United States Environmental Protection Agency Risk Reduction Engineering Laboratory Cincinnati OH 45268 Research and Development EPA/600/S2-91/007 July 1991 EPA Project Summary Emissions of Metals and Organics from Municipal Wastewater Sludge Incinerators Michael A. Vancil, Charles R. Parrish, and Michael A. Palazzolo In order to provide data for a sludge regulations development effort, emis- sions of metals and organics from a series of four wastewater sludge Incin- erators were measured. Three multiple hearth units and one fluldlzed bed combustor were tested. Emissions were controlled with a combination of venturl and/or tray Impingement scrubbers. One site Incorporated an afterburner as well. Flue gas testing was conducted at the Inlet and outlet to the air pollution con- trol devices at two of the plants. Feed sludge was also extensively tested for moisture, metals, and organlcs, as well as overall feed rate and heating value. Testing operating conditions were cat- egorized as short-term versus normal or long-term conditions, which include transients, start-up, feed interruptions, etc. All test results are fully documented In individual site reports. Emission test results for particulate matter/metals sampling are separated into short-term versus long-term tests. Gas concentra- tions, mass emissions rates, metals-to- particulate ratios, and emission factors are presented. Results are given for chromium VI sampling efforts. Metals concentrations in the various process streams (sludge feed, scrubber water, and bottom ash) are also given. Volatile and semivolatlle test results ara also presented for flue gas samples as well as sludge feed samples. Certain compounds were detected at higher mass rates in the flue gas than in the sludge, designating them as products of incomplete combustion (PICs). All other test results including CEM data, PSD data, CDD/CDF data, and op- erating data are all presented In the report volumes. This Project Summary was devel- oped by the principal Investigators and EPA's Risk Reduction Engineering Laboratory, Cincinnati, OH, to announce key findings of the research project that Is fully documented In the reports listed at the end of this summary. (See Project Report ordering Information at back.) Introduction The U.S. Environmental Protection Agency (EPA) has drafted regulations for air emissions from municipal wastewater sludge incinerators that are based on can- cer risk by inhalation of various metals and organics. The regulations were authorized under Section 405d of the Clean Water Act. A proposal soliciting public comments was published in the Federal Register on February 6, 1989. Final regulations are scheduled for publication in the Federal Register in January 1992. To provide data for these regulations, Radian Corporation performed emissions stack testing. These tests were performed at four operating municipal wastewater sludge incinerators from April to October 1987. The project was jointly funded by EPA's Risk Reduction Engineering Labo- ratory (RREL) and its Office of Water Regulations and Standards (OWRS). During the project, metals and organics data were collected to determine: • Long-term stack emissions over a range of operating conditions; Printed on Recycled Paper ------- • Long-term and short-term stack emis- sion rates as related to sludge com- position; • tf short-term stack emissions data taken during periods of best operation can approximate long-term stack emissions; The efficiency of wet scrubbers in removing metal and organic stack emissions; and • Cause and effect relationships be- tween incinerator operation and emissions (including the use of an afterburner). Test Methods At Sites 1 and 3, emissions testing was performed only at the control device outlet (exhaust stack). At Sites 2 and 4, emis- sions were measured at both the control device inlet and outlet. Also, at all four sites, samples of the sludge feed, scrub- ber water, and bottom ash were collected. Analyses of particle size distribution (PSD) were performed for Sites 2 and 4 and analyses of chlorinated dibenzo-p-dioxins and dibenzofurans (CDD/CDF) were per- formed for Site 4. Particulate matter (PM) and metals sam- pling was conducted at the scrubber inlet/ outlet according to EPA Reference Method 12 (Alternate). After gravimetric analysis of the filters, the particulate was digested in nitric acid and combined with the impinger solutions for analysis. Atomic adsorption (AA) analysis was used for the determina- tion of arsenic and lead. The determination of beryllium, cadmium, chromium, and ntekel was performed using the inductively coupled argon plasma (ICAP) technique. Flue gas sampling for volatile organics was performed using the most recently developed method by EPA. This method, using the volatile organic sampling train (VOST) (SW-846, Method 0030 for sam- pling and Method 5040 for analysis), is designed to collect volatile organic com- pounds with boiling points between 30'C and 100"C. The organics are collected on two resin traps in series containing Tenax resin and charcoal. The sample is col- lected at 1 L/min for 20 min for each pair of traps. Four pairs of traps are collected per test run. The resin traps are analyzed by the purge and trap techniques followed by gas chromatography/mass spectrometry (GC/MS). Semivolatile samples of the flue gas were collected according to the semi-VOST method developed by EPA. The method is basically a modification of EPA Reference Method 5 with a condenser and adsorbent module added after the filter and before the impinger train to collect semivolatile organics. The particulate filter, resin trap and impinger solutions are extracted with- organic solvent, concentrated, and ana- lyzed by GC/MS. Grab samples of the process samples, which included feed sludge, bottom ash, and scrubber influent and effluent water, were collected at regular intervals during flue gas sampling. The sludge feed was sampled from the feed conveyor after de- watering. Bottom ash was collected from an intermediate point on the conveyor system prior to combination with other ashes. Scrubber water was collected from taps in the pipes. Hourly or 30 min grab samples were combined at the end of a test run and analyzed following similar analytical schemes used for the flue gas samples. Continuous emissions monitoring was also conducted at all four test sites. Gases such as O2, CO2, CO, SO2, NOX and total hydrocarbons (THC) were continuously monitored daily. All results are tabulated and graphically presented in the individual site reports. The key operating parameters that were monitored include incinerator operating pa- rameters, sludge feed characteristics, and wet scrubber system operating data. Results The metals found in greatest concen- trations in the sludge were lead, chro- mium, and nickel. The highest metal emission rates (Table 1) were of lead and cadmium. Chromium, arsenic, and nickel were the metals most effectively removed by the scrubbers (Table 2). Lead emis- sion:! appeared to increase with increasing maximum hearth temperature. Testing for organics, in terms of volatile species (B.P. 30°C - 100°C) (Table 3) and semivolatile species (Table 4), took place. For the volatile species, toluene had the highest concentration in the sludge and acrylonitrilo, benzene, toluene, chloroform, and vinyl chloride had, the highest emis- sion rates. Certain compounds were de- tected in higher amounts at the stack when compared to the sludge indicating that they were PICs (Table 5). Certain species also appeared to be stripped from the primary and secondary treatment effluent used in the scrubbers. Few of the target semivolatile com- pounds were detected in either the sludge feed or at the stack. Bis(2-ethylhexyl) phthalate had the highest concentration in the sludge whereas phenol, naphthalene, and dichlorobenzene had the highest emission rates at the stack. The full reports were submitted in fulfill- ment of Contract No. 68-02-4288 by Ra- dian Corporation under the sponsorship of the U.S. Environmental Protection Agency. A paper containing data summaries has also been published in Process Safety and Environmental Protection, Transactions of the Institution of Chemical Engineers (En- gland), Part B, Volume 69, Number B1, pp 20-28, February 1991. Tabla 1. Particulate and Metals Stack Emission Factors for Steady State and Normal Operation Emission factors (g metal emitted/g metal fed) Site 1 Site 2 Site3 Site 4 (all steady state) Pollutant PM (g/kg dry sludge feed) Arsenic Beryllium Cadmium Chromium Lead Nickel Steady state 3.18 <0.01ff> ND° 0.10 0.002 0.12 0.010 Normal 2.63 <0.02Sf ND 0.15 0.001 0.21 0.006 Steady state 0.41 0.031 ND 0.21 0.0065 0.030 0.013 Normal 0.38 0.075 0.002 0.22 0.0038 0.047 0.0097 Steady state 0.396 0.0011 ND 0.041 0.0025 0.0013 0.0049 Cool ABoff 1.2 0.0026 ND 0.20 NA 0.10 0.0013 Hot ABorf 0.55 0.0017 ND 0.23 NA 0.19 0.0007 Hot ABoff 1.3 0.0013 ND 0.18 NA 0.14 0.0013 Cool, AB off* Cool furnace, afterburner off. Hot, AB on " Hot furnace, afterburner on. Hot, ABoff*= Hot furnace, afterburner off. 6 Arsenic not detected in sludge. Detection limit used to calculate emission factor. ND = Not detected. ------- Tables. Metals and Paniculate Removal Efficier Site 2 Element Arsenic Beryllium Cadmium Chromium Lead Nickel PM Steady state 77.2 >74.& 62.8 79.1 76.5 53.1 95.1 Normal 77.7 87.9 68.1 90.6 78.1 80.3 95.4 icy across Scrubber (%) Site 4 (Steady state Cool AB off) 97.2 NA" 47.1 98.0 36.6 95.4 97.1 Not detected at outlet Detection limit used to calculate removal efficiency. * NA = Not available. Beryllium not detected at inlet but detected at outlet .Jaftfe 3... yOQ.Steck Emission Rates under Steady State, (gram/hr) Site 4 Compound Acrylonitrile Benzene Carbon tetrachloride Chlorobenzene Chloroform 1 ,2-Dichloroethane trans- 1 ,2-Dichloroethane Ethylbenzene Methylene chloride Tetrachloroethene Toluene 1 1 1-Trichloroethane Trichloroethene Vinyl chloride Butene Methylhexene Xylene Trimethylbenzene Thiophene Pentene Site 1 6.23 7.87 0.0474 0.490 2.27 0.012 0.0952 0.795 1.04 5.74 2.36 0.134 0.643 2.49 1.14 0.342 2.08 0.092 0.262 0.625 . Site 2 12.6 5.29 0.0026 0.356 0.609 ND 0.009 0.445 0.577 0.882 11.9 0.020 0.157 7.97 0.152 ND 1.00 1.59 1.84 0.123 Site 3 NO" 0.401 0.014 0.0051 3.89 ND ND 0.024 0.070 0.151 0.067 0.043 0.011 ND ND ND 0.405 0.051 ND ND Steady state 21.6 4.40 9.20 0.536 0.251 ND 0.0297 1.06 1.47 0.892 4.15 1.10 1.51 1,10 1.63 0.204 0.287 0.020 0.346 1.54 Hot furnace, afterburner on 0.317 0.107 0.0055 0.176 0.318 0.0196 ND 0.0125 0.270 0.596 0.429 0.896 0.990 ND ND ND 0.038 0.200 ND ND 'ND = Not detected. Table 4. Emission Rates for Semivolatiles (gram/hr) Site 2 Compound Phenol Naphthalene Bis(2-ethylhexyl)phthalate 1,2-Dichlorobenzene 1,3-Dichlorobenzene 1,4-Dichlorobenzene 2-Nitrophenol S/teV (controlled) ND ND 0.89 1.0 0.83 2.2 ND (uncontrolled) 49 18 1.1 0.44 ND 0.48 5.5 (controlled) 2.3 2.4 0.85 0.51 0.05 0.62 1.6 Site 3 (controlled) ND ND 0.3 ND ND ND ND Site 4 (uncontrolled) 30.1 13.1 ND ND ND ND •&U.S. GOVERNMENT PRINTING OFFICE: 1991 - 548-028/40017 ------- Tablo 5. Summary of VOCs Formed as Products of Incomplete Combustion SitB 1 Acrylonitrile Benzene Mothylene chloride Tetrachtoroethene Toluene Vinyl chloride Si to 2 Acrylonitrile Benzene Vinyl chloride Site 3 Chloroform Site 4 Cool furnace, afterburner off Acrylonitrile Benzene Chlorobenzene Ethylbenzene Toluene Vinyl chloride Hot furnace, afterburner on Acrylonitrile Michael A. Vancil, Charles R. Parrish, and Michael A. Palazzolo are with Radian Corporation, Research Triangle Park, NC 27709. Harry Bostlan is the EPA Project Manager (see below). The complete report, entitled "Emissions of Metals and Organics from Municipal Wastewater Sludge Incinerators," consisting of eight volumes, will be sold as a set (Order No. PB91-151472; Cost $160.00, subject to change) or singly. "Volume I: Summary Report," (Order No. PB91-151480; Cost: $15.00, subject to change) presents a summary of all the emission test data. "Volume H:Site 1 Final Emission Test Report," (Order No. PB91-151498; Cost: $31.00, subject to change), "Volume III: Site 2 Final Emission Test Report" (Order No. PB91-151506; Cost: $31.00, subject to change), "Volume IV: She 2 Final Emission Test Report—Appendices," (Order No. PB91-151514; Cost: $11.00, subject to change), "Volume V: Site 3 Final Emission Test Report," (Order No. PB91-151522; Cost: $23.00, subject to change), "Volume VI: Site 4 Final Emission Test Report,"(Order No. PB91-151530; Cost: $31.00, subject to change), "Volume VII: Site 4 Final Emission Test Report—Appendices," (Order No. PB91-151548; Cost: $23.00, subject to change), present the detailed test results from each individual incinerator test program. "Volume VIII: GC/MS Tapes Review Report," (Order No. PB91-151555; Cost: $23.00, subject to changd) presents the findings from the review of the original GC/MS organics data. The GC/MS chromatograms were reviewed and additional volatile and semivolatile organics data were retrieved. AH volumes of this report will be available from: National Technical Information Service 5285 Port Royal Road Springfield, VA 22161 Telephone: 703-487-4650 The EPA Project Officer can be contacted at: Risk Reduction Engineering 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/S2-91/007 ------- |