X-/EPA United States Environmental Protection Agency Industrial Environmental Researcl Laboratory Research Triangle Park NC 27711 Research and Development EPA-600/S7-81-077 July 1982 Project Summary Environmental Assessment: Source Test and Evaluation Report—Exxon Miniplant Pressurized Fluidized-Bed Combustor with Sorbent Regeneration R. J. Kindya, R. R. Hall, G. T. Hunt, W. Piispanen, and P. F. Fennelly The report gives results of a compre- hensive emission sampling and analy- sis program conducted at the EPA- sponsored Exxon Miniplant, a pres- surized coal-fired fluidized-bed combustor and sorbent regeneration system. The sampling and analysis methods used provide screen ing data on organic and inorganic pollutants and indications of biological activity; however, in general, they are not designed to provide final quantitative results. Air pollutant emissions of trace elements were measured and com- pared to appropriate emissions goals. Seven inorganic trace elements ex- ceeded emissions goals in the com- bustor flue gas, indicating a need for further investigation. Air pollutant emissions of total organics were less than for comparable conventional combustion systems. Limited further analyses for specific polynuclear aromatic compounds indicated that emissions of one of these compounds exceed its emis- sions goal. Analysis of laboratory-generated leachates from solid waste samples revealed trace metal concentrations well below Federal hazardous waste criteria. Positive results for mutagenicity and cytotoxicity screening tests re- quire further investigation. Similar results have been reported for other coal-fired fluidized-bed combustors and conventional combustion systems. This Project Summary was devel- oped by EPA's Industrial Environ- mental Research Laboratory, Research Triangle Park. NC. 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 The development of fluidized-bed combustion (FBC) is being supported by the Federal government, private industry, and utility groups because of its potential advantages over conven- tional coal combustion methods. Re- duction of S02 during the combustion process is the primary advantage of FBC because it eliminates the need for add- on flue gas desulfurization equipment. Other advantages include a potential reduction in capital costs (compared to a conventional coal-fired boiler) and the capability to burn a wide variety of fuels, including such low-grade fuels as anthracite culm, coal cleaning wastes, and industrial wastes. An additional ------- advantage of pressurized fluidized bed technology is the potential to achieve higher fuel-to-electricity efficiencies than conventional systems. In fluidized-bed combustion, a mix- ture of coal and limestone is supported on a grid at the bottom of a boiler. Combustion air passes through the grid at high velocities, typically 1.2 - 2.4 m/s (4 - 8 ft/s). The upward flow of the air holds the solids in suspension, creating a quasi-f lu id that possesses many of the properties of the liquid. The most important liquid-like property to the boiler designer is the fact that bed material is exceptionally well mixed and flows throughout the system without agitation. This well-mixed semiliquid state produces high heat transfer rates and permits combustion at temperatures in the 760 - 930°C (1400 - 1700°F) range. The EPA-sponsored Exxon Miniplant was a pressurized fluidized-bed com- bustor (PFBC) and sorbent regeneration system with a coal-firing capacity of 1.8 MW (6.3 x 106 Btu/hr). Exxon operated the Miniplant from early 1974 to the summer of 1979, when the program ended. During the several thousand operating hours, extensive investiga- tions of sulfur capture, NOX emissions and control, high-pressure/high-tem- perature particulate control, combustion efficiencies, and many other aspects of FBC were completed. Sorbent regener- ation was demonstrated in 1975 and an experimental program including sorbent regeneration was conducted during the first half of 1979. This report discusses results of comprehensive sampling and analysis conducted by GCA/Technology Division at the Exxon Miniplant m May 1979.* These efforts were based on a phased approach to environmental assessment developed by EPA's Process Measure- ments Branch at the Industrial En- vironmental Research Laboratory at Research Triangle Park, NC (IERL-RTP). The first phase, Level 1, involves a screening approach using sampling and analytical techniques that sacrifice accuracy and compound specificity in order to identify any possible problem areas in a cost-effective manner. Level 1 should yield final analytical results within a factor of ±3. These results can be used to: provide preliminary envi- *GCA/Technology Division conducted the field measurement program under U S EPA Contract 68-02-2693, Exxon Research and Engineering operated the Miniplant and supported the field program under U S EPA Contract 68-02-1312 ronmental assessment data; identify problem areas; and formulate the data needed to rank energy and industrial processes, streams within a process, and components within a stream, for further consideration in the overall assessment. The second phase. Level 2, is directed by Level 1 results and is designed to provide additional, more specific, accurate, and quantitative information that will confirm and expand the data gathered in Level 1. The primary focus of the sampling and analysis discussed in this report was at Level 1. Some Level 2 analytical work was conducted. Facilities Description and Emission Streams Sampled Figure 1 is a simplified schematic diagram of the Exxon Miniplant as it operated during the Level 1 sampling program. As indicated, 11 streams were sampled for Level 1 analysis at the Miniplant. These samples are listed and described in Table 1. Individual com- ponents of the process are briefly described below. Process Description Coal and sorbent are injected pneu- matically into the combustor through a single port, 28 cm (11 in.)-above the water-cooled fluidizing grid. The flow of coal is controlled to maintain constant temperature in the combustor. The combustor is a 9.75 m (32 ft) high refractory-lined vessel with an i.d. of 33 cm {13 in.). Heat of combustion is removed by water-cooled tubes in the fluidized bed. Coal feed rates of 230 kg/hr (500 Ib/hr) and expanded bed heights of 6.1 m (20 ft) are possible, but the unit usually operates at about half these values. The unit is water cooled with both the cooling water temperature and metal temperature continuously measured. Solids are rejected from the com- bustor through a port abovethefluidizing grid. From this port, the solids flow by gravity through a steel pipe into a pulse pot. The solids are then pneumatically transported by controlled nitrogen pulses to a pressurized lockhopper from which they are periodically dumped into metal drums. A similar system, not including a pressurized lockhopper, is used to transfer solids tothe regenerator. Combustion and fluidizing air are provided by a mam air compressor (shown in Figure 1). Pressure in the combustor is controlled by maintaining a specified gas flow, across an appro- priately sized ceramic-coated orifice, b dilution of the flue gases with higl pressure air as shown in the top c Figure 1 . The sorbent regenerator consists of ; refractory-lined vessel with an i.d. of 2'. cm (8.5 in.) and an overall height of 6.' m (22 ft). Operating temperatures a high as 1 100°C (2000°F) and pressun up to 1000kPa (10atm)canbeachievei in the regenerator. Typical superficia velocity is 0.6 m/s (2 ft/s) with ai expanded bed height of 2.3 m (7.5 ft). The regeneration process is based 01 the one-step reductive decomposition o CaSCU by the reaction: CaS04 CaO S02 An undesirable competing reactior involving the formation of CaS als< occurs: CaS04 + 4 H2 CO CaS + 4 Therefore, an oxidizing zone is providet in the regeneration vessel to conver CaS to CaS04: CaS + 202 CaSO4 (3 At the Miniplant, natural gas is burned in the plenum below the fluidizing grid to achieve the reactior temperature. Additional fuel is injectec directly into the bed, just above the fluidizing grid, to create a reducing zone in which reaction (1) occurs. Supple mentary air is injected into the fluidizec bed to create an oxidizing zone tc convert CaS to CaSO4 via reaction (3). Flue Gas and Flue Gas Particulate Handling Flue gas and entrained solids (fly ash and sorbent) exit the top of the com- bustor and enter a three-stage cyclone system. Solids separated by the first- stage cyclone drop through a stee dipleg and enter a pulse pot from whicr they are pneumatically conveyed bacl< to the combustor (100 percent rein jected). Solids (primarily fly ash) escaping the primary cyclone enter more efficiem second- and third-stage cyclones where finer sizes of solids are captured. The third-stage cyclone operates at 85 to 94 percent efficiency. The final flue gases generally contain 0.03 to 0.15 g/Nm3 o1 particulates with a mass median diam- eter of 1 to 3 /urn. The collected solids from these cyclones pass thr-ougl" separate diplegs and enter pressurizec ------- To ESP To Scrubber Scrubber Slurry (£/ . 'Coal and Limestone Feed Supply A uxiliary Air Compressor Indicated Stream Sampled a Natural Gas Compressor Main Air Compressor Figure 1. Schematic of the Miniplant PFBC as it operated during the Level 1 environmental assessment with Level 1 sampling points indicated. lockhoppers from which solids are periodically dumped into metal drums. After leaving the third-stage cyclone, the flue gas expands through a converg- ing nozzle. A secondary source of high pressure air is metered through a ball valve with a pneumatic actuator and positioner. Superimposing this sec- ondary flow of air on the primary flow of flue gas through the nozzle, maintains gas pressure in the combustor at the desired level, typically 950 kPa (9.5 atm). During the Level 1 tests, the EPA mobile electrostatic precipitator was used to remove additional paniculate from the cooled, depressurized flue gases. This experiment was conducted because the final paniculate concen- tration of 0.03 to 0.15 g/Nm3 might be adequate for process performance, but emissions would need to be limited to 13 ng/J (about 0.035 g/Nm3) to meet Federal New Source Performance Standards for utility boilers. Hot flue gases from the regenerator pass through a cyclone to remove entrained particles Next the gases are cooled from 930°C (1700°F) to about 200°C (390CF) in a water-cooled heat exchanger. Gases are depressurized before entering a scrubber for final cleanup before venting to the atmos- phere. Operating Conditions Combustor and regenerator operating conditions during the EPA tests are listed in Table 2 Champion coal (with a sulfur content of 1.7 percent) andGrove limestone were used. It was necessary to feed significant quantities of fresh limestone to compensate for elutnation and to maintain the bed in the com- bustor. Because high sulfur coal was not available, the resultant Ca/S ratio was 1.29, much higher than desirable for commercial regenerative operation. Also, system pressure was 700 kPa (7 atm), instead of the normal 950 kPa (9.5 atm), to achieve adequate fluidizing velocities in the regenerator. Because the pressure was 30 percent lower than previous experimental runs, coal feed rate was reduced to maintain the desired excess air at the specified fluidizing velocity. Sampling and Analytical Methodology Sarppling Techniques Six solid streams were sampled at the Miniplant: two feed streams and four waste streams. Samples for chemical and most biological analyses were collected every 2 hours during the flue gas sampling. All solid samples were split for organic and inorganic analysis. The individual organic and inorganic samples were each composited during the test run to provide a representative sample of each solid stream To provide samples of the combustor flue gas and the regenerator offgas for Level 1 Environmental Assessment analysis, the Source Assessment Sampling System (SASS) was used to collect samples of the paniculate and gaseous components of each indicated gaseous stream. The SASS tram collects particles in a series of three cyclones with nominal ------- Table 1. Summary of Stream Sample Characteristics Sample Point Identification No. Stream Description Physical State Collected By Important Characteristics 1 Diluted combustor flue gas (cooled) Gas (ESP hopper catch) and solid 2 Undiluted combustor flue gas (hot) Gas 3 Regenerator flue gas (cooled) Gas 4 High pressure dilution air Gas 5 Solids from regenerator cyclone Solid 6 Spent combustion bed solids Solid 7 Solids from second combustor cyclone Solids from third combustor cyclone 9 10 11 Cool feed Sorbent feed Scrubber slurry Solid Solid Solid Solid Liquid GCA Fly ash entrained in combustion gases, particle concer tration about 0.15 g/Nm3, mass median particle sizi below 5 cm. Temperature 175°C (350°F), pressure 13 kPa (5 psig). GCA Similar to (1) but temperature is 750°C (1500°F) and pressure is 700 kPa (7 atm). GCA Sorbent particles entrained in off gases, low particle loading, temperature and pressure similar to (1). GCA Compressor output containing organic residue from lubricating oil, pressure is 700 kPa (7 atm). Exxon No special characteristics. Exxon Solids stream containing spent sorbent and some botton ash, discharge temperature approximately 900° C (1700°F). Exxon Stream contains fly ash, particles of mass median diameter approximately 17 cm, temperature approxi- mately 150 to 300°C (300 to 600°F). Exxon Stream contains fly ash, particles of mass median diameter approximately 4 cm, temperature approximatel 150 to 300°C (300 to 600°F). Exxon No special characteristics. Exxon No special characteristics. Exxon Liquid stream containing fly ash from stream 3 to condensed compounds, also ammonia, temperature 25 tc 40°C (70 to 100°F). cut points of 10 /urn, 3/um, and 1 /urn. A 150-mm filter collects the particles that are less than 1 /urn in diameter. The volatile organics are captured by 150 g of XAD-2 resin in a temperature- controlled trap. A series of impingers follows the resin trap to capture volatile metals. Setup and performance of the SASS train followed Level 1 specifi- cations. The SASS train samples of the diluted combustion flue gas (stream 1) were obtained from a temporary duct leading to the mobile ESP. Samples were collected on May 3 and 4, 1979. Because organic contamination of the diluted combustor flue gas by the compressed air used for dilution was suspected, additional sampling was conducted before dilution (stream 2). The SASS train cyclones, filter, and oven were not used at this sampling location because the Balston filter in the sample treatment system had already collected the particulates. The Balston filter operated at 260°C (500°F). A SASS train organic module was used to collect volatile and nonvolatile organic species. Sampling was accomplished by connecting a flexible stainless steel line to the existing metering valve. The regenerator flue gases were also sampled with the SASS train. Sampling was conducted at approximately iso- kinetic conditions in the center of the 6.4cm (2.5 in.) i.d. pipe transporting the regenerator flue gases. Sampling was conducted on May 2 and 3, 1979. A small resin trap containing 25 g of clean XAD-2 was used to collect organics in the dilution air. For sample collection, the resin trap was adapted t< a glass EPA Method 5 sampling train The sampling train was attached to ar existing tap on the compressed ai supply line. A metering valve was use< to control the sample flow rate am reduce the pressure to acceptable levels. The samples were recovered ty transferring the XAD-2 to an ambei glass jar and then rinsing the resin trap with methylene chloride (distilled-in glass grade). Gaseous components of the Mini plant flue gas streams were sampled fo subsequent analysis using a combina tion of continuous withdrawal, gral: sampling, and special impinger trair techniques. Analyses were conductec ------- Table 2. Summary of Miniplant PFBC Operating Conditions Parameter Combustor Regenerator Length of run, hr Pressure. kPa Average bed temperature, °C Expanded bed height, m Superficial velocity, m/s Ca/S molar ratio Coal feed rate, kg/hr Coal type (percent S) Coal higher heating value, kJ/kg Coal size, mesh Sorbent feed rate, kg/hr Sorbent type Sorbent size, mesh Excess air, percent Flue gas oxygen content, percent 99 700 894 3.1 1.5 1.29 77 Champion (1 .7) 31,400 81 705 1010-1031 (oxidizing-reducing) 1.9 0.6-0.8 (oxidizing-reducing) 5.4 Grove limestone 8x25 46 4.1 Grove limestone 0.3 for CO, CO2, 02, N2, SO2, H2S, COS, CS2, ammonia, and cyanide. Grab samples of the four gaseous streams for low-boiling (< 100°C) organic analysis were obtained in evacuated 2-liter glass sampling bulbs. Inorganic fixed gas samples were obtained as integrated Tedlar bag samples. Exxon personnel provided a single sample of scrubber slurry for Level 1 testing. Analytical Techniques Inorganic constituents of Miniplant effluent stream samples were quanti- fied using a combination of instrumental and wet chemical techniques. The primary Level 1 inorganic analysis technique is spark source mass spectrometry, which provides sensitive detection limits for about 70 elements Interferences, such as variations in the ion source discharge conditions and the photoplate interpretation techniques used in Level 1, provide only semi- quantitative data accurate to within a factor of 2 or 3. Miniplant bulk solid streams, having the potential to be disposed of in a landfill or another area where leaching could occur, were subjected to inor- ganic analysis of both the solid material and laboratory-generated distilled water leachates. Atomic absorption spectrom- etry was used to accurately quantify selected elements in the leachates. The Level 1 test protocol attempts to identify the major organic compound classes within each sample stream tested. Methylene chloride extracts of the samples are analyzed. Qualitative and some quantitative data are gener- ated, using gravimetry, gas chromatog- raphy, liquid chromatography, infrared spectroscopy, and low resolution mass spectrometry. These Level 1 techniques, in general, do not provide data on specific compounds. Level 1 methods were supplemented with high per- formance liquid chromatography using fluorescence detection for poly nuclear aromatic compounds. Volatile organics (boiling points below 100°C) are separated into six boiling point ranges by onsite gas chromatog- raphy. Moderately volatile organics (boiling points 100 - 300°C), in methy- lene chloride extracts, are analyzed in the laboratory by gas chromatography. Flame ionization detection is used in both of the above cases. Nonvolatile organics (boiling points above 300°C) are measured by gravimetric methods in methylene chloride extracts. These organic concentration data provide some qualitative indication of the types of compounds that may be present. Level 1 liquid chromatographic (LC) separation was designed to separate samples into seven reasonably distinct classes of organic compounds and was applied to all samples that contained a minimum of 15 mg combined volatile and nonvolatile organics. A sample was placed on a silica gel liquid chromat- ographic column, and a series of eluants of sequentially increasing polarity were used to separate the sample into fractions for further analysis. Infrared analysis was used to deter- mine the functional groups in an organic sample or liquid chromatography frac- tion of a partitioned sample. The interpreted spectra provide information on functionality (e.g., carbonyl, aromatic hydrocarbon, alcohol, amine, aliphatic hydrocarbon, and halogenated organic). Level 1 bioassays are a cost-effective initial screening tool that indicates potential health or ecological effects. As such, the test results should be used to point out areas requiring further in- vestigation. Health effects tests con- sisted of the Ames test for mutagenicity, and mammalian cell cytotoxicity assays using rabbit alveolar macrophages (RAM) and Chinese hamster ovary (CHO) cells. Fathead minnows, daph- nids, and algae were used to test for acute ecological effects. Results Data Handling Criteria or standards for air, water, and solid waste pollutants are needed to properly determine the implications of test results. Federal standards exist for some pollutants, such as total particu- lates, NOX, and S02 in boiler flue gases. Federal criteria are also available to determine if a solid waste is considered hazardous. However, emission standards do not exist for most of the pollutants measured in this and other environ- mental assessment programs. IERL-RTP has developed a set of conservative Discharge Multimedia Environmental Goals (DMEGs). They are derived using models incorporating available exposure or recommendations data such as industrial Threshold Limit Values (TLV), NIOSH recommendations for worker exposure, drinking water criteria, results of toxicity experiments using animals, and EPA/NIOSH order- ing numbers or animal data on carcino- genicity. These goals are emission concentrations that are used in IERL- RTP research programs to provide perspective on potential environmental hazards, to provide direction for control technology 'research programs, and to rank emission streams for future investigation. These conservative goals are a screening tool to provide focus for further, more detailed investigation. The simplest model used to derive DMEG limits incorporates TLVs as air pollutant emission goals. Emission concentrations below the TLV are assumed to be safe, since dispersion usually produces ground-level concen- ------- trations lower than stack concentra- tions by a factor of 1000 or more. This dilution factor should, in general, provide adequate protection for chronic exposure of the general population. The other goals and models are based on similar but more complex (and, at times, more tenuous) extrapolations. Measured trace element concentra- tions for each Miniplant effluent stream sample were compared to their in- dividual DMEG specific for the media of interest (air, water, solid wastes). Elements in excess of their goals were "flagged," providing a mechanism to estimate potential hazards associated with emission of that stream. Such estimates may be made to reflect both human health and ecology. Elements in excess of their DMEG indicate a need for further investigation. Summary of Test Results Data generated from Level 1 analyses of Miniplant samples were of three general types: inorganic analysis rely- ing on spark source mass spectroscopy (SSMS), atomic absorption spectrometry (AA), or wet chemical techniques; organic analysis using gravimetry, liquid chromatographic separation, infrared spectrophotometry, or low resolution mass spectrometry (and onsite gas chromatography for gaseous streams); and bioassay results of specific health or ecological effects testing. Inorganic Data Table 3 summarizes inorganic ele- mental data for Miniplant samples. Data are from SSMS or AA for gaseous waste stream samples, solid stream samples, and laboratory-generated distilled water leachates. Measured concentra- tions were compared to their respective appropriate emission goals (DMEGs). Table 3 data show seven elements exceeding emissions goals in com- bustor flue gas. Flagging of these elements indicates a potential area for Level 2 investigation. However, Level 2 efforts would have to be preceded by validation of the Level 1 SSMS results. Some elemental concen-trations, especially Cr, Ni, and Fe, may have been high because of contamination from the stainless steel of the sampling train. Although four elements exceed their DMEG in regenerator flue gas, further analyses of this stream are unlikely. Regenerator flue gas would be treated Table 3. Summary of Inorganic Trace Element Data for Miniplant Samples Stream Description Number of Chemical Species >DMEG Identity of Chemical Species >DMEG Gaseous waste streams3 Regenerator flue gas 4 Combuster flue gas6 7 Solid streams0 Regenerator cyclone solids 14 ESP hopper ash 16 Second combustor cyclone 14 solids Third combustor cyclone 15 solids Spent combustion bed 4 material Laboratory-generated, distilled water leachatesd Regenerator cyclone solids 0 Second combustor cyclone solids 0 Third combustor cyclone solids 0 Spent combustion bed material 0 Coal feed 0 Sorbent feed 0 V, Cr, Ni, Rh P, Ca, V, Cr, Fe, Ni, As Be, Al, P, Ca. Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Cd A I, P, Ca. Ti, V, Cr. Mn, Fe. Ni. Cu, Zn, As, Se, Cd, Ba, Pb Al. P, Ca. Ti, V. Cr, Mn, Fe. Ni, Cu.Zn.As.Cd.Pb Al, P. Ca. Ti, V. Cr. Mn. Fe, Ni. Cu, Zn. As, Se, Cd, Pb Ca, P, Fe, Ni aAir DMEGs used for comparison. '"Results represent emissions for the total flue gas stream. Dilution air was not analyzed and is assumed not to contribute to the totals of inorganics analyzed. cLand DMEGs used for comparison. d Water DMEGs used for comparison. before venting to the atmosphere and thus does not represent a true emission stream. Bulk solid waste streams from the Miniplant PFBC were chemically evalu- ated in two ways. Solid samples were analyzed for trace elements by SSMS (AA for Hg and Sb) and compared to land DMEG emission goals. In addition, distilled water leachates were prepared, analyzed in a similar manner, and the results compared to water DMEGs. As seen in Table 3, numerous, albeit similar, trace elements exceeded their respective land DMEGs in all solids col- lected by the various control devices used at the Miniplant. Only four elements exceeded one or both land DMEGs for Spent Combustor Bed Material. When laboratory leachates of these bulk solid materials were pre- pared and analyzed, however, no element in any sample exceeded any discharge goal. In fact, most elemental concentrations in the leachates were more than two orders of magnitude below their goals. Based on these leachate data, leaching of potentially toxic species from disposed solid waste streams at the Miniplant would not appear to be a problem. Solid waste streams would, therefore, be at a lower priority for subsequent Level 2 analysis than would flue gas particles. Organic Data Samples from the Miniplant generally contained low levels of organic com- pounds compared to DMEGs and Level 1 organic analysis criteria. The SASS train organic module (XAD- 2 resin adsorbent extracted with ChfeClz) from the regenerator flue gas streams and the diluted combustor flue gas stream were the only samples analyzed that contained sufficient organic mate- ------- Table 4. Summary of Bioassay Results of Miniplant PFBC Samples Health Effects Tests Ecological Effects Tests Sample Description Scrubber slurry XAD blank Combustor flue gas - XAD Regenerator flue gas - XAD Fine SASS paniculate Coarse SASS paniculate SASS filter-control ESP hopper ash Regenerator cyclone Combustor bed material 2nd Cyclone catch 3rd Cyclone catch Ames RAM Mutagenicity* Cytotoxicity /V N + N + N + N + N N + Low Low Low Low Moderate CHO Cytotoxicity" _ - - High N N N N N N N N Fish (96-hour LCso) High N N N N N N N High High High Low Daphnids (48-hour LCscJ High N N N N N N N High High High Moderate Algae [ECscJ Moderate N N N N N N N High High High High *+/- = positive/negative mutagenic response; no detectable toxicity. b/V = not run for indicated sample. °- = negative CHO cytotoxicity response rial to require liquid chromatographic separation. Because organic concentra- tions were so low, the infrared spec- trometry and low resolution mass spectrometry analyses provided only general results that were of limited use Samples analyzed from the Miniplant generally contained such low levels of organic compounds that these data were interpreted as: 1. Initial Level 1 organic data were compiled, including totals for volatile species (TCO-total chro- matographable organics), non- volatile species (GRAV-gravimet- ric), and onsite GC spectra where applicable. 2. A survey was made of all DMEG values that have been adopted for organic compounds or classes of compounds (586 to date). 3 It was assumed that the total weight of organics present in the sample analyzed was representa- tive of one compound, as a worst case, and all species whose DMEG was lower than this total were listed This exercise resulted (for some samples) in a list of compounds of "potential concern " In other samples, this exercise resulted in eliminating organic compounds as an area of concern for future investigation. 4. These compounds were then re- viewed based on knowledge of process chemistry, operating conditions, and the available Level 1 bioassay results. This review eliminated some species that could not possjbly be present in these FBC emission streams. 5 A final list (on a stream-by-stream basis) of organic compounds of potential concern was compiled. Organic compounds of concern in Miniplant emission streams appear to be limited to polynucleararomatic(PNA) species that might be present in SASS tram samples (particles and XAD) from combustor and regenerator flue gases. Bioassay Data Results of testing Miniplant samples in the Level 1 bioassay screen are sum- marized in Table 4. Results are listed based on qualitative Level 1 bioassay response criteria, except Ames results, which are listed as positive/negative. Five samples were positive (muta- genic) in the Ames test. Except for the third cyclone catch, all streams exhibited low toxicity to RAM cells. Regenerator flue-gas XAD extract was the only sample toxic to CHO cells. Regenerator cyclone catch leachate, spent combus- tion bed material leachate, and second cyclone catch leachate all exhibited high toxicity in all ecological effects tests Third cyclone catch leachate was variably toxic in these tests depending on the organism exposed. The toxicity. found in the ecological tests is probably attributable to high pH. The resulting three sets of data from Level 1 analysis for each tested stream from the Miniplant PFBC were com- pared Inorganic species that were flagged as exceeding one of their emission goals, organic species of potential concern possibly present in a sample (as determined above), and the response of a sample in the Level 1 battery of biological tests were all considered in making the final evalua- tion of which streams should receive priority for level 2 analysis. Radioassay of Miniplant Samples Multimedia samples collected during the May 1979 Level 1 sampling program at the Miniplant were analyzed for selected radioisotopes. Radioisotope emissions data from FBC are required ------- by the EPA's Office of Radiation Programs to evaluate the need, if any, for emissions limitations or other standards or criteria as instructed by the Clean Air Act Amendments. Also, these data serve as an initial effort toward incorporation of radioactivity (as an environmental pollutant) into the en- vironmental assessment methodology developed by the EPA Office of Research and Development through IERL-RTP. Seven solid samples were analyzed. Coal and sorbent feedstocks were analyzed for isotopic uranium (234U, 2351J, 238U) and isotopic thorium (228Th, 230Th). ESP hopper ash was not available m sufficient quantity to permit analysis for thorium isotopes but was analyzed for isotopic uranium, 226Ra, 228Ac, 210Pb, and 210Po. Regenerator cyclone solids, solids captured by second and third combustor cyclones, and spent bed material were assayed for all nine isotopes. Data indicate that most of the radio- isotopes leave the system as part of the second and third combustor cyclone catches. Radioisotopes escaping the plant in the Miniplant flue gases or in a commercial FBC facility would probably be 1 - 20 percent of those measured in the ESP hopper catch. R. J. Kindya, R. R. Hall. G. T. Hunt, W. Piispanen, and P. F. Fennelly are with GGA/Technology Division, Bedford, MA 01730. John 'O. Mi/liken is the EPA Project Officer (see below). The complete report, entitled "Environmental Assessment: Source Test and Evaluation Report—Exxon Miniplant Pressurized Fluidized-Bed Combustor with Sorbent Regeneration," (Order No. PB82-196 858; Cost: $ 18.00, subject to change) will be available only from: National Technical Information Service 5285 Port Royal Road Springfield, VA22161 Telephone: 703-487-4650 The EPA Project Officer can be contacted at: Industrial Environmental Research Laboratory U.S. Environmental Protection Agency Research Triangle Park, NC 27711 United States Environmental Protection Agency Center for Environmental Research Information Cincinnati OH 45268 Postage and Fees Paid Environmental Protection Agency EPA 335 Official Business Penalty for Private Use S300 ------- |