United States Environmental Protection Agency Office of Air Quality EMB Report 83-ASP-4 Planning and Standards ADDENDUM Research Triangle Park NC 27711 March 1985 Air vvEPA Asphalt Concrete Industry Emission Test Report T.J. Campbell Company Oklahoma City Oklahoma Volume 1 Addendum ------- CORPORATION DCN 222-078-03-15 EMISSION TEST REPORT T.J. CAMPBELL ASPHALT CONCRETE PLANT OKLAHOMA CITY, OKLAHOMA Addendum Prepared for: Mr. Clyde E. Riley Task Manager Emissions Measurement Branch Office of Air Quality Planning and Standards U.S. Environmental Protection Agency Research Triangle Park, North Carolina 27711 EPA Contract No. 68-02-3850 Work Assignment 03 ESED Project No. 83-05 Prepared by: M. R. Fuchs E. P. Anderson L. A. Rohlack A. E. Behl Radian Corporation 15 March 1985 8501 Mo-Pac Blvd. / P.O. Box 9948 / Austin, Texas 78766 / (512)454-4797 ------- INTRODUCTION This addendum presents revisions and new data to be included with the report, "Emission Test Report T.J. Campbell Company, Oklahoma City, Okla- homa" (EMB Report 83-ASP-4). The purpose of this addendum is threefold: • to present smoke point/flash point results for the recycled asphalt pavement and asphalt cement which were not available when the report was published; • to include total organic carbon (TOC) results determined according to the analytical protocol of EPA Method 5E; and • to separate condensible hydrocarbons data from the extract- able organics data presented in the report. The term condensible hydrocarbons is new to the report. As explained in the original report, extractable organics are related to the gravimetric analysis of the ether/chloroform extract of the 0.1 N NaOH impinger solu- tions. The extractable organics results in the original report included the gravimetric analysis of the trichloroethane (TCE) rinse of the impingers glassware. In this addendum, condensible hydrocarbon results are from the gravimetric analysis of the TCE rinse. The gravimetric analysis results of the TCE rinse have been removed from the extractable organics presentation. Because of the above revisions, several sections of the report have been rewritten. Section 2.2, Total Organic Carbon Results, has been revised to present TOC results determined by the EPA Method 5E analytical protocol. Tables 2-1, 2-2, 2-3, and 2-4 contain the revised TOC values. Section 2.3, Extractable Organics Emissions Results, contains results from the 0.1N NaOH impinger solution ether/chloroform extract only. Tables 2-7, 2-8, 2-9, and 2-10 contain the revised extractable organic emission results. Section 2.4, Comparison of TOC and Extractable Organic Emission Results, reflects the EPA Method 5E TOC results and ether/chloroform extract results. Section 5.2, ------- RADIAN CORPORATION Analytical Methodology, discusses the new or revised methods for TOC and extractable organics analysis. Table 6-2 has been addended to include TOC quality control data for the 0.1N NaOH impinger solutions reanalysis. In addition, three new sections have been added. Section 2.11 contains a discussion of the flash point and smoke point data which are presented in Table 2-24. Section 2.12 contains a discussion of the condensible hydrocar- bon results which are presented in Table 2-25. Section 2.13 contains a comparison of the two analytical methodologies used to analyze the 0.1N NaOH impinger solutions for TOC. The data are presented in Table 2-26. ------- 2.2 TOTAL ORGANIC CARBON RESULTS Controlled and uncontrolled total organic carbon (TOC) mass samples were collected simultaneously with particulate mass samples using the modi- fied EPA Method 5E sampling train. The TOC content of the 0.1N NaOH im- pinge r and rinse solutions were analyzed directly using an instrumental technique. TOC results, identified in the data tables as the "back-half catch," are presented and discussed in this section. 2.2.1 Conventional Operation TOC Emission Results Uncontrolled and controlled TOC results for conventional operation are presented in Table 2-1 (English units) and Table 2-2 (metric units). Uncon- trolled TOC loadings were 0.242, 0.0512, and 0.0562 gr/DSCF for Runs C-l, C-2, and C-3, respectively. The controlled TOC loadings were 0.0410, 0.0501, and 0.0494 gr/DSCF for Runs C-l, C-2, and C-3, respectively. The TOC (back-half catch) collection efficiency of the wet venturi scrubber was 83.1, 0.39, and 15.0 percent for Runs C-l, C-2, and C-3, respectively. 2.2.2 Recycle Operation TOC Emission Results Table 2-3 (English units) and Table 2-4 (metric units) present results of the uncontrolled and controlled TOC measurements performed during recycle operation. Uncontrolled TOC loadings were 0.0534, 0.0523, and 0.389 gr/DSCF for Runs R-l, R-2, and R-3, respectively. The controlled TOC loadings were 0.0643, 0.0421, and 0.0185 gr/DSCF for Runs R-l, R-2, and R-3, respectively. The TOC collection efficiency of the wet venturi scrubber was 6.65, 12.9, and 95.2 percent for Runs R-l, R-2, and R-3, respectively. 2.2.3 Discussion of TOC Test Results The uncontrolled TOC loadings varied from 0.0521 to 0.242 gr/DSCF during conventional operation and from 0.0523 to 0.389 gr/DSCF during re- cycle operation. The controlled TOC loadings varied from 0.0410 to 0.0501 ------- TABLE 2-1. SUMMARY OF PARTICULATE AND TOTAL ORGANIC CARBON EMISSIONS DURING CONVENTIONAL OPERATION (ENGLISH UNITS) Date Run Dumber Type Eni.aai.oni Scrubber Pressure Drop (in. H,0) Scrubber Water Flow Rate Production Rate (ton/br) Froce» Mix Type Average Opacity (Percent) Range (GPMJ Hean, 11/12 C-l Uncontrolled Controlled 13.5 219 244 B-Hix 0 (0-1. 5) 11/13 C-2 Uncontrolled Controlled 13.4 219 235 B/C Mix 0 (-0-) 11/14 C-3 Uncontrolled Controlled 13.5 215 213 M-Mix H/A Average Uncontrolled Controlled 13.5 218 231 0 Participate and Total Organic Carbon (TOO Reaulta Front Half Catch - farticulate (probe, cyclone, and filter) mg-maa a gr/DSCF Iba/hr* Iba/ton production Collection Efficiency Percent** Back Half Catch - TOC (impinger solutiona and rinse* ) mg-maa a gr/DSCF Iba/br* Iba/ton production Collection Efficiency Percent** Total Catch mg-maa a gr/DSCF Iba/hr* Iba/ton production Collection Efficiency Percent** 9360 7.60 762 3.12 299 0.242 24.3 0.0995 9660 7.84 785 3.22 172 0.0550 5.53 0.0226 99.3 128 0.0410 4.11 0.0168 83.1 300 0.0961 9.63 0.0395 98.8 10.800 8.49 910 3.87 65 0.0512 5.13 0.0218 10,900 8.53 855 3.64 244 0.0814 8.29 0.0353 99.1 150 0.0501 5.11 0.0217 0.39 394 0.132 13.4 0.0571 98.4 6950 5.58 599 2.81 70 0.0562 6.01 0.0282 7020 5.64 604 2.83 104 0.0332 3.45 0.0162 99.4 155 0.0494 5.11 0.0240 15.0 259 0.0823 8.53 0.0400 98.6 9040 7.22 757 3.27 145 0.116 11.8 0.0498 9190 7.34 748 3.23 173 0.0565 5.76 0.0247 99.2 144 0.0468 4.78 0.0208 59.5 318 0.103 10.5 0.0455 98.6 Average emiaaion rate of concentration and area-ratio metboda (Table 2-10) H/A - not available *lba/hr controlled emiaaion rate baaed on gaa flow rate uaing aaturation volume for the moiature content of the gaa "Collection efficiency percent determined uaing Iba/br valuea ------- TABLE 2-2. SUMMARY OF PARTICULATE AND TOTAL ORGANIC CARBON EMISSIONS DURING CONVENTIONAL OPERATION (METRIC UNITS) Date Run Number Type Emissions Scrubber Pressure Drop (in. H-0) Scrubber Water Flow Bate (LPSJ Production Kate (Eg/8) Procesa Mix Type Average Opacity (Percent) Mean, Range 11/12 C-l Uncontrolled Controlled 34.3 13.8 61.5 B-Mix 0 (0-1.5) 11/13 C-2 Uncontrolled Controlled 34.0 13.8 59.2 B/C Mix 0 (-0-) 11/14 C-3 Uncontrolled Controlled 34.3 13.6 53.7 M-Mix N/A Averatte Uncontrolled Controlled 34.3 13.7 58.1 0 99.3 Participate and Total Organic Carbon (TOO Reaulta Front Half Catch - Particulate (probe, cyclone, and filter) mg-mas s mg/DSCM g/e* g/kg production Collection Efficiency Percent** Back Half Catch - TOC (imp inger solutions and rinses) mg-mas a mg/DSCM g/s* g/kg production Collection Efficiency Percent** 9360 17,400 96.1 1.56 172 126 0.697 0.0113 10,800 19.400 115 1.94 244 186 1.05 0.0177 6950 12.800 75.5 1.41 104 76.0 0.435 0.00810 9040 16.500 95.5 1.64 173 129 0.726 0.0125 83.1 99.1 99.4 299 554 3.06 0.0498 128 93.8 0.518 0.0084 65 117 0.647 0.0109 150 115 0.644 0.0108 0.39 15.0 Total Catch ing-mass 9660 300 10.900 394 mg/DSCM 17.900 220 19.500 302 g/s* 99.0 1.21 108 1.69 g/kg production 1.61 0.0198 1.82 0.0286 Collection Efficiency Percent** 98.8 98.4 7020 12.900 76.2 1.42 259 188 1.08 0.0200 99.2 70 129 0.758 0.0141 155 113 0.644 0.0120 145 265 1.49 0.0249 144 107 0.602 0.0104 59.5 9190 16.800 94.3 1.62 318 236 1.32 04)228 98.6 98.6 Average emission rate of concentration and area-ratio methods (Table 2-10) N/A - not available *g/s controlled emission rate based on gas flow rate uaing saturation volume for the moisture content of the gas "Collection efficiency percent determined using g/s values ------- TABLE 2-3. SUMMARY OF PARTICULATE AND TOTAL ORGANIC CARBON EMISSIONS DURING RECYCLE OPERATION (ENGLISH UNITS) Date Run Number Type Emission* Scrubber Pressure Drop (in. H,0) Scrubber Water Flow Rate (GPH) Production Rate (ton/hr) Process Mix Type Average Opacity (Percent) Mean, Range 11/11 R-l Uncontrolled Controlled 13.8 223 229 Recycle-A 1.4 (0-5.8) 11/11 R-2 Uncontrolled Controlled 13.8 220 250 Recycle-A 0.3 (0-1.7) 11/12 R-3 Uncontrolled Controlled 13.9 219 236 Recycle-A N/A Average Uncontrolled Controlled 13.8 221 238 0.85 Particulate and Total Organic Carbon (TOO Results Front Half Catch - Particulate (probe, cyclone, and filter) mg-maas 4380 84.0 gr/DSCF 3.24 0.0227 Ibs/hr 411 2.72 Ibs/ton production 1.79 0.0119 Collection Efficiency Percent** 99:3 Back Halt Catch - TOC (impinger solutions and rinaes) mg-masa gr/DSCF Ibs/hr Ibs/ton production Collection Efficiency Percent** -6.65 Total Catch mg-mass 4450 322 gr/DSCF 3.30 0.0870 Ibs/hr 418 10.4 Ibs/ton production 1.82 0.0456 Collection Efficiency Percent** 97.5 5.260 4.37 499 2.00 88.2 0.0229 2.76 0.0110 99.4 72.0 0.0534 6.77 0.0296 238 0.0643 7.22 0.0337 63.0 0.0523 5.51 0.0220 162 0.0421 4.80 0.0192 12.9 5320 4.42 466 1.86 250 0.0650 7.41 0.0296 5570 3.75 474 2.01 111 0.0286 3.42 0.0145 99.3 95.2 6150 4.14 496 2.10 183 0.0470 5.63 0.0239 5070 3.79 461 1.94 94.5 0.0247 2.97 0.0125 99.4 576 0.389 46.6 0.198 72.0 0.0185 2.22 0.0094 237 0.165 19.6 0.0832 157 0.0416 4.91 0.0208 74.9 5310 3.95 460 1.93 252 0.0663 7.81 0.0330 98.4 98.9 98.3 Average emission rate of concentration and area-ratio metbode (Table 2-10) N/A - not available *lbe/hr controlled emission rate based on gas flow rate using saturation volume for the moisture content of the gas "Collection efficiency percent determined using Ibs/hr values ------- TABLE 2-4. SUMMARY OF PARTICULATE AND TOTAL ORGANIC CARBON EMISSIONS DURING RECYCLE OPERATION (METRIC UNITS) Date Run Number Type Emiajions Scrubber Pressure Drop (in. H.O) Scrubber Water Flow Bate (LPS) Production Rate (Kg/S) Process Mix Type Average Opacity (Percent) Mean. Range Particulate and Total Organic Carbon Front Half Catch - Particulate (probe, cyclone, and filter) mg-maa a og/DSCM g/a* g/kg production Collection Efficiency Percent** Back Half Catch - TOC (impinger aolutiona and rinses) mg-maaa mg-DSCH g/a* g/kg production Collection Efficiency Percent** Total Catch ing-mass mg/DSCM g/s* g/kg production Collection Efficiency Percent** 11/11 B-l Uncontrolled Controlled 5.43 14.1 57.8 Recycle-A 1.4 (0-3.8) (TOC) Reaults 4380 84.0 7420 51.9 51.8 0.343 0.896 0.00593 99.3 72.0 238 122 147 0.854 0.910 0.0148 0.0168 -6.65 4450 322 7550 199 52.7 1.31 0.910 0.0228 97.5 11/11 11/12 R-2 R-3 Uncontrolled Controlled Uncontrolled Controlled 5.43 5.47 13.9 13.8 63.1 59.6 Recycle-A Recycle-A 0.3 (0-1.7) H/A 5.260 88.2 5570 111 10,000 52.5 8590 65.4 62.9 0.348 59.8 0.431 0.919 0.00550 1.01 0.00726 99.4 99.3 63.0 162 576 72.0 120 96.4 890 42.3 0.965 0.605 5.88 0.280 0.0110 0.0096 0.0990 0.0047 12.9 95.2 5320 250 6150 183 10.100 149 9480 108 58.8 0.934 62.6 0.710 0.930 0.0148 1.05 0.0120 98.4 98.9 Averafte Uncontrolled Controlled 5070 8670 58.2 0.942 237 378 2.47 0.0416 5310 9040 58.0 0.965 5.44 13.9 60.2 0.85 94.5 56.6 0.374 0.00622 99.4 157 95.2 0.619 0.0104 74.9 252 152 0.985 0.0165 98.3 Average emission rate of concentration and area-ratio methoda (Table 2-10) N/A - not available *g/s controlled emission rate based on gas flow rate using saturation volume for the moisture content of the gas "Collection efficiency percent determined using g/a valuea ------- gr/DSCF during conventional operation and from 0.0185 to 0.0643 gr/DSCF during recycle operation. With the limited data available, it is difficult to develop any correlations between process operation and the degree of < variability in the uncontrolled and controlled TOG emissions during conven- tional and recycle operation. The average uncontrolled TOC loading was 29.7 percent greater during recycle operation (0.165 gr/DSCF) than during conventional operation (0.116 gr/DSCF). However, the average controlled TOC loading during recycle opera- tion (0.0416 gr/DSCF) was 14.4 percent less than the average conventional operation loading (0.0486 gr/DSCF). The average removal efficiency of the venturi scrubber was 74.8 percent during recycle operation and 64.1 percent during conventional operation. ------- CORPORATMM 2.3 EXTRACTABLE ORGANICS EMISSION RESULTS Analysis for extractable organics was performed on the 0.1N NaOH im- pinge r solutions. Aliquots of the 0.1N NaOH samples were extracted with chloroform and diethyl ether. The solvent was evaporated at room tempera- ture to dryness and the mass of extractable organics determined gravimetri- cally. Tables 2-7 and 2-8 contain a summary of uncontrolled and controlled extractable organics and particulate emission results. Extractable organics are identified as the "back-half catch" in Tables 2-7 and 2-8. 2.3.1 Conventional Operation Extractable Organics Emission Results Uncontrolled extractable organics loadings were 0.0032, 0.0111, and 0.0169 gr/DSCF for Runs C-l, C-2, and C-3, respectively. The controlled extractable organics loadings were 0.0227, 0.0131, and 0.0193 gr/DSCF for Runs C-l, C-2, and C-3, respectively. 2.3.2 Recycle Operation Extractable Organics Emission Results Uncontrolled extractable organics loadings were 0.0186, 0.0077, and 0.0140 gr/DSCF for Runs R-l, R-2, and R-3, respectively. Controlled extrac- table organics loadings were 0.0121, 0.0286, and 0.0162 gr/DSCF for Runs R-l, R-2, and R-3, respectively. 2.3.3 Discussion of Extractable Organics Emission Test Results The uncontrolled extractable organics loadings varied from 0.0032 to 0.0169 gr/DSCF during conventional operation and from 0.0077 to 0.0186 gr/DSCF during recycle operation. The controlled extractable organics loadings varied from 0.0131 to 0.0227 gr/DSCF during conventional operation and from 0.0121 to 0.0286 gr/DSCF during recycle operation. Based on the limited data available, it is difficult to develop any correlations between process operation and the degree of variability in the uncontrolled and ------- TABLE 2-7. SUMMARY OF UNCONTROLLED PARTICULATE AND EXTRACTABLE ORGANICS EMISSIONS DATE RUN HO. PROCESS OPERATION VOLUME GAS SAMPLED (DSCF) STACK GAS FLOW RATE (DSCFM) STACK TEMPERATURE CF) PERCENT MOISTURE BY VOLUME PERCENT ISOKINETIC PRODUCTION RATE (tons/br) 11/12 C-l CONVENTIONAL 19.0 11.700 298 38.0 110 244 11/11 R-l RECYCLE 20.8 14,800 296 24.4 95 229 11/13 C-2 CONVENTIONAL 19.6 11.700 289 39.6 113 235 11/11 R-2 RECYCLE 18.6 12,300 314 31.5 117 250 11/14 C-3 CONVENTIONAL 19.2 12,500 304 36.7 104 213 11/12 B-3 RECYCLE 22.9 14,000 317 27.7 111 236 CONVENTIONAL 19.3 12,000 297 38.1 109 231 RECYCLE 20.8 13,700 309 27.9 108 238 PARTICULATE - EXTRACTABLE ORGANIC8 RESULTS FRONT HALF CATCH - PARTICULATE (probe, cyclone, and filter) rag-masa gr/DSCF Ibe/hc Iba/ton production BACK HALF CATCH - EXTRACT- ABLE ORCANICS 9360 7.60 762 3.12 4380 3.24 411 1.79 10,800 8.49 910 3.87 5260 4.37 499 2.00 6950 5.58 599 2.81 5570 3.75 474 2.01 9040 7.22 757 3.28 Average emIBaion rate of concentration and area-ratio methods (Table 2-10). 'Percent Extractable Organic8 determined using Ibs/hr values and is tbe percentage of extractable organic8 of the total catch. 5070 3.79 461 1.94 (impinger solutions & riases) ing-mas s gr/DSCF Ibs/br Iba/ton production PERCENT EXTRACTABLE ORGANICS* 4.0 0.0032 0.325 0.0013 0.04 25.1 0.0186 2.36 0.0103 0.57 14.1 0.0111 1.11 0 .0047 0.12 9.3 0.0077 0.811 0.0032 0.16 21.1 0.0169 1.81 0.0085 0.30 20.8 0.0140 1.68 0.0071 0.35 13.1 0.0104 1.08 0 .0048 0.14 18.4 0.0134 1.62 0.0069 0.35 ------- TABLE 2-8. SUMMARY OF CONTROLLED PARTICULATE AND EXTRACTABLE ORGANICS EMISSIONS DATE RUN NO. PROCESS OPERATION VOLUME GAS SAMPLED (DSCF) STACK CAS FLOW RATE (DSCFH) STACK TEMPERATURE (°F) PERCENT MOISTUBE BY VOLUME PERCENT ISOKINETIC PRODUCTION RATE (tono/hr) PARTICULATE - EXTRACTABLE ORGANICS RESULTS 11/12 C-l CONVENTIONAL 48.2 11.700* (11.400) 159 32.0 (32.3) 102 (105) 244 11/11 R-l RECYCLE 57.1 14.000 147 21.3 104 229 11/13 C-2 CONVENTIONAL 46.2 11,900 (11.400) 155 29.0 (32.3) 96 (100) 235 11/11 R-2 RECYCLE 59.3 13,300 (12,700) 152 26.6 (30.6) 111 (116) 250 11/14 C-3 CONVENTIONAL 48.5 12,100 (11.800) 153 27.5 (29.7) 99 (102) 213 11/12 R-3 RECYCLE 60.1 14.000 143 20.7 107 236 CONVENTIONAL 47.6 11.900 (11.500) 156 29.5 (32.1) 99 (102) 231 RECYCLE 58.8 13.800 (13.600) 147 22.9 (24.2) 107 (109) 238 FRONT HALF CATCH - PARTICULATE ' (probe, cyclone, and filter) mg-masa gr/DSCF Iba/br Iba/ton production BACK HALF CATCH - EXTRACT- ABLE ORGANICS (impinger solutions & rinses) ng-mas s gr/DSCF Iba/br Iba/ton production PERCENT EXTRACTABLE ORGANICS* 172 0.0550 5.53 (5.36) 0.0227 (0.0220) 71.0 0.0227 2.28 (2.22) 0.0093 (0.0091) 29.2 (29.3) 84.0 0.0227 2.72 0.0119 44.7 0.0121 1.45 0.0063 34.8 244 0.0814 8.29 (7.95) 0.0353 (0.0338) 39.3 0.0131 1.34 (1.28) 0.0057 (0.0054) 13.9 (13.9) 88.2 0.0229 2.76 (2.49) 0.0110 (0.0100) 110 0.0286 3.25 (3.11) 0.0130 (0.0124) 54.1 (55.5) 104 0.0332 3.45 (3.36) 0.0162 (0.0158) 60.7 0.0193 2.00 (1.95) 0.0094 (0.0092) 36.7 (36.7) 111 0.0286 3.42 0.0145 63.0 0.0162 1.94 0.0082 36.2 173 0.0565 5.76 (5.56) 0.0247 (0.0239) 57.0 0.0184 1.88 (1.81) 0.0081 (0.0078) 24.6 (24.6) 94.5 0.0247 2.97 (2.88) 0.0125 (0.0123) 72.6 0.0190 2.24 (2.21) 0.0094 (0.0093) 43.0 (43.4) NOTE: Top number based on saturation volume for moisture content of gas: (bottom number) is moisture content calculated using impinger catcb indicating the presence of water niat. Average emission rate of concentration and area-ratio methods (Table 2-10). Percent Extractable Organica determined using Ibs/br values and is the percentage of extractable organic a of the total catcb. ------- controlled extractable organics emissions during conventional and recycle operation. The average uncontrolled extractable organics loading during recycle operation (0.0134 gr/DSCF) was approximately 22 percent greater than during conventional operation (0.0104 gr/DSCF). The average controlled extractable organics loading during recycle operation (0.0190 gr/DSCF) approximated the average controlled organics loading during conventional operation (0.0184 gr/DSCF). The average uncontrolled extractable organics loadings are less than the average controlled extractable organics loadings during both recycle and conventional operation. Controlled emissions of extractable organics were 27.7 percent higher than uncontrolled emissions during recycle operation and 42.6 percent higher during conventional operation. A review of the data indicates that the results are representative of conditions. The mass of extractable organics per unit volume measured in the controlled emissions was significantly higher than the mass of extractable organics measured in the uncontrolled emissions. A possible explanation is that the scrubber water contributes to the extractable organics concentration of controlled emissions due to the concentration of extractable organics in the water mist carried over from the venturi. The scrubber water would include organic compounds that are water soluble or miscible that would concentrate in the scrubber water to a degree depending on gas phase concentration, water re- cycle, and make-up. Condensible hydrocarbons on the other hand would tend to condense on particulate and be physically removed by the venturi. The con- densible hydrocarbons would then be removed with the venturi pond sludge or appear as an oily film on the pond water which would not be recycled. The results indicate that the venturi controls condensible hydrocarbons by an average of 82.0 percent during recycle operation and 76.8 percent during conventional operation. 12 ------- RADIAN CORPOOATIOM 2.4 COMPARISON OF TOG AND EXTRACTABLE ORGANICS EMISSION RESULTS Two analytical procedures were used during this program to quantify the concentration of uncontrolled and controlled organic emissions generated during conventional and recycle operation. An instrumental technique was used to determine the concentration of TOG present in the 0.1N NaOH impinger solutions generated during EPA Method 5E testing. The same samples were also analyzed using a extraction/gravimetric technique to determine the concentration of extractable organics. The main objective of performing both analyses on the same samples was to provide data that could be used to assess the utility of both procedures in characterizing organic emissions from asphalt concrete plants. 2.4.1 Comparison of Uncontrolled TOG and Extractable Organics Emission Results Table 2-9 presents a comparison of uncontrolled TOG and extractable organics emissions during conventional and recycle operation. The average uncontrolled TOG loadings during recycle operation (0.165 gr/DSCF) were 29.7 percent higher than during conventional operation (0.116 gr/DSCF). The average uncontrolled extractable organics loadings during recycle operation (0.0134 gr/DSCF) were 22.4 percent higher than during conventional operation (0.0104 gr/DSCF). During recycle operation, the average extractable organics loading was 8.1 percent of the TOG loading and 9.0 percent during conventional operation. 2.4.2 Comparison of Controlled TOG and Extractable Organics Emission Results Table 2-10 presents a comparison of controlled TOG and extractable organics emissions during conventional and recycle operation. Average con- trolled TOG loadings during recycle operation (0.0416 gr/DSCF) were 12.5 percent lower than during conventional operation (0.0468 gr/DSCF). Average controlled extractable organics loadings during recycle operation (0.0190 13 ------- TABLE 2-9. COMPARISON OF UNCONTROLLED TOG AND EXTRACTABLE ORGANICS EMISSIONS RUN NUMBER PROCESS OPERATION DATE VOLUME GAS SAMPLES (DSCF) STACK GAS FLOW RATE (DSCFM) STACK TEMPERATURE (*F) PERCENT MOISTURE BY VOLUME PERCENT ISOKINETIC PRODUCTION RATE (TONS/HE) BACK HALF CATCH ORGANICS RESULTS (impinger solutions & rinses) rag-mass gr/DSCF Ibs/hr Ibs/ton production C-l C-2 CONVENTIONAL CONVENTIONAL 11/12 19.0 11,700 298 38.0 110 244 EXT** TOC* ORG . 299 4.0 0.242 0.0032 0 24.3 0.325 0.099S 0.0013 0 11/13 19.6 11.700 289 39.6 113 235 EXT TOC ORG. 65.0 14.1 .0512 0.0111 5.13 1.11 .0218 0.0047 C-3 CONVENTIONAL 11/14 19.2 12,500 304 36.7 104 213 EXT TOC ORG. 70.0 21.1 0.0562 0.0169 6.01 1.81 0.0282 0.0085 R-l RECYCLE 11/11 20.8 14,800 296 24.4 95 229 EXT TOC ORG. 72.0 25.1 0.0534 0.0186 6.77 2.36 0.0296 0.0103 R-2 RECYCLE 11/11 18.6 12,300 314 31.5 117 250 EXT TOC ORG. 63.0 9.30 0.0523 0.0077 5.51 0.81 0.0220 0.0032 R-3 EffiYCLE 11/12 22.9 14,000 317 27.7 111 236 EXT TOC ORG 576 20.8 0.389 0.0140 46.6 1.68 0.198 0.0071 AVERAGE CONVENTIONAL 19.3 12,000 297 38.1 109 231 EXT TOC ORG. 145 13.1 0.116 0.0104 0 11.8 1.08 0.0498 0.0048 0. RECYCLE 20.8 13,700 309 27.9 108 238 EXT TOC ORG. 237 18.4 .165 0.0134 19.6 1.62 0832 0.0069 * TOC - Total Organic Carbon "EXT. ORC. - Extractable Organics ------- TABLE 2-10. COMPARISON OF CONTROLLED TOC AND EXTRACTABLE ORGANICS EMISSIONS RUN NUMBER PROCESS OPERATION DATE VOLUME GAS SAMPLES (DSC?) STACK GAS FLOW RATE (DSCFM) STACK TEMPERATURE ("F) C-l CONVENTIONAL 11/12 48.2 11.700* (11.400) 159 PERCENT MOISTURE BY VOLUME 32.0 PERCENT ISOKINETIC PRODUCTION BATE (TONS/US) BACK HALF CATCH ORCAHIC8 RESULTS (impinger solutions & rinses) mg-maa a gr/DSCF Ibs/br Ibs/ton production (34.3) 102 (105) 244 C-2 CONVENTIONAL 11/13 46.2 11,900 (11,400) 155 29.0 (32.3) 96 (100) 235 EXT*** EXT TOC** ORG. 128 71.0 0.0410 0.0227 4.11 2.28 0.0168 0.0093 TOC ORG. 150 39.3 0.0501 0.0131 5.11 1.34 0.0217 0.0057 C-3 CONVENTIONAL 11/14 48.5 12,100 (11,800) 153 27.5 (29.7) 99 (102) 213 EXT TOC ORG. 155 60*7 0.0494 0.0193 5.11 2.00 0.0240 0.0094 R-l RECYCLE 11/11 57.1 14,000 147 21.3 104 229 EXT TOC ORG. 238 44.7 0.0643 0.0121 7.22 1.45 0.0337 0.0063 R-2 RECYCLE 11/11 59.3 13,300 (12,700) 152 26.6 (30.6) 111 (116) 250 EXT TOC ORG. 162 110 0.0421 0.0286 4.80 3.25 0.0192 0.0130 R-3 RECYCLE 11/12 60.1 14,000 143 20.7 107 236 EXT TOC ORG. 72 63.0 0.0185 0.0162 2.22 1.94 0.0094 0.0082 AVERAGE CONVENTIONAL 47.6 11,900 (11,500) 156 29.5 (32.1) 99 (102) 231 EXT TOC ORG . 144 57.0 0.0468 0.0184 4.78 1.88 0.0208 0.0081 RECYCLE 58.8 13.800 (13,600) 147 22.9 (24.2) 107 (109) 238 EXT TOC ORG. 157 72.6 0.0416 0.0190 4.91 2.24 0.0208 0.0094 *NOTE: Top number based on saturation volume for moisture content of gas: (bottom number) is moisture content calculated using impinger catch results indicating the presence of water mist. ** TOC - Total Organic Carbon ***EXT. ORG. - Extractable Organica ------- gr/DSCF) were slightly higher (3.2 percent) than during conventional opera- tion (0.0184 gr/DSCF). The extractable orgenies loading was 45.7 percent of the TOC loading during recycle operation and 39.3 percent during conven- tional operation. 2.4.3 Discussion of TOC and Extractable Organics Emissions Results Because of the limited quantity of available data, it is difficult to develop an accurate comparison between the TOC and extractable organics results. To formulate an opinion about the two procedures, one must first evaluate the analytical procedures. It is important that several factors be kept in mind. First, the TOC analysis results are indicative of the total mass of soluble carbon, as organic species, in the sample. The extractable organics analysis results are related to the mass of organic species having a boiling point greater than 300°F. Also, the TOC analysis procedure is a direct instrumental technique requiring a minimal amount of sample prepara- tion (refer to Section 5.2). On the other hand, the extractable organics analysis procedure requires sample preparation (refer to Section 5.2) by means of extraction with chloroform and diethy 1 ether. The remaining ex- tract is then evaporated to dryness at room temperature before weighing. It is believed that the TOC analysis procedure is more suitable than the extractable organics procedure for characterizing organic emissions from asphalt concrete plants. 16 ------- RADIAN 2.11.4 Recycled Asphalt Pavement and Asphalt Cement Smoke Point and Flash Point Results Smoke point determination was performed on a single sample of recycled asphalt pavement (RAP) collected during the Campbell test program. The sample was analyzed by the Oklahoma Testing Laboratory and by Radian. The smoke point test results are presented in Table 2-24. The smoke point determined by Oklahoma Testing Laboratory was 340°F. The smoke point deter- mined by Radian was 370°F. Samples of the asphalt cement (AC) used during the Campbell test pro- gram were analyzed for smoke point and flash point. The AC smoke point and flash point analyses were performed by the Oklahoma Testing Laboratory. The smoke point and flash point data are presented in Table 2-24. 17 ------- TABLE 2-24. SUMMARY OF RECYCLED ASPHALT PAVEMENT (RAP) SMOKE POINT RESULTS AND ASPHALT CEMENT (AC) SMOKE POINT AND FLASH POINT RESULTS Collection Date Sample Description Sample Type Oklahoma Testing Smoke Point Radian3 Smoke Flash Point Point 11-12-83 Recycled Asphalt Pavement RAP 340 370 11-08-83 McGee Asphalt Cement AC 420 640 11-12-83 Allied Chemical Asphalt AC Cement 345 550 aFlash point and smoke point analysis of the AC performed by Oklahoma Testing Laboratories only. 18 ------- 2.12 CONDENSIBLE HYDROCARBONS EMISSION RESULTS The sample fraction which condensed on the walls of the chilled glass- ware is referred to as condensible hydrocarbons. A trichloroethane (ICE) rinse was used to recover the condensed hydrocarbons from the impingers. The TCE was evaporated to dryness at room temperature to determine the mass of condensible hydrocarbons. Condensible hydrocarbons results are presented in Table 2-25. 2.12.1 Conventional Operation Condensible Hydrocarbons Emission Results Uncontrolled condensible hydrocarbons loadings were 0.173, 0.0457, and 0.114 gr/DSCF for Runs C-l, C-2, and C-3, respectively. The controlled condensible hydrocarbons loadings were 0.0558, 0.0140, and 0.0086 gr/DSCF for Runs C-l, C-2, and C-3, respectively. 2.12.2 Recycle Operation Condensible Hydrocarbons Emission Results Uncontrolled condensible hydrocarbons loadings were 0.136, 0.133, and 0.0619 gr/DSCF for Runs R-l, R-2, and R-3, respectively. The controlled condensible hydrocarbons loadings were 0.0114, 0.0311, and 0.0173 gr/DSCF for Runs R-l, R-2, and R-3, respectively. 2.12.3 Discussion of Condensible Hydrocarbons Emission Results The uncontrolled condensible hydrocarbons loadings varied from 0.0457 to 0.173 gr/DSCF during conventional operation and from 0.0619 to 0.136 gr/DSCF during recycle operation. The controlled condensible hydrocarbons loadings varied from 0.0086 to 0.0558 gr/DSCF during conventional operation and from 0.0114 to 0.0311 gr/DSCF during recycle operation. With the limited data available, it is difficult to develop any correlations between process operation and degree of variability of the controlled and uncon- trolled condensible hydrocarbon emissions during conventional and recycle operation. 19 ------- TABLE 2-25. SUMMARY OF CONDENSIBLE HYDROCARBONS EMISSIONS Corrected TCE Date Run Description Rinse Wt (mg)a gr/DSCF Ibs/hr Ibs/ton CONTROLLED EMISSIONS Recycle Operation 11-11-83 11-11-83 11-12-83 Run R-l Run R-2 Run R-3 Average 42.1 120 67.3 76.3 0.0114 0.0311 0.0173 0.0199 1.36 3.54 2.07 2.32 0.0060 0.0142 0.0088 0.0097 Conventional Operation 11-12-83 11-13-83 11-14-83 Run C-l Run C-2 Run C-3 Average 174 41.8 27.0 81.0 0.0558 0.0140 0.0086 0.0261 5.59 1.43 0.89 2.64 0.0229 0.0061 0.0042 0.0111 UNCONTROLLED EMISSIONS Recycle Operation 11-11-83 11-11-83 11-12-83 Run R-l Run R-2 Run R-3 Average 183 160 91.9 145 0.136 0.133 0.0619 0.110 17.2 14.0 7.42 12.9 0.0750 0.0559 0.0315 0.0541 Conventional Operation 11-12-83 11-13-83 11-14-83 Run C-l Run C-2 Run C-3 Average 213 58.2 142 138 0.173 0.0457 0.114 0.111 17.3 4.58 12.2 11.4 0.0710 0.0195 0.0571 0.0492 aCorrected for trichloroethane blank residue 20 ------- RADIAN The average uncontrolled condensible hydrocarbons loading during re- cycle operation (0.110 gr/DSCF) approximated the average uncontrolled con- densible hydrocarbons loading during conventional operation (0.111 gr/DSCF), The average controlled condensible hydrocarbons loading during recycle oper- ation (0.0199 gr/DSCF) was approximately 24 percent less than the conven- tional operation condensible hydrocarbons loading (0.0261 gr/DSCF). The average removal efficiency of the venturi scrubber was 82.0 percent during recycle operation and 76.8 percent during conventional operation. 21 ------- RADIAN 2.13 COMPARISON OF TOC ANALYTICAL METHODS Two analytical methods were used to determine the TOC concentrations of the 0.1N NaOH impinger solutions. The original method (the values reported in the original report) consisted of acidifying the sample below pH 2 with H2SO^ and purging with nitrogen to remove inorganic carbon. This method was specified in the test plan for the T.J. Campbell emission test. The second method was the EPA Method 5E protocol (see Appendix Section J.I). To determine if the two methodologies yielded different results, the original samples were reanalyzed using both methods. Table 2-26 presents a comparison of the original analysis (acidification) and the reanalysis using both methods (EPA Method 5E and acidification). Results of the sample reanalysis indicate that EPA Method 5E protocol yields lower results than the acidification and purge technique. A possible explanation for the lower values obtained by EPA Method 5E is that the absence of inorganic carbon is verified and if present the results are corrected accordingly. With the acidification and purge method, this step is not performed and if there is incomplete inorganic carbon removal, a high bias would occur. 23 ------- TABLE 2-26. SUMMARY OF T.J. CAMPBELL TOTAL ORGANIC CARBON (TOG) EMISSION RESULTS COMPARING TWO ANALYTICAL METHODS Original Campbell TOC Emissions: Method la Campbell TOC Reanalysis: Method la Campbell TOC Reanalysis: Method 2 1\UU ii» " ' gr/DSCF Ibs/hr Ibs/ton gr/DSCF Ibs/hr Ibs/ton gr/DSCF Ibs/hr Ibs/ton UNCONTROLLED EMISSIONS Recycle Run 1 Run 2 Run 3 Average Convent ional Run 1 Run 2 Run 3 Average 0. 0. 0. 0. 0. 0. 0. 0. 448 655 504 536 205 434 297 312 56.8 68.9 60.5 62.1 20.6 43.6 31.9 32.0 0.248 0.276 0.256 0.260 0.0843 0.186 0.150 0.140 0.685 1.16 0.963 0.936 0.958 0.684 0.602 0.748 86.8 122 115 108 96.0 68.5 64.4 76.3 0.379 0.490 0.489 0.453 0.394 0.291 0.302 0.329 0.0534 0.0523 0.389 0.165 0.242 0.0512 0.0562 0.116 6.77 5.51 46.6 19.6 24.3 5.13 6.01 11.8 0.0296 0.0220 0.198 0.0832 0.0995 0.0218 0.0282 0.0498 CONTROLLED EMISSIONS Recycle Run 1 Run 2 Run 3 Average Conventional Run 1 Run 2 Run 3 Average 0. 0. 0. 0. 0. 0. 0. 0. a Ac id if icat iona nd purge bEPA Method 5E protocol 0592 0975 159 105 0532 139 129 107 7.10 11.1 19.0 12.4 5.32 14.2 13.4 11.0 0.0310 0.0444 0.0808 0.0521 0.0218 0.0604 0.0627 0.0483 0.290 0.159 0.190 0.213 0.188 0.154 0.233 0.192 34.8 18.1 22.8 25.2 18.9 15.7 24.1 19.6 0.152 0.0724 0.0964 0.107 0.0773 0.0669 0.113 0.0857 0.0643 0.0421 0.0185 0.0416 0.0410 0.0501 0.0494 0.0468 7.72 4.80 2.22 4.91 4.11 5.11 5.11 4.78 0.0337 0.0192 0.0094 0.0208 0.0168 0.0217 0.0240 0.0208 analysis analysis ------- RADIAN CORPORATION 5.2 ANALYTICAL METHODOLOGY The previous section described sampling procedures. This section describes the analytical procedures and points out where samples for analysis were retrieved from the various sample streams. The majority of analyses for this project were performed at Radian's Austin laboratories. Samples for analysis resulted from the following: • particulate, TOC/extractable organics/condensible hydrocar- bons sampling train for controlled and uncontrolled air emissions; • particulate, TOC/extractable organics/condensible hydro- carbons, and trace metals sampling train for controlled and uncontrolled air emissions; • polynuclear aromatic hydrocarbons sampling train for controlled and uncontrolled air emissions; • scrubber water to and from the venturi; and • virgin aggregate and recycled asphalt pavement. Figures 5-7 through 5-10 present analytical schemes for the three sampling trains, scrubber waters, and process samples. These figures indi- cate where samples were retrieved from the various systems and the analyses performed. The following analyses were performed: • gravimetric analysis of solvent rinses, • gravimetric analysis of ether chloroform extract of impingers, • total organic carbon, 25 ------- CORPOOATIOI • major organics and benzo(a)pyrene, • trace metals, • total solids, • pH and temperature, and • moisture. Analysis of Extractable Organics—The extractable organics sample con- sisted of the material obtained by extracting the 0.1N NaOH impinger solu- tions with a mixture of chloroform and diethy1 ether. The extractable organics content of the NaOH impinger samples was determined using the following procedure. First, a 400 ml sample aliquot was adjusted to pH 7 using HC1 to improve extraction efficiency. The sample was then extracted with three portions of a 3:1 mixture of chloroform and diethyl ether for a total of 200 mis. The solvent was then filtered. The filtrate was evapo- rated to dryness at room temperature (70-75°) and weighed to a constant weight following desiccation. Analysis of Condensible Hydrocarbons—The condensible hydrocarbon sam- ple consisted of the material that condensed on the walls of the chilled glassware. The condensed hydrocarbon content was determined using the following gravimetric procedure. The impingers and associated glassware were rinsed with trichloroethane (TCE). The volume of each rinse was deter- mined gravimetrically, the entire sample was transferred to a tared beaker, and evaporated at room temperature. When dry, the beakers were desiccated 24 hours and weighed to a constant weight to determine the mass of condensed hydrocarbon. Each sample weight was corrected for the residue contributed by the solvent. Total Organic Carbon (TOG) Analysis—The TOC content of the EPA Method 5E sodium hydroxide impinger solutions and scrubber water filtrate samples 26 ------- was determined instrumentally using the procedure specified in EPA Method 5E. A Beckman Model 915B Total Carbon Analyzer was used to determine the total carbon content and total inorganic carbon content of the sample. The concentration of carbon present in the sample was determined by comparing the sample results with the results of standards prepared using potassium hydrogen phthalate. The total organic carbon content was determined by subtracting the total inorganic carbon content from the total carbon content, Gravimetric Analysis of Solvent Rinses—The sampling train for particu- late and TOC/extractable organics and the train which combined trace metals with particulate and TOC/extractable organics produced several solvent rinses requiring gravimetric analysis. The solvent rinses included: • acetone probe rinse, and • trichloroethane probe rinse. The rinse samples were placed in glass bottles and transported to Radian's Austin laboratories for analysis. The volume of solvent in each sample was determined gravimetrically and then the entire sample was evapo- rated at room temperature. The sample could not be dried at elevated tem- peratures because of the potential loss of hydrocarbons. When dry, the beakers were desiccated for 24 hours and then weighed to a constant weight. A constant weight is defined as two weighings that agree within 0.5 mg or 1 percent of the residue mass. The residue in the solvent probe rinses collected during the trace metals runs was dissolved in HC1, HNOo, and H^Oo and was analyzed by Induc- tively Coupled Argon Plasma Emissions Spectroscopy (ICAPES). Smoke Point Determination of Recycled Asphalt Pavement—The smoke point of the RAP samples was determined using a test procedure developed by the Oklahoma Testing Laboratory. Based on this method, a sample of RAP is first dried to a constant weight in an oven set at 140°F. 500 grams of the dried 27 ------- RADIAN sample is then placed in a stainless steel bowl and heated at a rate of 25 to 30°F per minute while stirring the RAF with a stainless steel spatula. When the sample temperature is approximately 250°F, the heating rate is decreased so that the sample temperature rise is 5° to 10°F per minute until the smoke point is reached. The smoke point is recorded as the temperature at which the RAP starts to smoke. Smoke Point and Flash Point Determination of Asphalt Cement—The smoke point and flash point of the asphalt cement used during testing was deter- mined by the ASTM D92-Cleveland Open Cup procedure. Based on this method, the test cup is filled to a specified level with the asphalt sample. The temperature of the sample is increased rapidly at first and then at a slow constant rate as the smoke point is approached. As soon as the smoke is detected, the temperature of the sample is noted. To determine the flash point, the temperature is increased and at specified intervals, a small test flame is passed across the cup. The lowest temperature at which application of the test flame causes the vapors above the surface of the liquid to ignite is taken as the flash point. Annual Book of ASTM Standards, "Standard Test Method for Flash and Fire Points by Cleveland Open Cup," Part 23, Petroleum Products and Lubricants (I), D92-72, pages 27-32. 28 ------- CORPORATION TABLE 6-2. SUMMARY OF TOTAL ORGANIC CARBON AUDIT SAMPLE MEASUREMENTS Sample No. Date of Analysis (A) Actual Values (R) Radian Analysis Values (mg/L) Percent Error R-A/A x 100 EPA Prepared Sample Results (9/9/83) EPA 1 10-28-83 EPA 2 thru EPA 3 11-02-83 EPA 5 Radian Prepared Sample Results Set 1 - Submitted 11-30-83 Radian #1 Radian #2 Radian #3 Radian #4 Radian #5 Radian #6 Set 2 - Submitted 12-12-83 Radian #la Radian #2 Radian #3 Radian #4 Radian #5 Radian #6 4.1 61.2 61.2 4.1 80 40 80 4 4 40 80a 20b 20a 80b 80a 20a 4.5 70 69 3 85 45 81 4 3 41 85 21 19 84 77 21 9.76 14.4 12.7 -26.8 6.25 12.5 1.2 0 -25.0 2.5 6.25 5.0 -5.0 5.0 -3.75 5.0 fSample in 0.1 in. NaOH matrix Sample in distilled water Sample Number Radian 1 Radian 2 Radian 3 Date of Analysis Submitted 8-09-84 (A) Actual Value 593 119 59.3 (R) Radian Analysis Method la 562 108 40.9 Percent Error R-A/AxlOO -5.2 -9.2 -31.0 (R) Radian Analysis Method 2b 604 167 128 Percent Error R-A/AxlOO 1.8 40.3 116 aEPA Method 5E Protocol Acidification 29 ------- |