data a linear fit was developed for each analyzer. The voltages for each analyzer were recorded and used in the following formula:

Y = mx+ b Where: b = Intercept m = Slope X = Analyzer or transducer voltage Y = Engineering Units After each test point and upon completion of a test day, calibrations were conducted by reintroducing the zero and span gases directly to the back of the analyzers. The analyzers' stabilized responses were recorded. No adjustments were made during testing or during the final calibration check. Initial calibration values and all calibration checks were recorded for each analyzer during the daily test program.

The before and after calibrations checks were used to determine the zero and span drift for each test point for the CO, CO,, OZ, THC, methane/ non methane, and NOx analyzers. The zero and span drift checks for all test points and all test days were less than ~ 2.0% of the span value of each analyzer used during the daily test program. The calibration data sheets are presented in the test report generated by EECL. Table 6.2 presents the types and frequencies of the analyzer calibrations conducted by EECL.

6.2.4 Analvzer Linearitv Check Analyzer linearity checks were done before beginning the test program. The oxygen, carbon monoxide, total hydrocarbon, methane/ non methane, and oxides of nitrogen analyzers were " zeroed" using either zero grade nitrogen or hydrocarbon free air. The analyzers were allowed to stabilize, their output was recorded and then spanned using the mid level calibration gases. The analyzers were allowed to stabilize a second time and their output was recorded. From this data a linear fit was developed for each analyzer. The voltage for each analyzer was recorded and used in the following formula:

Final Report  Caterpillar 3508 EUI 6 7 September 200 1 TABLE 6.2 TYPES AND FREQUENCIES OF CEMS ANALYZER CALIBRATIONS Calibration Type Gas Calibration Gas Calibrant Concentration ( units Frequency Injection of % of span ( l)) Point Validation Criterion ACE t2) 02, co2, co, NO,

Methane/ Non Methane Hydrocarbons 0 to 0.25, 40 to 60, 80 to 100 0 to 0.1, 25 to 35, 45 to 55, 80 to 90  3% of analyzer span for each gas Before each Directly into , engine test the analyzer < 5% of respective cal. gas value ZSD t3) 02, co2, co, NO,

Methane/ Non Methane Hydrocarbons 0 to 0.25, 40 to 60 or 80 to 100 (`)

25 to 35, 45 to 55 Before and after each test run Directly into the analyzer All errors < 3% of span All errors < 3% of span SSB t4) NO,

MethaneMon Methane Hydrocarbons 0 to 0.25, 40 to 60 or 80 to 90 (` I 0 to 0.25, 25 to 35, 45 to 55 or 80 to 90 (`) Before and after each Both directly test day into the Both errors analyzer and into the inlet x5% of Before and after each of the sample analyzer spar line test day (*)  The span must be 1.5 to 2.5 the concentration expected for each pollutant t2)  Analyzer calibration error check t3)  Zero and span drift check t4)  Sampling system bias check t5)  Whichever is closer to the exhaust gas concentration Final Report  Caterpillar 3508 EUI 6 8 September 200 1 where: Y = mx+ b b = Intercept m = Slope X = Analyzer or transducer voltage Y = Engineering Units Using the linear fit, the linear response of the analyzer was calculated. Low level and high level calibration gases were individually introduced to the analyzers. For each calibration gas, the analyzers were allowed to stabilize and their outputs were recorded. Each analyzer's linearity was acceptable. The predicted values of a linear curve determined from the zero and mid level calibration gas responses agreed with the actual responses of the low level and high level calibration gases within & 2.0% of the analyzer span value. The methane/ non methane analyzers' linearity was acceptable as the predicted valued agreed with the actual response of the low level and high level calibration gases within & 5.0% of the actual calibration gas value. This procedure was done for one range setting for each analyzer. The Linearity Check data sheets are presented the test report generated by EECL.

6.2.5 NO, Converter Check EECL did NO, converter checks before the test program began. A calibration gas mixture of known concentration between 240 and 270 ppm nitrogen dioxide ( NO,) and 160 to 190 ppm nitric oxide ( NO) with a balance of nitrogen was used. The calibration gas mixture was introduced to the oxides of nitrogen ( NO,) analyzer until a stable response was recorded. The converter was considered acceptable if the instrument response indicated a 90 percent or greater NO, to NO conversion. The NO2 Converter Check data sheets are presented in the test report generated by EECL.

6.2.6 Sample Line Leak Check The sample lines were leak checked before the engine test program. The leak check procedure was done for both pre catalyst and post catalyst sample trains. The procedure was to close the valve on the inlet to the sample filter found just downstream of the exhaust stack probe. With the sample pump operating, a vacuum was pulled on the exhaust sample train. Once the maximum vacuum was reached, the valve on the $ ressure side of the pump was closed, thus sealing off the vacuum section of the sampling system. The pump was turned off and the pressure in the sample system was monitored. The leak test was acceptable as the vacuum gauge reading dropped by an amount less than 1 inch of mercury over a period of 1 minute. The Sample Line Leak Check data sheets are presented the test report generated by EECL.

Final Report  Caterpillar 3508 EUI 6 9 September 200 1 6.2.7 Sample Line Inteeritv Check A sample line integrity check was done before and upon completion of each test day. The analyzers' response was tested by first introducing a mid level calibration gas directly to the NOx analyzer. The analyzer was allowed to stabilize and the response recorded. The same mid level calibration gas was then introduced into the analyzer through the sampling system. The calibration gas was introduced into the sample line at the stack, upstream of the inlet sample filter. The analyzer was allowed to stabilize and the response recorded. The analyzer response values were compared and the percent difference did not to exceed & 5% of the analyzer span value.

The sample line integrity check was to be done for both the NO, and methane/ non methane analyzers. Due to time constraints, EECL performed the integrity check for the NO, analyzers only. The SSB procedure was done for the methane/ non methane analyzers before and upon completion of the test program. The Sample Line Integrity Check data sheets are presented in the test report generated by EECL.

6.2.8 Carbon Balance Check One of the methods used to calculate mass emissions was a carbon balance calculation developed by Southwest Research Institute specifically for the American Gas Association. The calculations consist of a theoretical O2 calculation based upon measured exhaust stack constituents and fuel gas composition. The theoretical exhaust O2 is then compared to the measured exhaust 0,. The percent difference between the actual and theoretical O2 measurements was within 55 % of the measured O2 reading. The O2 balance was done for every 1  minute average and the 33 minute averaged valued for each test point.

6.2.10 Fuel Factor Oualitv Assurance Checks Besides the CEMS calibration and QC checks, carbon dioxide and oxygen . measurements were validated by calculating the fuel factor, F,, using the following equation:

F,' 20.9 % 02 o/ oco2 The values of F, at the inlet and the outlet for each sampling run are presented in Table 6.3. For distillate fuel oil combustion, the value of F, should be approximately 1.35. The F, values were within 10% of the expected F, for all of the runs conducted. Based upon these results, the integrity of the CEMS sample stream was not compromised due to leaks in the sampling system.

Final Report  Caterpillar 3508 EUI 6 10 September 200 1 TABLE 6.3 SUMMARY OF FUEL FACTOR VALUES Run Number Inlet F,

1 1.44 2 1.45 Outlet F,

1.36 1.41 I 3 1.38 1.40 I 1.41 1.35 1.34 I 1.36 I 13 1.34 II 14 1.35 II II PAHl I 1.36 I 1.33 II PAH 2 PAH 3 Final Report  Caterpillar 3508 EUI 6 11 September 200 1 6.2.11 CEMS Detection Limits For each of the sample runs, the mass detection limits of the CEMS were presented previously in Table 6.1. For each run, the detection limit was calculated using analytical detection limit data supplied by EECL. Table 6.4 summarizes these values.

TABLE 6.4 SUMMARY OF CEMS ANALYTICAL DETECTION LIMITS II Parameter I Inlet Detection I Outlet Detection Limit Limit II Oxygen I 0.01 % volume I 0.01 % volume II Carbon Dioxide I 0.25 % volume I 0.15 % volume II Nitrogen Oxides I 0.1 ppm I 0.1 ppm II Carbon Monoxide I 10 PPm I 2 PPm ir Methane I 2 PPm I 2 PPm Non methane Hydrocarbons 2 PPm 0.2 ppm Total Hvdrocarbons 0.04 ppm 0.04 ppm 6.3 GCMS QA/ QC PROCEDURES Each day the GCMS measurement system was tuned according to the criteria identified in the method. Achieving the criteria for a valid mass spectral tune and achieving the internal standard relative mass abundances during each GCMS run ( see Tables 3 and 4 of Alternate Method 17) verifies continuing instrument performance and ensures that the QA/ QC criteria of the method are achieved. Achieving the criteria for a valid tune also allows searches of the NIST Mass Spectral library and verification of compounds that are not contained in the instrument specific calibration.

Daily system calibrations were conducted to check both the validity of the initial instrument calibration and the effectiveness of the sampling system to transport the target analytes to the instrumentation. Daily system calibration checks were conducted at 1 ppm using the blended mixture of test program analytes. For system calibrations, the gas standard was directed through the entire sampling system ( including the filter). The certified standard Final Report  Caterpillar 3508 EUI 6 12 September 200 1 used for this procedure was independent from that used to generate the initial calibration. All target analytes met the method system calibration criteria of 20% except for toluene on September 1, 1999 that was 24%. Immediately following the system continuing calibration, nitrogen was allowed to flow through both measurement systems and a system blank was acquired. No analytes were detected in any of the system blank analyses. The results of the continuing calibration checks are presented in Table 6.5.

Periodic analyte spiking was conducted at 1 ppm on August 3 1, 100 ppb on September 1, and at multiple concentration levels on September 2 to determine the extent of the soot adsorption for benzene and toluene. The analyte spike was delivered at a ratio of exactly 1 part of spike gas to 9 parts of effluent as measured by calibrated mass flowrneters. The analyte spike mixture was injected into the sampling system immediately upstrp of the particulate filters in both measurement systems so that the combined effect of the effluent matrix and the diesel soot could be evaluated.

From the analyte spiking procedures conducted on August 3 1, it was observed that the soot adsorbed about 60% of these compounds at the 1 ppm concentration level. The adsorption was fairly consistent with time at this spike level.

Because the 1 ppm analyte spike concentration was about 10 times greater than the effluent concentration of benzene and toluene, analyte spikes at 100 ppb were conducted on September 1. The purpose was to document more fully the extent of the adsorption at applicable concentration levels. Filter changes at the beginning of the day combined with sampling ambient air between runs minimized the adsorption of the benzene and toluene and yielded acceptable recoveries at the 100 ppb level after the first few runs. At the end of the day however, soot build ups again reduced the analyte spike recoveries to the levels seen the previous day.

Analyte spiking done on September 2 was conducted at multiple concentration levels. Recoveries for benzene were within the acceptable 30% tolerance. Toluene recoveries ranged from 50 60% of the expected values. Table 6.6 presents the results for the analyte spiking procedures conducted during this test program.

One is tempted to correct actual measurement data based on the results of analyte spikes. Such corrections may sometimes decrease the accuracy of the data. The following factors should be considered:

1. Calculation of analyte spike recoveries may be adversely affected due to actual changes in the underlying native concentrations for compounds present during the spiking procedure. In these tests, our recovery calculations assume that the benzene concentration preceding the spike is the same as the native benzene concentration during the spike. However, the benzene concentration was Final Report  Caterpillar 3508 EUI 6 13 September 200 1 TABLE 6.5 SUMMARY OF GCMS CONTINUING CALIBRATIONS Compound Expected Value ( PPW August 31,1999 September 1,1999 September 2,1999 Result VW Result c w Result W) ( PPN Diff. ( PPN Diff. ( PPN Diff.

Catalyst Inlet Hexane 1.03 1.02  0.97 0.95  7.77 1 . oo  2.91 Benzene 1.04 0.88  15.4 0.94  9.62 1 . oo  3.85 Toluene I 1.01 1 0.81 1  19.8 1 0.77 1  23.8 1 1.01 I 0 Ethyl Benzene I 1.04 I 0.91 I  12.5 I 1.01 I  2.88 1 1.01 I  2.88 m/ p Xylene I 2.06 1 1.86 1  9.71 I 1.93 I  6.31 1 2.00 1  2.91 Styrene 1.04 1.02  1.92 0.83  20.2 1 . oo  3.85 o Xylene 1.03 0.91  11.7 1.01  1.94 1 . oo  2.91 1,3  Butadiene 1.03 Hexane 1.03 Benzene 1.04 Toluene 1.04 Ethyl Benzene 1.04 m/ p Xylene 2.06 Styrene 1.04 o Xylene 1.03 Catalyst Outlet 1.00  2.91 1.09 5.83 1.01  1.94 1.01  1.94 1.01  1.94 1.01  1.94 1.01  2.88 1.03  0.96 1.01  2.88 1.00  3.85 1.09 4.81 1.00  3.85 1.01  2.88 1.10 5.77 1.01  2.88 2.02  1.94 2.14 3.88 2.03  1.46 1.00  3.85 1.07 2.88 1 . oo  3.85 1 . oo  2.91 1.03 0 1 . oo  2.91 i *

 I Final Report  Caterpillar 3508 EUI 6 14 September 200 1 TABLE 6.6 GCMS ANALYTE SPIKE RECOVERIES I Benzene Toluene Inlet Recovery W) Outlet Recovery VW Inlet Recovery rw Outlet Recovery ( 0 OO August 31,1999 ( 1 ppm standard)

Run1 I 39 I 88 I 28 I 60 Run 14 I 42 I 88 I 30 I 60 Run 13 I 42 I 88 I 30 I 60 Run 10 I 42 I 88 I 29 I 60 Run9 I 42 I 88 I 29 I 60 September 1,1999 ( 100 ppb standard)

Run4 I 81 I 104 I 74 I 58 Run 11 I 83 I 107 I 26 I 48 Run 12 I 83 I I 26 I Run2 I 57 I 89 I 69 I 48 September 2,1999 ( 100 ppb standard)

Run3 I 71 I 117 I 54 7 58 Run3 76 126 61 48 Run3 71 120 67 48 Final Report  Caterpillar 3508 EUI 6 15 September 200 1 observed to vary significantly among the four samples analyzed for certain test ll. UlS.

2. The analyte spike procedure used equipment that is not part of the method and thus may have added errors. Calculation of spike recoveries includes measurement errors associated with the sample flow system ( rotameter or mass flow meter that is normally used only for assuring constant rate sampling) and the mass flow meter used to monitor the spike rate. Both measurements contribute some additional uncertainty due to their accuracy and precision. The sample flow meter is also susceptible to changes in composition and molecular weight of the sample gas.

3. The 1 ppm analyte spikes were significantly greater than the sample concentrations and thus may affect the dynamic equilibrium between the benzene and soot in the exhaust stream.

4. The 100 ppb analyte spikes involve the use of a second calibration standard, different from the calibration standard used for the fundamental multi point calibration. This too, may have introduced another source of uncertainty. ( Note: the tolerance allowed for audit of the calibration curve using the 1 ppm gas is 20%.)

5. Both the unspiked and the spiked concentration measurements are influenced by noise or imprecision associated with the mass spectrometer measurements particularly at very low concentration levels. ( Note that the tolerance for the daily continuing calibration checks is 20% and that replicate injections are performed to minimize the effects of noise in constructing the fundamental calibration curve.)

6. The limitations of the analyte spiking procedure require that the normal acceptable tolerance be 70% to 130% recovery of a 1 ppm spike. The spike criterion is less restrictive than the + 20% tolerance for the continuing calibration checks because it reflects the limitations stated above. The spike criterion applied to a 100 ppb spike becomes very restrictive. ( i. e., 30 ppb for a 100 ppb spike versus 300 ppb for a 1 ppm spike)

6.3.1 GCMS Detection Limits Tables 6.7 and 6.8 present the GCMS Detection Limits at the pre catalyst and the post catalyst sampling locations. PES used the analytical detection limits supplied by EM1 to calculate the run by run mass detection limits.

Final Report  Caterpillar 3508 EUI 6 16 September 200 1  I " l r . 1". LI I  u ,  x  . TABLE 6.7 DETECTION LIMITS OF GCMS COMPOUNDS AT CATALYST INLET Run 11) 1 Run1 1 Run2 1 Run3 I Run4 I Run9 I Run10 I Run11 1 Run12 I Run13 I Run14 I PAH 1 I PAH 2 I PAH 3 1 H B T fwmvd 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 No data ,3 Butadiene pg/ bhp hr 2000 3000 2000 2000 4000 3000 3000 4000 2000 3000 3000 3000 Nodata plb/ hr 5000 5000 3000 4000 8000 6000 7000 8000 4000 7000 7000 5000 No data wmvd 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 0.15 No data lexane pg/ bhp hr 1000 1000 1000 1000 2000 1000 2000 2000 1000 2000 1000 1000 No data plb/ hr 2000 2000 1000 2000 4000 3000 4000 4000 2000 4000 3000 2000 No data ppmvd 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 No data enzene pg/ bhp hr 100 100 100 100 100 100 100 100 100 100 100 100 No data plb/ hr 200 200 100 200 300 200 300 300 200 300 300 200 No data wmvd 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 No data oluene pg/ bhp hr 100 100 100 100 200 100 200 200 100 200 200 200 No data plb/ hr 200 200 200 200 400 300 400 400 200 400 400 300 No data wmvd 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 No data thyl Benzene pg/ bhp hr 100 200 100 100 200 100 200 200 100 200 200 200 No data plb/ hr 300 300 200 200 500 300 400 400 300 400 400 300 No data wmvd 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 No data / p Xylene pg/ bhp hr 300 300 300 200 400 300 400 400 200 400 400 400 No data plb/ hr 600 500 400 400 900 700 900 900 500 900 800 600 No data ppmvd 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 No data tyrene pg/ bhp hr 1700 2400 1800 1400 2800 2000 2600 2700 1600 2700 2400 2600 No data plb/ hr 3700 3600 2400 2800 6100 4400 5700 5800 3400 5800 5300 4000 Nodata wmvd 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 No data , Xylene pg/ bhp hr 300 300 300 200 400 300 400 400 200 400 400 400 No data plb/ hr 600 500 400 400 900 700 900 900 500 900 800 600 No data E m Final Report  Caterpillar 3508 EUI 6 17 September 200 1 A I TABLE 6.8 DETECTION LIMITS OF GCMS COMPOUNDS AT CATALYST OUTLET tun ID Run1 Run2 Run3 Run4 Run9 Run10 Run11 Run12 Run13 Run14 PAH 1 PAHZ PAH3 wmvd 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 No data ,3 Butadiene pg/ bhp hr 500 1000 1000 1000 1000 500 500 1000 500 1000 500 1000 No data plb/ hr 1000 1000 1000 1000 2000 1000 1000 2000 1000 2000 1000 1000 No data ppmvd 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 No data lexane pg/ bhp hr 500 1000 370 1000 500 500 500 500 500 500 500 1000 No data plb/ hr 1000 1000 500 1000 1000 1000 1000 1000 1000 1000 1000 1000 No data wmvd 0.02 0.02 0.02 0.02 0.02 0.02 0.03 0.08 0.02 0.02 0.02 0.02 No data lenzene pg/ bhp hr 100 100 100 100 100 100 300 800 100 100 100 100 No data vlb/ hr 200 200 100 200 300 200 600 1700 200 300 300 200 No data wmvd 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 No data oluene pg/ bhp hr 100 100 100 100 200 100 200 200 100 200 200 200 No data plb/ hr 200 200 200 200 400 300 400 400 200 400 400 300 No data ppmvd 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 No data thy1 Benzene pg/ bhp hr 100 200 100 100 200 100 200 200 100 200 200 200 No data plb/ hr 300 300 200 200 500 300 400 400 300 400 400 300 No data wmvd 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 No data I/ p Xylene pglbhp hr 300 400 300 200 400 300 400 400 200 400 400 400 No data plb/ hr 600 600 400 400 900 700 900 900 500 900 800 600 No data wmvd 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 No data tyrene pg/ bhp hr 500 1000 1000 1000 1000 500 500 500 500 500 500 1000 No data plb/ hr 1000 1000 1000 1000 2000 1000 1000 1000 1000 1000 1000 1000 No data ppmvd 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 0.03 No data . Xylene pglbhp hr 500 1000 300 200 500 500 500 500 500 500 500 1000 No data plb/ hr 1000 1000 400 400 1000 1000 1000 1000 1000 1000 1000 1000 No data Final Report  Caterpillar 3508 EUI 6 18 September 200 1 6.4 CARB 429 QA/ QC PROCEDURES The following text describes the QA/ QC procedures employed by PES and ERG during the PAH sampling and analysis.

6.4.1 Calibration of CARB 429 Sampliw Apparatus Because no mechanism exists for an independent measurement of emissions from the source, careful preparation, checkout, and calibration of the sampling and analysis equipment is essential to ensure collection of high quality data. PES maintains a comprehensive schedule for preventive maintenance, calibration, and preparation of the source testing equipment.

<IP_ADDRESS> Barometers. PES used aneroid barometers calibrated against a station pressure value reported by a nearby National Weather Service Station and corrected for elevation.

<IP_ADDRESS> Temperature Sensors. The responses of the Type K thermocouples used in the field testing program were checked using Calibration Procedure 2e as described in the Quality Assurance Handbook. The response of each temperature sensor was recorded when immersed in an ice water bath, at ambient temperature, and in a boiling water bath; each response was checked against an ASTM 3F reference thermometer. Table 6.9 summarizes the results of the thermocouple checks and the acceptable levels of variance. Digital temperature readouts were checked for calibration using a thermocouple simulator having a range of O 2400 " F.

<IP_ADDRESS> Pitot Tubes. PES used Type S Pitot tubes or Standard Pitot tubes constructed according to EPA Method 2 specifications. Type S Pitot tubes were calibrated against the dimensional criteria described in Method 2 using Calibration Procedure 2a as described in the Quality Assurance Handbook, Volume III, 1994. Type S Pitot tubes meeting these criteria are assigned a pitot coefficient ( C,,) of 0.84. Standard Pitot tubes were checked for dimensional criteria using Calibration Procedure 2b as described in the Quality Assurance Handbook, Volume III, 1994. Standard Pitot tubes meeting these criteria were assigned a pitot coefficient ( C,) of 0.99. Table 6.10 summarizes the results of the pitot tube checks and the acceptable levels of variance.

<IP_ADDRESS> Differential Pressure Gawes. PES used Dwyer inclined/ vertical manometers to measure differential pressures including: velocity pressure, static pressure, and orifice meter pressure. PES chose manometers having sufficient sensitivity to measure pressures over the entire range of expected values accurately. Manometers are primary standards and require no calibration.

Final Report  Caterpillar 3508 EUI 6 19 September 200 1

TABLE 6.9 CARB 429 SAMPLE TRAIN SUMMARY OF TEMPERATURE SENSOR CALIBRATION DATA Temp. Sensor I. D. Usage RMB 15 Dry Gas Meter Inlet RMB 15 Dry Gas Meter Outlet I MB 1 1 Dry Gas Meter Inlet MB 1 1 Dry Gas Meter Outlet SH 1 I Impinger Exit SH 5 Impinger Exit Temperature, " R Absolute Difference 493 493 534 535 668 668 T 0 0.19 0 492 492 0 534 534 0 670 668 0.30 492 492 0 534 534 0 668 668 0 492 492 0 536 536 0 668 668 0 492 493 0.20 531 531 0 667 667 0 EPA Criteria %

 1.5  1.5  1.5  1.5 e1.5 ti1.5  1.5  1.5  1.5 e1.5 ck1.5 e1.5  1.5 e1.5 e1.5 e1.5  1.5 e1.5 Final Report  Caterpillar 3508 EUI 6 20 September 200 1 TABLE 6.10 CARB 429 SAMPLE TRAIN SUMMARY OF PITOT TUBE CALIBRATION DATA Measurement EPA Criteria aI < 10' Pitot HPP 1 0" Pitot HPP 2 0'

a2 I < 10" I 0" I 1"

2 A I I 3 l/ 32 I 3 l/ 32 W= Atany I ~ 0.125 in. I 0.0160 I 0.0122 W= Atan8 I ~ 0.0.3 125 in. I 0.0160 I 0 I 0.1875 in. s D, < 0.375 in. I 318 318 Ai2D, 1 1.05 5 P*/ D, 5 1.50 I 1.29 I 0.29 I Acceptable ?: I YES I YES I Assigned Coeffkient: I 0.84 I 0.84 Final Report  Caterpillar 3508 EUI 6 21 September 200 1 <IP_ADDRESS> Drv Gas Meter and Orifice. The CARB Method 429 dry gas meters and orifices were calibrated according to Calibration Procedure 5 in the Quality Assurance Handbook. This procedure requires direct comparison of the dry gas meter to a reference dry test meter. PES calibrates its reference dry test meter annually against a wet test meter. Before its initial use in the field, the metering system was calibrated at several flow rates over the normal operating range of the metering system. Individual meter calibration factors ( y) cannot differ from the average by more than 0.02, and the results of individual meter orifice factors ( AH& cannot differ from the average by more than 0.20. After field use, the metering system calibration was checked at the average flow rate and highest vacuum observed during the test period. The results of the post test meter correction factor check cannot differ by more than 5% from the average meter correction factor obtained during the initial, or thereafter, the annual calibration. Table 6.11 presents the results of the dry gas meter and orifice calibrations. All dry gas meters and orifices used in this test program met the method calibration requirements.

TABLE 6.11 CARB 429 SAMPLE TRAIN SUMMARY OF DRY GAS METER AND ORIFICE CALIBRATION DATA Meter Box No. Dry Gas Meter Correction Factor ( y) Meter Orifice Coefficient ( AH&

Pre test Post test % Diff. EPA Criteria Average Range EPA Criteria MB 10 0.999 0.999 0.0 < 5% 1.89 1.83  1.94 1.69  2.09 RMB 15 1.001 0.997  0.40  6% 1.87 1.79  1.98 1.67  2.07 6.4.2 Reagents and Glassware Prenaration Before field testing, PES pre cleaned all sample train glassware following the procedures in CARB Method 429. Specifically, the glassware was cleaned according to the following protocol.

1. 2. 3. 4. 5. Wash in hot soapy water with Alconox. Rinse three times with tap water. Rinse three times with reagent ( i. e., deionized) water. Soak in 10% ( v/ v) nitric acid ( HNO,) solution for a minimum of 4 hours. Rinse three times each with pesticide grade acetone, hexane, and methylene chloride, and allow to air dry.

Final Report  Caterpillar 3508 EUI 6 22 September 200 1 After preparation of the glassware, the openings were sealed with Teflon tape to prevent contamination, and the glassware wrapped and packed for transport to the EECL. ERG prepared the XAD 2@ sorbent resin traps. ERG then pre spiked the traps with surrogates and capped them with glass balls and sockets. Impinger water used was organic free, reagent grade. Pesticide grade acetone, hexane, and methylene chloride were used as recovery solvents.

6.4.3 On site Measurements The on site QA/ QC activities included:

<IP_ADDRESS> Measurement Sites. Before sampling, PES checked the dimensions of the exhaust duct to assure that the port locations complied with Method 1 criteria. PES confirmed the distances to upstream and downstream disturbances and test port locations. PES also measured inside stack dimensions through perpendicular ports to assure uniformity of the stack cross sectional area. PES measured the inside stack dimensions, stack wall thickness, and sample port lengths to the nearest 0.1 inch.

<IP_ADDRESS> Velocitv Measurements. PES assembled, leveled, zeroed, and leak checked all velocity measurement apparatus before and after each sampling run. The stack static pressure was determined at a single point. PES selected a point of average velocity pressure found during the pre test velocity traverse.

<IP_ADDRESS> Moisture. During sampling, the exit gas temperature of the last impinger in each sampling train was maintained below 68 ° F to ensure condensation of stack gas water vapor. The moisture gain in the impinger train due to flue gas moisture was determined gravimetrically using a digital top loading electronic balance with a resolution of 0.1 g.

6.4.4 Analytical Oualitv Assurance PES and ERG personnel employed several methods to ensure the quality of the PAH analytical data. These methods included analysis of reagent blanks, a laboratory method blank, and field blanks. In addition, the XAD 2 sorbent traps were spiked with isotopically labeled internal standards. The recovery efficiency of the internal standards is used to evaluate method performance. The results of these QA checks are discussed in the following paragraphs.

<IP_ADDRESS> Blank Analyses. During the field testing, PES personnel collected blanks of& e CARB 429 sampling train reagents to quantify contamination levels. Field blank trains were assembled, transported to each sampling site, and leak checked. The field blank trains were then returned to the PES field laboratory, where they were recovered in the same manner as the trains used for sampling. The field blank train impingers and connecting glassware were the same components used during actual sampling. Since the sampling glassware is cleaned Final Report  Caterpillar 3508 EUI 6 23 September 200 1 after each run and reused, analysis of field blank trains is used to find out if poor cleanup technique caused cross contamination between sampling runs. Per CARB Method 429, PES did not correct any of the PAH results for blank results. The results of the reagent and field blank analyses are presented in Table 6.12. The levels of any unlabeled analyte quantified in the blank train must not exceed 20 percent of the level of that analyte in the sampling train.

<IP_ADDRESS> Internal Standard Recoveries. Table 6.13 presents the recovery efficiencies of isotopically labeled surrogate compounds. Recovery efficiency gives a measure of the capture efficiency and the efficiency of the solvent extraction for specific compounds. Recoveries for each of the internal standards must be greater than 50 percent and less than 150 percent of the known value. This criterion is used to assess method performance. Because this is an isotope dilution technique, it should be independent of internal standard recovery. Lower recoveries do not necessarily invalidate the analytical results for PAH, but they may result in higher detection limits.

6.4.5 CARB 429 Detection Limits Tables 6.14 and 6.15 present the in stack detection limits of each PAH compound before the catalyst and after the catalyst.

Final Report  Caterpillar 3508 EUI 6 24 September 200 1 TABLE 6.12 SUMMARY OF CARB 429 BLANK RESULTS Compound Laboratory Blank Result ( pg) Reagent Blank Result ( W' Inlet Field Outlet Blank Field Blank Result ( pg) Result ( pg)