600SR97024 United States Environmental Protection Agency National Risk Management Research Laboratory Cincinnati OH 45268 Research and Development EPA/600/SR-97/024 July 1997 Project Summary Testing the Performance of Real-Time Incinerator Emission Monitors S.B. Ghorishi, W.E. Whitworth, Jr., C.G. Goldman, and LR. Waterland In a recently completed test program at the U.S. Environmental Protection Agency (EPA) Incineration Research Fa- cility (IRF), ten prototype or developing continuous emission monitors (OEMs) for measuring trace metal or trace or- ganic species concentrations were tested. Of the ten OEMs tested, four measured concentrations of several specific volatile organic compounds (VOCs), one measured total paniculate- bound polynuclear aromatic hydrocar- bon concentrations, two measured concentrations of up to 14 trace met- als, and three measured mercury con- centrations. While the testing consisted of obtaining quantitative measurement data on the four measures of GEM per- formance checked in a relative accu- racy test audit as described in 40 CFR 60 Appendix F—relative accuracy (RA), calibration drift (CD), zero drift (ZD), and response time—the primary project objective focused on the RA measure- ment. The RA measurement was achieved by comparing the monitored analyte concentration reported by the CEM to the concentration determined by the EPA reference method (RM) for the analyte. Four series of tests were performed, each simultaneously test- ing up to three monitors measuring the same or similar analyte type. Each test series consisted of performing tripli- cate RM measurements at each of three target flue gas monitored analyte con- centrations while the tested OEMs were in operation. All measurements were taken in the wet scrubber exit flue gas from the pilot-scale rotary kiln incin- eration system at the IRF. The test program results clearly showed the prototype nature of most approaches tested, and the clear need for further development. Mercury OEMs will require the least development and are nearly commercial offerings. How- ever, the approaches tested for multi- metals and VOC determinations require further development. Given this need, the importance of continuing test pro- grams of the scope and scale of this one cannot be overemphasized. This Project Summary was developed by EPA's National Risk Management Research Laboratory, Cincinnati, OH, to announce key findings of the research project that is fully documented in a separate report of the same title (see Project Report ordering Information at back). Introduction EPA is currently developing more strin- gent emission standards and considering changes in the way that permits for waste combustion facilities are handled. More public involvement in the process has been proposed. Because the public's apparent perception of incinerators is that high con- centrations of hazardous compounds are continually being released from the stacks of the thermal treatment devices, a means by which the "real-time" (defined as rang- ing from instantaneous to within several hours) organic and metals emissions can be monitored would be of great benefit to both regulators and the regulated commu- Printed on Recycled Paper ------- nity. The ability to have "immediate" knowl- edge of stack emissions would provide assurances that the thermal treatment de- vice is operating correctly or indicate the change of operating conditions needed to adjust stack emissions. Thus, having this monitoring capability would constitute one means of responding to and allaying the public's fears by showing that good, safe, and clean combustion practices can be demonstrated. Several developers have designed moni- toring units that they claim will measure various regulated hazardous compounds using a number of different innovative con- cepts and technologies. The development of these GEM approaches for both trace metal and trace organic analyte classes has advanced to the state that several candidate approaches are now in the pro- totype instrument stage. Given this, the general objective of the project reported herein was to test several prototype in- struments and establish or estimate for each unit the effectiveness, reliability, ac- curacy, and detection limit. For this test program, ten developing GEM approaches were tested. These are listed in Table 1 by monitored analyte class. As shown, included in the list of CEMs tested in this program are one semivolatile organic constituent (SVOC), four VOC, two multi-metal, and three mer- cury CEMs. Table 1. Participants in the GEM Test Program Test Program The selected approaches evaluated in this test program were performed in the pilot-scale rotary kiln incineration system (RKS) at EPA's IRF, located in Jefferson, AR. The testing consisted of obtaining quantitative measurement data on four measures of GEM performance checked in a relative accuracy test audit of a GEM as described in 40 CFR 60 Appendix F. These measures are RA, CD, ZD, and response time. Measuring a CEM's RA requires com- paring the monitored analyte concentra- tion reported by the GEM to the concentration determined by the RM for the analyte. In this program, the RM for trace metal (including mercury) monitors was draft Method 29, the EPA multiple metals method documented in the boiler and industrial furnace rules. The RM for VOCs was Method 0030 with analysis us- ing thermal desorption, purge and trap by Method 5040, and quantitation by Method 8015A. The RM for SVOCs was Method 0010 with analysis by Method 8270B. Test Facility Figure 1 is a process schematic of the RKS as configured for these tests. The RKS consists of a primary combustion chamber, a transition section, and a fired afterburner chamber. After exiting the af- terburner extension, flue gas flows through a quench section that is followed by a Monitored Analyte Developer Approach SVOCs VOCs EcoChem EcoLogic Marine Shale Processors (MSP) Oak Ridge National Laboratory (ORNL) EPA, Air Pollution Prevention and Control Division (APPCD) Multi-metals Sandia National Laboratories (SNL) Metorex Mercury Perkin-Elmer Senova EcoChem Photoionization of aerosol-bound polycyclic aromatic hydrocarbons Continuous chemical ionization mass spectrometry Continuous online mass spectrometry Direct sampling ion trap mass spectrometry Online gas chromatography with dual flame ionization, electron capture detection Laser induced plasma spectroscopy Extractive beta gauge particulate monitor with x-ray fluorescence metals analysis Gold trap amalgamation collection, cold vapor atomic absorption spectroscopy analysis Noble metal film solid state chemical microsensor Cold vapor atomic absorption spectroscopy primary air pollution control system (ARCS). The initial element of the primary ARCS for these tests was the venturi scrubber/packed-column scrubber combi- nation shown in Figure 1. This scrubber system removes from the flue gas most of the coarse particles and any acid gas, such as HCI. Following the scrubber sys- tem, the flue gas is reheated to about 120°C (250°F) by a 100-kW electric duct heater, then passed through a fabric filter (baghouse). The baghouse removes most of the remaining flue gas particles. Down- stream of the baghouse, a backup, sec- ondary ARCS, comprised of an activated-carbon adsorber and a high-effi- ciency particulate air filter is in place. The CEMs tested in this program sampled flue gas at the scrubber exit location. Testing Procedures The test program consisted of four se- ries of tests; each series tested one set of CEMs, generally monitoring the same ana- lyte set. Up to three CEMs were tested at the same time during each of the four test series. The major portion of the test pro- gram consisted of performing three se- quential RM measurements, while the tested CEMs were in operation, at each of three flue gas concentrations of monitored analytes. Thus, each test series was de- signed to supply nine sets of parallel RM and CEM reading data, three at each of three analyte concentrations. These nine sets of parallel RM and CEM data sup- ported the calculation of each CEM's RA. Thus, up to three RAs were calculated for each CEM, one at each of the three flue gas concentrations tested. Other test ef- forts supported the measurements of CD, ZD, and response time. Test Waste Feed The incinerator feed material was a syn- thetic hazardous waste comprised of an attapulgite clay solid sorbent combined with a mixture of 14 trace metals and VOCs. The mixture of VOCs added to the sorbent base contained 76% toluene by weight, with 12% each of chlorobenzene and tetrachloroethene. This mixture was combined with the clay sorbent in the ra- tio of 1.0 kg of organic constituent mixture to 2.4 kg of clay. The mixture was a free- flowing solid with no freestanding liquid and was continuously fed to the RKS via a screw feeder system. For all tests, the target clay/organic mixture feedrate was 68 kg/hr (150 Ib/hr). The target kiln exit gas temperature was 870°C (1,600°F), and the target afterburner exit gas tempera- ture was 1,065°C (1,950°F). f. *-: ------- Quench Air Natural liquid feed Transfer duct Primary Air Pollution Control System Carbon bed HEPA adsorber filter Baighouse Rotary Kiln Incinerator Redundant Air Pollution Control System Atmosphere Stack ID fan Figure 1. Schematic of the IRF rotary kiln incineration system. Multi-Metal and Mercury OEM Tests The trace metals of interest to the test program are listed in Table 2, which also notes the program target scrubber exit flue gas concentrations of each metal for the tests of multi-metals CEMs. For the mercury CEMs tests in Test Series 3, the low concentration targets were at half the levels noted in the low concentration col- umn in Table 2. The intermediate concen- tration targets were those noted in the low concentration column in Table 2. The high concentration targets were those noted in the intermediate concentration column in Table 2. This change was incorporated at the request of the mercury CEM develop- ers. Trace metals were added to the RKS, to result in scrubber exit flue gas levels, via two routes. Both routes used an aque- ous spike solution of the metals. A con- centrated solution was added for the multi-metal CEM test days at the high target flue gas metals concentration. This concentrated solution was diluted for the multi-metal CEM test days at the interme- diate and low target concentrations and for the mercury CEM tests. The two routes of metals addition were incorporated into the clay/organic mixture and atomized into the kiln main burner flame. VOC and SVOC CEM Tests The VOCs present in the scrubber exit flue gas for all tests included ben- zene, carbon tetrachloride, chloroben- zene, chloroform, 1,2-dichloroethane, 1,1-dichloroethene, tetrachloroethene, toluene, 1,1,1-trichloroethane, and tri- chloroethene. The target flue gas con- centrations of the compounds were in the 2, 20, and 200 ng/dscm ranges (low, in- termediate, and high concentrations). Naphthalene, phenanthrene, and pyrene were the SVOCs introduced into the flue gas for all tests, at the same target flue gas concentrations noted above. The VOCs and SVOCs were introduced into the flue gas by metering a solution of the spiking compounds in methanol through a length of fine bore stainless steel tubing into the afterburner extension at its centerline. The afterburner exit flue gas was partially quenched to a tempera- ture of between 360° to 427°C (680° and 800°F) by a water spray introduced at the Table 2. Test Trace Metals and Target Flue Gas Concentrations Target Flue Gas Concentration, ng/dscm Metal Antimony (Sb) Arsenic (As) Barium (Ba) Beryllium (Be) Cadmium (Cd) Chromium (Cr) Cobalt (Co) Lead (Pb) Manganese (Mn) Mercury (Hg) Nickel (Ni) Selenium (Se) Silver (Ag) Thallium (Tl) Low 10 5 50 0.5 5 20 10 50 5 20 10 40 5 5 Intermediate 40 20 200 2 20 80 40 200 20 80 40 200 20 20 High 400 200 2,000 20 200 560 400 2,000 200 800 400 2,000 200 200 ------- beginning of the afterburner extension. A concentrated organic spiking solution was prepared and used for the high target flue gas VOC and SVOC GEM tests. The con- centrated solution was diluted appropri- ately for the intermediate and low target flue gas concentration tests. Test Results VOC CEM Tests Tables 3 through 5 present the results of the three sequential RM measurements, along with the Oak Ridge National Labo- ratory (ORNL) and EcoLogic CEM results, for each of the three VOC concentrations tested in Test Series 1. The EcoLogic CEM data for the first day of testing at the low VOC concentration were not reported in EcoLogic's test report because of op- erator error that resulted in CEM readings that were inflated and incorrect. RAs cal- culated using the RM and CEM data in Tables 3 through 5 are summarized in Table 6. The data in Table 6 show that the calculated RAs for the ORNL CEM ranged from 123% to 305% at the low test concentration, with an average of 196% over the seven compounds reported. ORNL CEM RAs were improved at the intermediate test concentration, at 113% to 278%, with an average of 154% over the nine compounds reported. Further im- provement is seen at the high test con- centration, with an RA range of 84% to 144%, and an average of 105% over all ten compounds reported. In fact, the RA for all VOCs reported uniformly improved as the test concentration increased. Table 3. Measured Flue Gas Concentrations for the Test of the ORNL and EcoLogic CEMs at the Low VOC Concentration Concentration, ng/dscm IstDailvRM Compound Benzene Carbon tetrachloride Chlorobenzene Chloroform 1,2-Dichloroethane 1,1-Dichloroethene Tetrachloroethene Toluene 1,1,1- Trichloroethane Trichloroethene RM 32.4 31.2 55.6 40.8 2.4 86.4 89.9 352 2.5 6.9 ORNL 1.3 <0.4 0.76 0.56 2.5 3.2 1.7 9.2 <0.4 <0.4 Eco- Logic NO* NO NO NO NO NO NO NO NO NO 2nd Dailv RM RM 41.9 34.2 49.2 47.3 3.3 35.6 73.9 316 4.6 5.9 ORNL 1.6 <0.4 1.2 0.4 1.5 <0.4 1.3 9.2 <0.4 <0.4 Eco- Logic NO NO NO NO NO NO NO NO NO NO 3rd Dailv RM RM 59.6 38.0 86.7 41.6 2.6 16.9 126 462 6.4 3.9 ORNL 1.6 0.92 5.6 3.6 6.8 11.0 4.3 16 <0.4 <0.4 Eco- Logic NO NO NO NO NO NO NO NO NO NO aNO=CEM not operational. Table 4. Measured Flue Gas Concentrations for the Test of the ORNL and EcoLogic CEMs at the Intermediate VOC Concentration IstDailvRM Compound Benzene Carbon tetrachloride Chlorobenzene Chloroform 1 ,2-Dichloroethane 1,1-Dichloroethene Tetrachloroethene Toluene 1,1,1- Trichloroethane Trichloroethene RM 32.7 46.9 59.8 57.1 17.4 24.0 81.4 342 13.8 19.4 ORNL 12.0 10.1 25.8 23.9 43.3 55.3 11.1 147 <2.3 4.6 Eco- Logic 97 7.9 81 140 210 320 120 210 800 420 2nd Dailv RM RM 28.7 41.7 46.3 56.7 12.3 20.5 64.1 218 13.3 18.6 ORNL <2.3 3.8 7.2 9.6 16.6 26.7 2.5 71.8 <2.3 0.9 Eco- Logic 820 24 81 230 340 430 770 120 910 770 3rd Dailv RM RM 36.4 58.5 74.3 66.3 15.3 14.3 101 413 12.9 20.4 ORNL 5.5 6.4 27.6 18.4 29.5 40.5 7.4 103 <2.3 1.8 Eco- Logic 870 16 98 170 290 370 710 250 840 510 ------- Table 5. Measured Flue Gas Concentrations for the Test of the ORNL and EcoLogic CEMs at the High VOC Concentration Concentration, ng/dscm 1st Dailv RM Compound Benzene Carbon tetrachloride Chlorobenzene Chloroform 1 ,2-Dichloroethane 1,1-Dichloroethene Tetrachloroethene Toluene 1,1,1- Trichloroethane Trichloroethene RM 102 423 337 417 184 116 429 1,760 175 189 ORNL 36.8 101 138 101 88.4 38.7 62.6 847 24.9 15.7 Eco- Logic 140 380 250 330 450 350 690 1,300 170 340 2nd Dailv RM RM 89.1 409 299 411 174 140 374 1,393 164 176 ORNL 50.7 119 170 168 114 44.2 61.7 921 37.8 19.3 Eco- Logic 160 350 270 350 500 440 740 1,200 190 300 3rd Dailv RM RM 91.3 446 269 413 183 162 324 1,024 182 185 ORNL 28.6 76.4 97.6 91.2 6.3 35.9 37.8 460 20.3 14.7 Eco- Logic 190 360 280 390 540 480 690 760 210 360 Table 6. Relative Accuracies of the ORNL and EcoLogic CEMs RA,% ORNL Test Concentration Compound Benzene Carbon tetrachloride Chlorobenzene Chloroform 1 ,2-Dichloroethane 1,1-Dichloroethene Tetrachloroethene Toluene 1,1,1-Trichloroethane Trichloroethene Average6 Median" Low 173 NCa 164 123 305 299 162 145 NC NC 196 164 Intermediate 119 129 93 105 278 277 142 131 NC 113 154 129 High 98 100 84 97 144 115 113 88 110 103 105 100, 103 EcoLoqic Test Concentration Low NC NC NC NC NC NC NC NC NC NC NC NC Intermediate 5,020 135 74 396 2,890 2,520 1,640 65 7,320 5,140 2,520 1 ,640, 2,520 High 154 27 52 33 239 283 128 47 36 116 121 52, 116 " NC=Not calculated. b Average and median excludes NC entries. For the intermediate test concentra- tion, the RAs of the EcoLogic CEM ranged from 65% to 7,320%, with an average of 2,520%. Improved perfor- mance was seen at the high test con- centration, for which the RA ranged from 27% to 283% and averaged 121%. As seen for the ORNL CEM, the RAs for nine of the ten VOCs reported were im- proved at the high test concentration compared to the intermediate concen- tration. Tables 7 through 9 present the results of the three sequential RM measure- ments, along with the EPA/APPCD and MSP CEM results, for each of the three VOC concentrations tested in Test Se- ries 4. The tables indicate that, out of the nine sampling periods, MSP obtained data for only two periods. RAs corre- sponding to the RM/CEM concentration data given in Tables 7 through 9 are summarized in Table 10. The data in Table 10 show that the RAs for the EPA CEM ranged from 71% to 3,190% and averaged 638% for the low test concen- trations. The relatively high average RA was driven by the two very high RAs for 1,2-dichloroethane and 1,1-dichloroeth- ene. These two compounds were found in EPA/APPCD system blanks. EPA/ APPCD's decision not to blank-correct their data led to the corresponding high RAs. The median RA for the low con- centration test at a much improved 113% ------- Table?. Measured Flue Gas Concentrations for the Test of the EPA/APPCD and MSP CEMs at the Low VOC Concentration Concentration, ng/dscm 1st Daily RM Compound Benzene Carbon tetrachloride Chlorobenzene Chloroform 1 ,2-Dichloroethane 1,1-Dichloroethene Tetrachloroethene Toluene 1,1,1- Trichloroethane Trichloroethene aNO=Not operational Table 8. Measured RM 8.2 13.9 21.6 15.8 1.8 2.0 32.7 160.9 2.1 2.6 EPA/ APPCD 21.31 9.68 18.56 16.95 43.21 76.34 15.65 131.92 2.21 2.18 MSP NO" NO NO NO NO NO NO NO NO NO Flue Gas Concentrations for the Test of the RM 5.9 11.9 20.8 18.4 1.5 6.3 26.9 149.4 1.9 2.9 2nd Daily RM EPA/ APPCD 29.93 5.99 29.16 14.89 39.18 90.23 31.7 221.38 2.22 2.71 MSP 795 118 143 3,439 73.7 322 124 1,308 3.6 3,022 EPA/APPCD and MSP CEMs at the RM 8.4 13.3 16.0 15.8 1.6 5.1 20.6 97.1 1.8 3.0 Intermediate Concentration, ng/dscm 1st Daily RM Compound Benzene Carbon tetrachloride Chlorobenzene Chloroform 1 ,2-Dichloroethane 1,1-Dichloroethene Tetrachloroethene Toluene 1,1,1- Trichloroethane Trichloroethene RM 33.9 53.5 29.5 43.2 20.7 14.2 39.3 143 17.3 22.9 EPA/ APPCD 35.8 31.45 24.86 26.33 27.97 47.14 22.87 90.22 13.68 16.04 MSP NO" NO NO NO NO NO NO NO NO NO RM 32.9 57.8 64.6 62.1 18.1 11.3 92.7 498.5 16.2 20.6 2nd Daily RM EPA/ APPCD 42.41 37.58 54.15 31.61 34.9 54.48 58.32 306.1 14.33 16.63 MSP NO NO NO NO NO NO NO NO NO NO RM 33.6 64.1 75.0 63.5 16.6 9.9 96.8 551.8 17.4 19.1 3rd Daily RM EPA/ APPCD 22.21 4.99 18.8 9.25 30.33 84.49 8.56 57.85 3.53 1.74 MSP 707 126 60.2 1,515 78.5 271 107 814 4.1 1,602 VOC Concentration 3rd Daily RM EPA/ APPCD 50.34 40.55 40.73 43.31 55.71 101.19 30.3 163.48 14.54 15.74 MSP NO NO NO NO NO NO NO NO NO NO aNO=Not operational. to 137%, removes the dominant influence of the two compounds for which the GEM did poorly. The RAs for the EPA GEM were improved at the intermediate test concentration, ranging from 29% to 1,130% and averaging 213%. Poor performance in quantitating 1,2-dichloroethane and 1,1- dichloroethene again accounts largely for the high average RA. Again, the median RA at 83% to 98% better reflects the mean performance of the GEM by remov- ing the dominant influence of the RAs for the two VOCs poorly quantitated. Further improved performance of the EPA GEM was seen at the high test concentration, with an RA range from 34% to 133% and an average RA of 73%. In fact, at the high test concentration, the RAs for two com- pounds poorly quantitated at the low and intermediate test concentrations are more in line with those calculated for the other ------- Table 9. Measured Flue Gas Concentrations for the Test of the EPA/APPCD and MSP CEMs at the High VOC Concentration Concentration, ng/dscm 1 st Dailv RM Compound Benzene Carbon tetrachloride Chlorobenzene Chloroform 1 ,2-Dichloroethane 1,1-Dichloroethene Tetrachloroethene Toluene 1,1,1- Trichloroethane Trichloroethene RM 102.6 222.5 104.8 229.4 93.7 65.9 112.8 176.6 97.8 98.2 EPA/ APPCD 96.33 209.55 119.78 190.9 95.44 113.67 150.65 191.23 92.89 98.46 MSP NO NO NO NO NO NO NO NO NO NO 2nd Dailv RM RM 129.5 266.2 146.5 243.8 121.2 65.5 162.6 445.4 106.8 114.3 EPA/ APPCD 98.73 205.53 113.78 199.06 107.96 124.81 161.66 213.8 87.31 91.81 MSP NO NO NO NO NO NO NO NO NO NO 3rd Dailv RM RM 117.7 283.7 127.2 241.1 114.9 71.9 132.2 261.5 103.5 113.1 EPA/ APPCD 88.66 135.72 126.99 178.42 90.81 144.06 131.62 217.23 57.93 70.04 MSP NO NO NO NO NO NO NO NO NO NO aNO=Not operational. Table 10. Relative Accuracies of the EPA/APPCD and MSP CEMs RA,% EPA/APPCD Test Concentration Compound Benzene Carbon tetrachloride Chlorobenzene Chloroform 1 ,2-Dichloroethane 1,1-Dichloroethene Tetrachloroethene Toluene 1,1,1-Trichloroethane Trichloroethene Average Median Low Intermediate 429 86 87 76 3,190 2,040 137 113 150 71 638 113,137 83 45 98 71 334 1,130 134 158 29 45 213 83,98 High 48 95 53 34 40 133 50 138 73 70 73 53,70 MSP Test Concentration Low 18,300 1,200 3,150 85,800 6,740 10,700 673 3,040 315 384,000 51,400 3,150,6,740 eight compounds. For this reason, the median RA at 53% to 70% is comparable to the average RA. The calculated RAs based on the two available CEM/RM measurement pairs for the MSP GEM were quite large, ranging from 315% to 412,000% and averaging 54,600%. Even the median RAs for the MSP GEM, at 2,840% to 6,480%, are quite high. SVOC OEM Tests The SVOC GEM tests were performed at the same time as the second set of VOC GEM tests. Table 11 presents the results of the three sequential RM mea- surements performed each test day, and compares these to the EcoChem CEM results for the test days at the low and intermediate SVOC concentrations. Due to problems in the flue gas conditioning (moisture removal) system, the EcoChem CEM could not be brought into operation on the last day of testing at the high SVOC concentration. In addition, no CEM data were obtained during the first RM period on the intermediate concentration test day because the EcoChem CEM was not in operation, again due to problems with the flue gas moisture removal sys- tem. Table 11 also notes the RA of the EcoChem PAH CEM for the two test days the CEM was in operation. The table indicates that the RAs for the ------- Table 11. Measured Flue Gas Concentrations for the Tests of the EcoChem PAH CEMs Concentration, ng/dscm Test 1st Daily RM Low Concentration Test Naphthalene 1 .7 Phenanthrene 1 .3 Pyrene 1 .0 Total PAH 4.0 EcoChem CEM 6.9 Intermediate Concentration Test Naphthalene 1 7.5 Phenanthrene 15.7 Pyrene 9.1 Total PAH 42.3 EcoChem CEM NO High Concentration Test Naphthalene 97.0 Phenanthrene 91.4 Pyrene 68.2 Total PAH EcoChem CEM aNO=Not operational bNP=Not performed. cNC=Not calculated. Table 12. Measured 256. NO 6 2nd Daily RM 1.8 1.2 0.8 3.8 14.8 10.9 10.1 19.6 40.6 33.2 NP» NP NP NP NO Flue Gas Concentrations for the Test of the 3rd Daily RM RA,% SNL and 1.7 1.3 0.9 3.9 15.5 15.8 15.3 9.7 40.8 39.0 NP NP NP NP NO 527 99 NC Metorex CEMs at the Concentration, Metal Antimony (Sb) Arsenic (As) Barium (Ba) Cadmium (Cd) Chromium (Cr) Cobalt (Co) Lead (Pb) Manganese (Mn) Nickel (Ni) Selenium (Se) Thallium (Tl) RM 4.5 4.4 11.7 9.7 22.3 7.8 101 21.8 39.6 11.4 1.1 1st Daily SNL ND" ND ND ND ND ND ND ND ND ND ND RM Metorex ND 3.65 ND 2.63 2.49 12.11 11.51 5.89 27.52 1.51 ND RM 5.1 3.8 15.8 12.1 23.5 7.1 85.6 29.2 29.1 12.3 1.5 2nd Dailv SNL ND ND ND ND ND ND ND ND ND ND ND ng/dscm RM Metorex ND 0.83 ND ND 0.56 ND 9.06 ND 6.15 1.47 ND c Low Metals Concentrations RM 4.5 3.6 18.6 13.2 28.0 7.1 110 31.6 42.4 12.3 1.7 3rd Dailv SNL ND ND ND ND ND ND ND ND ND ND ND RM Metorex 5.13 1.19 6.23 10.02 22.29 14.68 12.36 19.43 21.87 3.62 ND •ND=Not detected. EcoChem CEM were 527% and 99%. As was seen in the VOC CEM tests, the RA at the higher test flue gas concentration was improved in comparison to the lower test concentration. Multi-Metal CEM Tests Tables 12 through 14 summarize the results of the three sequential RM mea- surements performed each test day and compares these to the Sandia National Laboratories (SNL) and Metorex CEM measurements. Neither CEM measured beryllium or mercury, so these metals are not included in the three tables. In addi- tion, results for silver are not included in the tables. Spike recovery from QA samples was poor, so silver concentra- ------- Table 13. Measured Flue Gas Concentrations for the Test of the SNL and Metorex CEMs at the Intermediate Metals Concentrations Concentration, iig/dscm Metal Reference Method 1 RM SNL Metorex Reference Method 2 RM SNL Metorex Reference Method 3 RM SNL Metorex Antimony (Sb) Arsenic (As) Barium (Ba) Cadmium (Cd) Chromium (Cr) Cobalt (Co) Lead (Pb) Manganese (Mn) Nickel (Ni) Selenium (Se) Thallium (Tl) 11.0 NDa 39.73 11.1 63 11.92 78.0 251 44.37 14.0 ND 7.22 54.7 ND 56.48 32.3 ND 14.72 141 144 107.07 24.2 ND 61.4 59.9 ND 26.48 43.2 ND 29.34 11.1 ND 12.96 11.6 ND 22.00 10.8 42 0.74 80.0 199 11.87 15.0 ND 26.93 59.5 ND 72.51 33.9 ND 20.79 141 93 51.80 24.6 ND 55.58 61.2 ND 21.26 54.5 ND 21.27 11.2 ND 4.49 9.5 ND 8.49 8.7 115 6.61 49.2 463 9.92 14.2 ND 10.09 50.3 ND 25.68 27.4 ND 9.79 136 106 40.86 18.2 ND 31.25 52.6 ND 15.76 53.2 ND 18.12 12.4 ND 2.72 aND=Not detected. Table 14. Measured Flue Gas Concentrations for the Test of the SNL and Metorex CEMs at the High Metals Concentrations Concentration, ng/dscm Metal Antimony (Sb) Arsenic (As) Barium (Ba) Cadmium (Cd) Chromium (Cr) Cobalt (Co) Lead (Pb) Manganese (Mn) Nickel (Ni) Selenium (Se) Thallium (Tl) Reference Method 1 "EKfl 5RE Metorex Reference Method 2 §NTMetorex 114 233 27.32 82.2 75 21.82 331 650 207.37 88.0 ND 33.58 425 ND 129.33 357 ND 100.16 1,650 ND 297.20 179 ND 52.89 550 ND 160.10 421 ND 102.52 114 ND 32.29 75.7 186 18.35 64.8 86 13.28 484.3 ND" 111.07 60.9 ND 31.73 299 ND 91.85 229 ND 67.47 1,082 ND 282.71 89.9 ND 35.25 347 ND 111.42 399 ND 96.70 94.3 ND 28.10 •ND=Not detected. tions as measured by the RM are highly suspect. The SNL GEM did not detect any of the test trace metals on the low con- centration test day, only arsenic, barium, and lead were reported on the intermedi- ate concentration test day, and only anti- mony, arsenic, barium, and lead for one or more RM periods were reported on the high concentration test day. The RAs corresponding to the mea- surement pair data in Tables 12 through Reference Method 3 SNL Metorex 43.5 131 6.59 54.8 65 4.68 285 ND 27.29 88.7 ND 22.18 241 ND 34.70 248 ND 37.62 2,176 54 167.04 95.6 ND 16.56 429 ND 67.89 383 ND 39.92 113 ND 16.84 14 are summarized in Table 15. The data in Table 15 show that the RAs for the SNL GEM ranged from 64% to 1,560% for the three metals reported on the interme- diate concentration test day, and from 65% to 188% for the two metals reported on the high concentration test day. RAs for the Metorex GEM ranged from 88% to 236%, with an average of 129% and a median of 116% for the low concentration test. Corresponding RAs for the interme- diate concentration test were 72% to 467%, with an average of 168% and a median of 135%, and, for the high con- centration test, 93% to 177%, with an average of 129% and a median of 121%. The RAs for the Metorex GEM were com- parable for each test concentration. No marked improvement as flue gas concen- tration increased, as observed for the VOC CEMs, is seen in the Metorex GEM data. ------- Table 15. Relative Accuracies of the SNL and Metorex CEMs RA,% Metal Antimony (Sb) Arsenic (As) Barium (Ba) Cadmium (Cd) Chromium (Cr) Cobalt (Co) Lead (Pb) Manganese (Mn) Nickel (Ni) Selenium (Se) Thallium (Tl) Average6 Median6 SNL Test Concentration Low NCa NC NC NC NC NC NC NC NC NC NC — — Intermediate NC 1,560 905 NC NC NC 64 NC NC NC NC 843 905 High 188 65 NC NC NC NC NC NC NC NC NC 127 65, 188 Metorex Test Concentration Low NC 125 NC 89 158 236 115 116 88 104 NC 129 116 Intermediate 467 174 135 177 94 72 112 261 77 113 171 168 135 High 158 101 153 123 113 118 177 146 121 93 111 129 121 "NC=Not calculated. bAverage and median exclude RAs NC. Mercury CEM Tests Table 16 summarizes the results of three sequential RM measurements performed each mercury CEM test day and com- pares these to the corresponding three mercury CEM measurements. Calculated RAs for each CEM are also given in the table for the three test days, each repre- senting a different flue gas mercury con- centration. The table indicates several periods during which the Perkin-Elmer and the Senova CEMs were not in operation. The data in Table 16 show that the EcoChem CEM had an RA of about 60% for both the low and the high concentra- tion tests. The RA at the intermediate concentration was increased, at 92%. The RA of the Perkin-Elmer CEM was 602% at the low mercury concentration and 1,150% (based on two measurement pairs) at the intermediate mercury concentration. The RA of the Senova CEM was 186% at the one test concentration having data. The full report was submitted in fulfill- ment of Contract No. 68-C4-0044, Work Assignments 0-4 and 1 -1, by Acurex En- vironmental Corporation under the spon- sorship of the U.S. Environmental Protection Agency. Table 16. Measured Flue Gas Concentrations and RAs for the Mercury CEM Tests "NO=Not operational. "NC=Not calculated. Mercury Concentration, ug/dscm Test Low Mercury Concentration RM1 RM2 RM3 RA,% Intermediate Mercury Concentration RM1 RM2 RMS RA,% High Mercury Concentration RM1 RM2 RMS RA,% RM 21 16 13 56 34 40 119 94 86 EcoChem CEM 22 20 19 60 83 43 56 92 137 81 62 61 Perkin-Elmer CEM 78 42 11 602 61 NO 125 1,150 NO NO 405 NC Senova CEM NO« NO NO NCb NO NO NO NC 232 116 165 186 10 ------- ------- S. B. Ghorishi, W. E. Whitworth, Jr., C. G. Goldman, andL R. Waterlandare with Acurex Environmental Corporation, Jefferson, AR 72079. R. C. Thurnau is the EPA Project Officer, and M. K. Richards is the Work Assignment Manager (see below). The complete report, entitled "Testing the Performance of Real-Time Incinerator Emission Monitors," (Order No. PB97-142871; Cost: $38.00, subject to change) will be available only from National Technical Information Service 5285 Port Royal Road Springfield, VA 22161 Telephone: 703-487-4650 The EPA Project Officer and Work Assignment Manager can be contacted at National Risk Management Research Laboratory U.S. Environmental Protection Agency Cincinnati, OH 45268 United States Environmental Protection Agency Center for Environmental Research Information Cincinnati, OH 45268 BULK RATE POSTAGE & FEES PAID EPA PERMIT No. G-35 Official Business Penalty for Private Use $300 EPA/600/SR-97/024 ------- |