SEPA United States Environmental Protection Agency Office of Air Quality Planning and Standards Research Triangle Park NC 27711 EMB Report 78-ISC-1 April 1979 Air Industrial Surface Coating: Automobile and Light-Duty Trucks Emission Test Report Ford Motor Company Pico Rivera, ------- Emission Test Report: Ford Motor Company Pico Rivera, California Report Number 78-ISC-l Emission Measurement Branch Emission Standards and Engineering Division U. S. Environmental Protection Agency Research Triangle Park, North Carolina 27711 July 1979 ------- Page I. INTRODUCTION 1 II. SUMMARY OF RESULTS 2 III. PROCESS DESCRIPTION 6 IV. DISCUSSION OF RESULTS 9 V. SAMPLING LOCATION 21 VI. SAMPLING AND ANALYTICAL PROCEDURES 21 VII. APPENDIX A-l *: Test Data Sheets * Velocity Traverse Data * Field Data Sheets * Analytical Data Sheets * Truesdail Laboratory Report * List of Participants DFIA -- Operating Conditions ------- LIST OF TABLES AND FIGURES TABLES Page TABLE 1 TEST LOG 3 TABLE 2 SUMMARY OF TOTAL GASEOUS NON-METHANE ORGANIC RESULTS 4 TABLE 3 CALCULATED INCINERATOR EFFICIENCY 5 TABLE 4 PAINT COMPOSITION 7 TABLE 5 PROCESS DATA 8 TABLE 6 STRATIFICATION RESULTS 10 TABLE 7 TOTAL COMBUSTION RESULTS ANALYSIS 11 TABLE 8 SUMMARY OF DIRECT FLAME IONIZATION ANALYSIS (DFIA) RESULTS 14 TABLE 9 INTEGRATED BAG SAMPLE ANALYTICAL RESULTS 16 TABLE 10 TOTAL ORGANIC CARBON TEST SUMMARY 17 TABLE 11 ALDEHYDE RESULTS 18 TABLE 12 GAS CHROMATOGRAPHY/MASS SPECTROMETRY RESULTS 19 TABLE is TRAVERSE POINTS 23 FIGURES FIGURE 1. FIGURE 2. FIGURE 3. FIGURE 4. INCINERATOR SCHEMATIC TCA SAMPLING APPARATUS DIRECT MEASUREMENT APPARATUS TOTAL ORGANIC CARBON APPARATUS 22 24 26 27 ------- I. INTRODUCTION During the period from April 24 to May 9, 1978, a three-person test crew from the Environmental Engineering Division of TRW, Inc. performed volatile organic carbon emissions testing at the Ford Motor Company assembly plant in Pico Rivera, California. The tests were performed at the inlet and outlet of a thermal incinerator (used to oxidize organic compounds) associated with a paint drying oven. The purpose of this test program was to obtain emission data by two different volatile organic carbon (VCC) test procedures. In order to evaluate the precision of each test method, compare the results of the different methods, and determine the control device efficiency, two test procedures were utilized to measure VOC emissions as total gaseous non-methane organics (TGNMO). These methods were (1) Total Combustion Analysis (TCA) , and (2) Direct Flame lonization Analysis (DFIA) supplemented with a methane determination of an integrated gas sample by gas chromatography. In addition, in order to identify specific organics in the effluent a third test procedure was utilized on a limited basis. The third test procedure for total organic carbon (TOC) consisted of a sampling train containing a solid resin adsorption system followed by an impinger train containing bisulfite solution for aldehyde collection. Salo, Albert E., William L. Oaks, and Robert D. MacPhee. Total Combustion Analysis. Air Pollution Control District. County of Los Angeles. August 1974. ------- In order to obtain data for evaluating the precision of the two TGNMO sampling methods, simultaneous sampling was conducted with multiple systems. The TCA tests were conducted simultaneously with three identical sampling trains. The DFIA tests were conducted with two or three different analyzers to monitor the total gaseous organic emissions. Table 1 is a test log summary. II. SUMMARY OF RESULTS Table 2 summarizes the total gaseous non-methane (TGNMO) results as measured by total combustion analysis (TCA) and the direct flame ionization analysis (DFIA) procedures. Data are presented by run number, test location, length of test period, TCA, DFIA, and integrated bag analysis results. The results reported for the TCA values are average values based on analysis of triplicate samples. The reported DFIA non-methane organic value is derived by subtracting the methane concentration determined by analysis of the integrated bag sample from the total concentration determined by the direct flame ionization analyzers. Table 3 outlines the incineration efficiency based on the results of both the TCA and DFIA procedures. The overall efficiency of the thermal incinerator ranges from ninety-four (94+) to ninety-nine (99+) percent. The results of several outlet sampling runs were suspect and consequently not included in determining the average outlet concentration with the TCA procedure. The deleted runs are indicated in the table. TOC results are discussed in section IV. ------- TABLE 1. TEST LOG Test Date Time 1 4-27 2 4-28 2A 5-1 1015-1105 3A 5-1 1330-1430 4A 5-2 0810-0910 5B 5-2 1005-1105 6B 5-3 0835-0840; 0920-1020 7B 5-3 1335-1435 8B 5-4 1400-1500 9A 5-5 1225-1322 9B 5-5 1245-1322 10B 5-8 0940-0950 1030-1045 1215-1300 11B 5-8 1350-1455 12B" 5-9 0825-0925 13B 5-9 1350-1500 INLET TCA / / / / / / DFIA / / / / / * / / / TOC / Integrated baq Cl / / / / \tf\~ V/- C. D / CO C02 °2 / / / OUTLET TCA / ' / / / ' / / / DFIA / / / / /] TOC / / / Integrated bag Cl / / / / / VC6 / ' / / / CO C02 °2 / / / / / / 2 Analyzers switched back and forth to inlet and outlet Beckman 402 Analyzer only ------- Run No. 02-A 03-A 04-A 09-A 05-B 06-B 07-B 08-B 09-B 10-B 11-B 12-B 13-B Location Inlet Inlet Inlet Inlet Outlet Outlet Outlet Outlet Outlet Outlet Outlet Outlet Outlet Sampling time (minutes) 50 60 60 57 60 48 60 60 57 65 65 60 70 VOLATILE ORGANIC EMISSIONS, ppm C Total combustion analysis (TCA)* Methane 51 46 60 53 < 5 < 5 < 5 < 5 < 5 < 5 < 5 < 5 < 5 Total non-methane 716 642 690 693 125 139 78 115 117 47 43 35 22 Direct flame lonization analysis (DFIA) Total 521 555 532 583 6.8 6.7 5.8 3.6 4.8 - - - - Total non-methane 474 509 482 530 6.8 6.7 0 3.6 0 - - - - Integrated bag Methane 45 40 46 54.2 N.D.** N.D. 20.8 - 22.6 - 10.4 10.8 18.2 * Represents average values from triplicate samples. ** N.D. not detected -TABLE 2. SUMMARY OF TOTAL-GASEOUS NON-METHANE ORGANIC RESULTS ------- Total Combustion Analysis (TCA) Average Inlet Outlet Efficiency (ppm) (ppm)* ' (%) Direct flame ionization analysis (DFIA) - Average Total Inlet Outlet Efficiency (ppm) (ppm) Non-methane Inlet Outlet Efficiency (ppm) (ppm) 685.25 36.75 94.6 549.35 5.5 98.99 498.75 3.4 99.3 * Note: Runs 5B, 6B, 7B, 8B, and 9B are deleted in calculating average. en Efficiency = 100 x [ Ppm TABLE 3. CALCULATED INCINERATION EFFICIENCY ------- III. PROCESS DESCRIPTION AND OPERATION The incinerator tested controlled the emissions from the "body first color" paint oven. This oven cures the body first color coating which is a sprayed enamel paint (approximately 21 different colors are used). Typical paint and solvent composition (supplied by the Ford Motor Company) is presented in Table 4. This plant assembles intermediate sized automobiles (LTD and Thunderbird) and during the testing approximately 50 cars were cured per hour; the actual number of cars painted during each test period is tabulated in Table 5. The incinerator tested is a direct-fired unit operating on natural gas. During the test period the incinerator operated i within a temperature range of 1425 to 1440 °F with a natural gas feed rate of between 10,100 and 10,420 CFH. Table 5 presents this information for each test run. ------- TABLE 4. PAINT COMPOSITION TYPICAL ENAMEL PAINT COMPOSITION Solids 40-48 Wgt % Solvents . 52-60 Wgt % Density 7.8 - 8.4 #/Gal. Component Typical Solvent Composition Hgt % Naptha 25-36 Aliphatic Hydrocarbons - 0-10 Aromatic Hydrocarbons 1-3 Butyl Alcohols 4-8 Isopropyl Alcohol - 0-.5 Butyl Acetate 1-24 Isopropyl Acetate 0-25 Cellosolve Acetate 26-35 ------- 00 Test 02A 03A 04A 05B 06B 07B 08B 09A 09B 10B 11B 12B 13B Average Incinerator Temperature °F 1440 1440 1430 1426 1430 1426 1440 1427 1427 1425 1425 1425 1423 Average Methane Flow Rate CFH 10,100 10,180 10,260 10,180 10,180 10,100 10,420 10,180 10,180 10,180 10,340 10,260 10,260 Production Rate Time Period 1015-1105 1330-1430 0813-0913 1006-1106 0920-1020 1335-1435 1400-1500 1225-1322 1245-1322 1035-1045 1215-1300 1350-1455 0825-0925 1350-1500 Cars Entering Oven 42 54 55 47 56 57 53 50 34 43 68 58 63 Cars/Hr 52 54 55 47 56 57 53 53 55 47 63 58 54 TABLE 5. PROCESS DATA ------- IV. DISCUSSION OF RESULTS Preliminary Tests Velocity traverses and duct stratification tests were performed prior to the VOC emission tests. Preliminary velocity traverses were made at both the inlet and outlet locations and are recorded in the appendix of this report. A S-type pi tot tube with a chrome V5 alumel thermocouple was used according to standard procedures. In addition, the ducts (inlet and outlet) were checked for volatile organic stratification. Table 6 records the results of these tests. No significant amount of stratification was found at either the inlet or the outlet. Total Combustion Analysis (TCA) Triplicate samples were performed for all total combustion analysis tests. This was accomplished by using a heated box containing three filter holders and four probes, one for the total hydrocarbon analyzer (DFIA) sample and three for the total combustion analysis samples. The probes were mounted so that all the samples were taken from the same location in the stack. The probes remained at a fixed position of average concentration as determined by the stack stratification test. Table 7 presents a complete summary of the TCA data. The TCA tests for the first run are invalid due to a leak in the sampling system (see discussion DFIA results). Run 2 was conducted with the TCA trains as a check out run to assure that the problem with the leak had been rectified; no DFIA data were taken during this run because of problems with the analyzers. ------- Data point Inlet 1 2 3 4 5 Outlet 1 2 3 4 5 6 Distance in stack (in.) Inlet 6 12 18 24 30 Outlet 7.5 14.5 21.5 28.5 35.5 40.0 Concentration (PPM)* Inlet 525 512.5 512.5 500 500 Outlet 5,5 5.5 5.5 5.0 4.5 4.5 TABLE 6. STRATIFICATION RESULTS * Measured by direct flame ionization analysis ------- DATE 4-27-78 4-28-78 5-01-78 5-01-78 5-02-7E 5-02-78 5-03-76 5-03-79 5-04-7E 5-05-78 5-05-7E 5-08-75 5-08-7 5-09-7 5-09-7 TEST 1 2 02 -A 03-A ,04-A 05-B 06-B 07-B 08-B 09-A 09-B 10-B 11-B i 12-B ! 13-B LOCATION Inlet Inlet Inlet Inlet Inlet Outlet Outlet Outlet Outlet Inlet Outlet Outlet Outlet Outlet - Outlet TANK # F306 F314 F312 A B C F117 F125 F313 A F321 C F312 F306 F314 D E F F156 G H F117 F125 Fll'3 A B C F321 F312 .F302 E F F314 F313 F125 F117 F156 H G A B C E ' F306 F321 CONCENTRATION PPM AS C1 TANKS CO 23 13 7 32 20 26 32 42 27 23 29 12 33 33 25 <5 <5 8 <5 <5 <5 21 <5 15 <5 18 <5 38 24 36 10 23 <5 19 10 <5 32 <5 8 9 14 10 31 17 24 Ci 9 <5 <5 30 44 37 48 58 47 51 46 41 57 49 45 <5 <5 <5 <5 <5 <5 <5 <5 <5 <5 <5 <5 56 51 53 <5 45 5 <5 <5 <5 <5 <5 <5 <5 <5 <5 <5 <5 <5 CO, .457 515 1,154 4,000 4,280 4,140 4,000 4,150 1,805 4,000 4,000 3,500 4,090 3,980 4,040 16,710 8,129 19,610 20,800 7,445 19,100 21 ,900 10,600 21,600 10,900 22,100 21,300 4,220 4,220 4,110 21,900 22,000 22,660 22,500 22,500 23,500 22,600 21,700 21,300 23,200 24,400 24,200 23,600 23,200 23,900 Organic <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 <20 TRAP Organic '. 71 176 135 711 717 . 714 704 709 735 698 628 600 731 655 685 164 140 170 282 84 52 59 37 138 31 249 66 668 691 720 166 42 144 38 45 58 56 33 39 71 21 13 16 24 25 TANK VACUUM IN/HG BEFORE 30 30 30 29 28.8 29.8 27 30 30 28 30 30 30 30 30 30 30 30 29 27 26 28 27 27 30 30 30 30 30 30 30 30 30 30 28 27 30 29.5 28 AFTER 8 8 14 13.5 10 10 6 6 12 n 16 18.5 8 14. 14.5 8 13 11 16 12 10 5 6 9 19.8 19.8 19.0 7 10 8 10 14 16 14 8.5 8 12 10 8 TABLE 7. TCA RESULTS 11 ------- Inconsistent results were obtained for tests 05-B through 09-B at the outlet; the source of the problem was never identified, although some sort of contamination is suspected. The possible sources of the problem are contamination of the probe, filter, filter holder, condensate trap, or an error in the analytical procedure. If the condensate trap is not totally baked out during analysis, organics would remain in the trap and would act as contamination for the next test run. During this test program the condensate traps used for runs 05B - 09B were the same traps used earlier for runs 1-5 at the incinerator inlet; a small amount of organic material left in the traps from the inlet run could show up as a significant amount at the outlet location. When the test results for runs 5B, 6B, and 7B were received, Truesdail laboratories was notified,and the problem of erratic results was explained. Truesdail indicated that thorough and proper bake out procedures were being applied. However, the problem still occurred (runs 8B and 9B). As a precaution the next set of traps that were received back from Truesdail were also baked out by TRW laboratories. In addition, the filter holders and probes were changed since these could have been a source of the problem (the filter holder is sealed with a viton 0-ring which could have been outgassing). The outlet test data collected after these steps were taken are much more consistent. However, it is still not possible to say whether the problem was contamination of the traps, or contamination of the probe and filter or filter holder. 12 ------- Direct Flame lonization Analysis (DFIA) Results Table 8 summarizes the DFIA results giving the range and average values for each analyzer. In addition, the instrument operating conditions and the calibration gas concentrations are tabulated in the appendix. As a rule, the DFIA demonstrated lower values than the TCA. The organic concentration was lower than expected during the check-out run (test 1); furthermore, a large cyclic fluctuation in the FID response occurred. After investigation, it was found that ambient air was being drawn into the stack through the outer jacket of the probe holder; consequently, the sample was being diluted. The problem was solved by removing the outer jacket and repacking the section where the probe exited the heated box. At the beginning of the test period, problems were encountered with the total hydrocarbon analyzers, particularly the Horiba and the Beckman 402. Neither instrument was able to establish a steady zero reading on hydrocarbon free air. The Horiba was taken back to the factory and the activated charcoal fuel filter was replaced. This is a strong indication that the fuel mixture (40 percent H2 in He) was contaminated with hydrocarbons. The instrument was put back on line and the same problem occurred. The fuel was changed to 40 percent hydrogen (H2) in nitrogen (N2). In addition, the fuel and air pressure were suppressed. The Beckman 402 was hand carried to their plant for repairs. Two problems with this instrument had developed; the instrument had excessive noise on range one and the sample pump was unable to produce the required pressure to operate the instrument. 13 ------- TOTAL ORGANIC, ppm C TEST 1 2 02-A 03-A 04-A 09-A 05-B 06-B 07-B 08-B 09-B BECKMAN Av. 536.0 553.0 531.0 562.0 5.6 8.9 5.5 2.4 4.8 RANGE High 550 625 575 675 7.5 11 7.5 7 8 Low 500 450 470 375 3 3 .5 0 3.5 HORIBA Av. - 566.0 570.0 534.0 7.8 6.1 6.7 - 4.8 RANGE High - 700 625 695 16 8.5 8 - 8 Low - 500 490 310 6 4 5 - 3.5 SCOTT Av. 513-0 550.0 537.2 551.0 7.2 5.3 5.2 3.9 6.7 RANGE High 570 620 580 690 10 7 7.2 5 10 Low 475 450 495 400 5 2 4 3 5.5 TABLE 8. SUMMARY OF DIRECT FLAME IONIZATION ANALYSIS (DFIA) RESULTS ------- Beckman installed a new pump, but a stable zero reading was still never achieved without suppressing the air, fuel, and sample pressures. In addition, range one (0-50 ppm) still had excessive noise, and a zero drift of between 20% positive 5% negative of full scale was experienced on this range. Therefore, this range was avoided throughout the test. Integrated Bag Samples The two reasons for these tests were 1) to provide methane results so that DFIA values could be calculated on a non-methane basis, 2) for several runs, to determine the presence of C, - Co hydrocarbons not collected in the solid adsorbent portion of the TOC test. In addition, several samples were analyzed for CO, C02 and 02 for comparison with values obtained by the TCA[procedure. Table 9 tabulates the analytical results of the integrated bag samples. The methane results by TCA and integrated bag sample agree well at the inlet, but not at the outlet. This would tend to indicate that the sensitivity of TCA is not sufficient for the low concentration range. Total Organic Carbon (TOO Tables 10-12 summarize the results of the TOC sampling. Table 10 presents the general test information for the four test runs conducted. Table 11 presents the results of the aldehyde analysis conducted on the impinger train. Results are presented as milligram Aldehyde absorbed; calculated values fon volume concentration,ppm formaldehyde, and mass concentration as carbon, mg/dscm,are also presented. Table 12 presents the GC/MS results for test runs 9A and 9B (runs 11B and 13B were not analyzed by GC/MS; the XAD-2 was extracted and the extract was retained for possible future analysis). The total mass (mg) collected for each 15 ------- '.-..''. CONCENTRATION -..-'.-'-- -. ' - ' DATE 5-1 -7p, ; 5-1-78 5-2-78 5-2-78 5-3-78 5-3-78 5-4-78 5-5-78 5-5-78 5-8-78 5-8-78 5-9-78 5-9-78 TEST . 02-A 03-A 04-A 05-B . . 06-B . 07-B 08-B 09 -A 09-B 10-B 11-B 12-B 13-B /' C1 PPM .'45 . 40 , ^46 . ND . . ND 20.8 - ND ; 54.2 22.6 x 10.4 10.8 18.2 % CO ; <0.01 <0.01 <0.01 . <0.01 <0.01 <0.01 ' x :: ''' X X X -X / 0.01 0.01 ; % C02 0.57 .; o.4i 0.33 -2.12 .. 2.20 ': ; 2.35 '-.; x ".' ' x X -.'' X -'v ' 'V:^ / . -2.51 .. -,;;.n.-73.'."-. % 02 14.6 ' 13.6 ; 13.0 11.1 .. n.o . 9.83 x . '_. ' x - .-'- x " -' - : .X"- -.'-.- ,'. -^ ' ' -. 8.70 -, 8.79 ;; C2 PPM , x -'. . x .-'.-" x ' :-' x ' "'. x x X 5.6 2.6 r X - :,8.1 -8-7 9.4 C3 PPM x x X X X X x 0.6 .ND x . . ND . . X ND C4 - C8 x x X / x x " :.~"~ x x :. "ND ND . x . ..' ND . ;^~~ " X . ND..; x - Not Analyzed ND - Not Detected C .Q 90MOI ------- TABLE 10 TOTAL.ORGANIC CARBON TEST SUMMARY DATE 4-25-78 4-25-78 5-08-78 5-09-78 TEST # 09-A, , 09-B 11-B 13-B TEST POSITION Inlet Outlet '.Outlet Outlet SAMPLE VOL.(SCF) 71.86 73.26 69.78 70.12 ĞM IN STACK 2.3 5.72 5.2. 5i4' GAS VELOCITY ft/ sec 37.27 54.03 ; 53.2 53.62 VOLUMETRIC FLOW RATE (SCFM) 12,387.44 .10,143.52 9,989.56 10,023.46 . : i ------- 00 TEST 09-A 09- B 11-B 13-B LOCATION INLET OUTLET OUTLET OUTLET TOTAL ABSORBED (mg) 54.8 5.4 5.5 3.9 TOTAL ALDEHYDE* CONCENTRATION (ppm) 21.6 2.1 2.2 1.6 CARBON** MASS 21.9 2.2 2.2 1.6 TABLE 11: ALDEHYDE RESULTS ** Carbon 1 * nnm = Mass, mg = (total /Total Absorbed, mg absorbed, mg) x .. .- . . - ^ v t 1 /12 mg Carbon \ *30 mg Formaldehyde 1 ^ ocuiipie vuiume, ubuii . -,r -,* ~£M Where M = Molecular weight Formaldehyde, (30.0) ------- Run 9A - Inlet Run 9B - Outlet Molecular Weight weight % Compound Identified (mw) carbon Xylene Styrene Di ethyl benzene Ethyl Styrene Napthalene Diphenyl Ethane Naphthalenes (substituted) Phthalate esters Adi pate esters Propanedioic Acid, dimethyl ester (dimethyl malonate) Butanedioic Acid dimethyl ester Pentanedioic Acid dimethyl ester Hexanedioic Acid dimethyl ester Unknown dioic acid ester * Above numbers +_ 100% ** Acetone washes showed none of the above com- pounds 106 90.6 104 92.3 134 89.6 132 90.9 128 75.0 182 92.3 128 75.0 -v-325 55 vl95 62 132 45.5 146 49.3 160 52.5 174 55.2 190 56.8 Mass Concentration Mass Mass Concentration Mass (mg) (ppm) Carbon (mg) (ppm) Carbon (ing) (mg) 4.0 .445 - - - trace - - 3.6 0.132 2.6 0.158 70 6.3 10 0.81 18 1.3 10 0.7 20 1.2 Sub Total Aldehydes Total Volume sampled, dscm Carbon Mass Concentration, mg/dson 3.6 0.4 0.045 0.2 0.023 0.5 0.045 0.9 0.081 0.6 0.055 0.2 0.013 0.3 0.028 2.0 10 0.358 1.6 20 1.2 31.8 4.9 - 9.5 5.5 11.4 70.3 21.9 91.2 2.03 45.4 0.36 0.18 0.45 0.82 0.45 0.18 0.23 5.5 12.3 - - - - - 20.47 2.16 22.6 2.07 10.9 TABLE 12. GAS CHROMATOGRAPHY/MASS SPECTROMETRY RESULTS ------- compound identified is presented. Calculated values for volume concentration (ppm), carbon mass (mg), and total carbon mass concen- tration (mg/dscm) are also presented. The total (aldehyde and GC/MS results) carbon mass concentration results for test runs 9A and 9B are 45.4 and 10.9 mg/dscm, respectively. Similarly, the calculated carbon mass concentration values for TCA runs 9A and 9B are 34.5 and 5.8 mg/dscm, respectively. 20 ------- V. SAMPLING LOCATIONS Figure 1 is a schematic of the two sampling locations indicating their relative positions to the thermal incinerator at the Pico Rivera plant. The inlet duct was thirty-six inches (36") in diameter, while the outlet stack was forty-one inches (41") in diameter. The traverse points are listed in Table 13. VI. SAMPLING AND ANALYTICAL PROCEDURES Total Combustion Analysis (TCA) Figure 2 is an illustration of the TCA sampling apparatus. The system was derived from the method entitled "Total Combustion Analysis.1 Differences between the sampling train specified by this procedure and the sampling train employed for this particular test include use of aluminum sample tanks, a heated filter, and a capillary orifice to regulate the flow at 80 ml/min. Analyses of the samples were conducted by Truesdail Laboratories, Inc., whose report is included in the appendix. The organic contents of the condensate trap were oxidized to carbon dioxide (C02) which was quantitatively collected and then measured by a non-dispersive infrared (NDIR) analyzer. A fraction of the sample collected in the evacuated tank was injected into a gas chromatograph in order to achieve separation of the non-methane organics from carbon monoxide, carbon dioxide, and methane. Once separated, the four fractions were oxidized to carbon dioxide and separately measured with the NDIR. The volume of sample Total Combustion Analysis; Air Pollution Control District, County of Los Angeles; Salo, Albert E.; Oaks, William L., and MacPhee, Robert D. August 1974. 21 ------- ro - ro PWNVIEW MOTOR ACCESS OOORU VIEW PORT 2 ACCESS DOOR #2 VIEW PORT 3 VIEW PORT 4 FIGURE .1. INCINERATOR SCHEMATIC ------- INLET POINT. ' -.TV-'.;. - . 2 _';.'.: .' 3 ;:: ". -/ V / ,5. ;. .- 6 DISTANCE . . ; 1.5" ';:..'' :. \,'V / ;; 5, 25" -,:'; -/;.;-;' . 10.75" '' . 25.25" 30.75" 34.5" . . .-:. OUTLET ' ; . POINT-. :::..''" V;;-! :-.V:' "- \ .;.;:; :;';v : 2 ;>,; ' . r ; '.-.;-.- '.3 '.,;/, ,;. ;';/:.;./;.' '4..';:.'.- .'"'.' -. - : : 5 '.-''. 6 ..'.DISTANCE :1.75- :; 6.0" ' 12.25" 28.75" - 35.0" . .39.0" TAULE 13, TKAVEKSE I'OINTS 23 ------- POTENTIOMETER THERMOCOUPLE IN3 PROBE r~ i FILTER HOLDER j Ğx 1 1 1 ^ys^^ss^ssssssssss^sa^E^eissrfTsss^^^^sss.'sssaia 1 1 1 JS53B3 -.^ CONDEiSiSATE TRAP i ^JL~~^ r~ sss=aKsss:K5= :s5tssfqj!3^~~!*sg! SSg 1 1 I "I i i i i i i i ; i I . . CAPILLARY ORIFICE ^/5/inD *> ^*ĞĞj/ iii /i i j~-~ i ~ ~-\J4XX/ j SHUT OFF VALVE VACUUM PRESSURE GAUGE .J HEATED BOX CRUSHED DRY ICE 8-LITER GAS COLLECTION TANK FIGURE 2. TCA SAMPLING APPARATUS ------- collected was calculated from vacuum and pressure readings of the evacu- ated sample tank before and after sampling. The measured CCL concen- trations and the sample volume collected were used to calculate the total gaseous non-methane organic concentration in the source as parts per million carbon. Direct Measurement Apparatus The direct measurement apparatus is illustrated in Figure 3. This sampling system incorporates the flame ionization analyzers and the integrated bag sampling system. The integrated bag sample was taken from the heated manifold as were the samples for the flame ionization analyzers. To insure that a valid sample was being delivered to the analyzer two procedures were performed. To leak check the inlet and outlet sample lines the inlet of the heat traced lines were capped and the lines were evacuated. The flow in the system was monitored at the exit of the pump with a rotameter; a zero flow rate indicated a leak tight system. To check for sample loss or contamination, a second pro- cedure was followed. A 50 liter bag was used to introduce calibration gas at the sample line inlet. A correct FID response insured that the I system was leak tight and that no contamination was introduced by the heated lines. Both of these procedures were conducted periodically i throughout the test period. ; Total Organic Carbon (TOG) '- Figure 4 is a schematic of the total organic carbon (TO.C) sampling \ train. The TOC train is basically a modified Method 5 train; with a J vessel containing XAD-2 solid adsorbent resin added after the filter. During the test, the adsorbent trap was maintained at 45°F. j| The filter 25 ------- ro NON- HEATED LINES HEATED LINES ZERO AIR LOW SPAN OUTLET BAG SAMPLE | INLET THREE-WAY VALVE TO .FLOW AMBIENT AIR THROUGH SYSTEM EXCESS SAMPLE "BYPASS FLOW FLOW METER FLOW METER OUTLET I THREE-WAY VALVE BECKMAN ANALYZER SCOTT ANALYZER A HORIBA ANALYZER 1 1 L. 1 PU HEA \ i MP ) Ihl k ^~ J MANII-UUU 1 1 HIGH SPAN 1 SILICAGEL TRAP ^j 1^ 1 J THREE-WAY I VALVE SILICAGEL TRAP I FLOW METER [J-{PUMP BYPASS FLOW FOR EFFLUENT STREAM NOT BEING SAMPLED FIGURE.3. . DIRECT MEASUREMENT APPARATUS ------- SOLID ADSORBENT TRAP THERMAL COUPLE HEATED BOX FILTER HOLDER r PROBE ro IMP'INGERS ^ -, _ THERMAL COUPLE ICE BATH ORIFICE GAUGE \ VACUUM GAUGE COARSE CONTROL VALVE 'DRY GAS METER FIGURE 4. TOTAL ORGANIC CARBON APPARATUS ------- was a forty-seven millimeter (47 mm) glass fiber filter which was maintained, along with the probe, at approximately two hundred and fifty degrees (250°F). The first two impingers were charged with a solution of sodium metabisulfite to collect aldehydes which are not collected by the resin. The third impinger was empty while the i fourth impinger contained 200 grams of silica gel to collect moisture and protect the pump and dry gas meter. The flow rate during sampling .i was maintained at approximately one cubic foot per minute (1 cfrri); the probe was maintained at a single point in the stack. Since this sampling train will not collect C, - Cg organics, the integrated bag samples taken during the TOC runs were analyzed for Cj - Cg compounds by GC. j For analysis the resin was refluxed in pentane to extract tlhe organics; the extract was then injected into a GC/MS system. Ajblank sample was also analyzed in order to establish background levels. GC/MS operation was as follows: COLUMN TYPE - 3% OV-17/CHROMASORB W COLUMN SIZE - 5 ft x 2.1 mm GLASS COLUMN TEMPERATURE PROGRAM - 50°C - 280°C @ 4°C/minute CARRIER FLOW RATE - 30 cc/minute He The Applied Technology Division (ATD) of TRW performed the' analysis. The filter portion of the sampling train was not ana; For further information regarding sampling and analysis with, refer to EPA level 1 assessment manual. IERL-RTP Procedures Manual: EPA 600/2-76-160A, June 1976. Level 1 Environmental Ass 28 XA GC/MS yzedi ent ------- The aldehydes trapped in the impinger solutions of the TOC.jtrain ij were analyzed by the sulfoxylate method described in the "Source Test ji Manual," Air Pollution Control District, County of Los Angeles.jjon page seventy-two (p. 72). tj ( 1 A more complete reference is contained in Goldman and Jragoda, Industrial Engineering Chemistry Annual Addition; 15-377, 29 ------- |