Respirable Aerosols from Fluidized Bed Coal Combustion. 3. Elemental Composition of Fly Ash Suzanne H. Welssman,t Robert L. Carpenter,* and George J. Newton
Inhalation Toxicology Research Institute, Lovelace Biomedical and Environmental Research Institute, Albuquerque, New Mexico 87 185
m
Fluidized bed coal combustion is a promising technology for using coal in an environmentally acceptable manner. Trace elemental constituents in fly ash from an experimental atmospheric pressure fluidized bed combustor (AFBC) are reported and compared with pulverized-coal combustor (PCC) ash data and those from other fluidized bed combustors. Bulk and size-separated particles were collected and analyzed by using spark source mass spectrometry. Fluidized bed combustor ash was similar to PCC ash in minor and trace element composition. However, AFBC ash showed less size dependence of elemental composition than has been reported for PCC ash. Bulk particle elemental composition varied with sampling position within the effluent stream. Penetration of elements through each cleanup stage and elemental enrichment were a function of the cleanup stage and the element under consideration.
Observed trace and minor element concentrations in ash from an experimental atmospheric pressure fluidized bed combustor (AFBC) are reported as part of a series of studies to determine the inhalation toxicity of AFBC effluents. The initial phase of these studies, a portion of which is reported here, was to study effluents from AFBCs and to indicate areas needing future research. Details on the combustor sampling system, aerosol properties, ash surface chemistry, and organic emissions have been published (1-4). Our data are confined to respirable (i.e., 26" 1.1 2.7 1.4 1.2 5 3.8 6.9 6.1 5.6 0.84 2.7 3.2 2.9 0.65 2.6 0.61 3 .O 17" 2.0 2.8 2.4 1.2 >0.81 5.8 1.2 0.22 1.5 1.4 0.39 0.57-7.6 1.6 3.1 0.66 9.5" 0.97 0.57 0.3 1.2 0.90 1.4 2.1 0.71 3.3 0.36 1.9 3.5 0.42 0.99 2.0 1.0 0.44-0.54 5.6 0.81 47 93 63 27 54 32
11 5.1 10
18 9.4 5.0 9.4 5.0 3.6 4.3 6.2
10 2.6 5.8 6.6 11
11
< 15 15 6.1 12 4.3
18
For no element does the penetration differ significant-
ly from zirconium.
Due to the factors affecting AFBC fly ash elemental composition, extrapolation of concentration data for minor and trace elements to nationwide release levels or airborne concentrations is not warranted at this time. On the basis of this study of an experimental AFBC and reported values for other FBCs and PCCs, the elemental emissions from atmospheric pressure fluidized bed coal combustion and from conventional coal combustion technologies do not differ significantly. The elemental composition of ash from FBCs needs to be studied further to adequately assess the hazards, if any, of increased use of fluidized bed combustion. In particular, future work should concentrate on those elements that are considered to be very toxic (e.g., As, Sb, Be, Cr, Pb, Se, and T1) and those that are enriched or depleted in stack breech ash, spent bed material, and small particles (e.g., B, Bi, Co, F, I, S, Sc, and Tb).
Acknowledgments The authors gratefully acknowledge the efforts of J. J. Kovach, U. Grimm, and W. E. Wallace of METC, who assisted in this project, as well as the technical and editorial assistance of many members of the Inhalation Toxicology Research Institute staff including R. 0. McClellan, C. H. Hobbs, R. F. Henderson, W. R. Griffith, E. R. Peele, R.
Tamura, D. D. Horinek, and J. A. Stephens. Registry No. Sb, 7440-36-0;As, 7440-38-2;Ba, 7440-39-3;Bi, 7440-69-9;B, 7440-42-8; Ce, 7440-45-1;Cl,, 7782-50-5; Cr, 744047-3; Co, 7440-48-4;Dy, 7429-91-6;Er, 7440-52-0;Eu, 7440-53-1; Gd, 7440-54-2; Ge, 7440-56-4; Hf, 7440-58-6; Ho, 7440-60-0; I, 7553-56-2; La, 7439-91-0; Pb, 7439-92-1; Lu, 7439-94-3; Mn, 7439-96-5; Mo, 7439-98-7; Nd, 7440-00-8; Ni, 7440-02-0; Nb, 7440-03-1; P, 7723-14-0;K, 7440-09-7;Pr, 7440-10-0;Rb, 7440-17-7; Sm, 7440-19-9; Sc, 7440-20-2; Se, 7782-49-2; Ag, 7440-22-4; Na, 7440-23-5; Sr, 7440-24-6; Tb, 7440-27-9; Th, 7440-29-1; Tm, 7440-30-4;Sn, 7440-31-5;Ti, 7440-32-6;W, 7440-33-7;U, 7440-61-1; V, 7440-62-2; Yb, 7440-64-4; Y, 7440-65-5; Zn, 7440-66-6; Zr, 7440-67-7.
Literature Cited (1) Newton, G. J.; Carpenter, R. L.; Yeh, H. C.; Peele, E. R. Environ. Sci. Technol. 1980, 14, 849. (2) Carpenter, R. L.; Newton, G. J.; Rothenberg, S. J.; DeNee, P. B. Emiron. Sei. Technol. 1980, 14, 854. (3) Hanson, R. L.; Carpenter, R. L.; Newton, G. J.; Rothenberg, S. J. Environ. Sei. Health 1979, A14, 223. (4) Rothenberg, S. J.; DeNee, P. B.; Holloway, P. Appl. Spectrosc. 1980, 34, 549. (5) Task Group on Lung Dynamics, Health Phys. 1966,12,173. (6) Smith, R. D. Prog. Energy Combust. Sei. 1980,6,53-119. (7) Coles, D. G.; Ragaini, R. C.; Ondov, J. M.; Fischer, G. L.; Silberman, D.; Prentice, B. A. Environ. Sei. Technol. 1979, 13,455-459. (8) Block, C.; Dams, R. Environ. Sei. Technol. 1976,10,1011. (9) Natusch, D. F. S.; Wallace, J. R.; Evans, C. A., Jr. Science (Washington, D.C.) 1974, 183, 202. (10) Davison, R. L.; Natusch, D. F. S.; Wallace, J. R.; Evans, C. A., Jr. Environ. Sei. Technol. 1974, 8, 1107. (11) Klein, D. H.; Andren, A. W.; Carter, J. A.; Emery, J. F.; Feldman, C.; Fulkerson, W.; Lyon, W. S.; Ogle, J. C.; Talmi, Y.; Van Hook, R. I.; Bolton, N. Environ. Sei. Technol. 1975 9, 973. (12) Newton, G. J.; Raabe, 0. G.; Mokler, B. V. J. Aerosol Sei. 1977, 8, 339. (13) Gluskoter, H. J. In “Trace Elements in Fuel”; Babu, S. P., Ed., American Chemical Society: Washington, D.C., 1975; Adv. Chem. Ser. No. 141, pp 1-22. (14) Kuhn, J. K.; Fiene, F.; Harvey R. “Geochemical Evaluation and Characterization of a Pittsburgh Number 8 and a Rosebud Seam Coal; Illinois State Geological Survey Report, METC/CR-78/8, Morgantom Energy Technology Center, Morgantown, WV, 1978. (15) Tukey, J. W. “Exploratory Data Analysis”;Addison-Wesley Publishing Co.: Reading, MA, 1977. (16) Raabe, 0. G. J. Air. Pollut. Control Assoc. 1976,26,856. (17) Ngtional Bureau of Standards Certificate of Analysis for Standard Reference Material 1633: Trace elements in Coal Fly Ash; 1975.
(18) Ondov, J. M.; Zoller, W. H.; Olmez, I.; Arm, N. K.; Gordon, G. E.; Rancitelli, L. A.; Abel, K. H.; Filby, R. H.; Shah, K. R.; Ragaini, R. C. Anal. Chem. 1975, 47, 1102. (19) Kato, T. Trans. Am. Nucl. SOC.Supp. 1975,21, 8. (20) Owens, J. W.; Gladney, E. S. At. Absorpt. Newsl. 1976,15, 95. (21) Millard, H. T.; Swanson,,V. E. Trans. Am. Nucl. Sac. 1975, 21, 108. (22) Nadkarni, R. A. Radiochem.Radioanal.Lett. 1975,21,161. (23) Williams, J. M.; Hensley, W. K.; Wewerka, E. M.; Wanek, P. L.; Olsen, J. D. “Trace Element Distributions in Several Coal Conversion Processes-An Exchange Program Between the Los Alamos Scientific Laboratory and the National Coal Board of England”; LA-7100-MS, Los Alamos Scientific Laboratory, Los klamos, NM, 1978. (24) Masters, W.; Larkin, R. “Proceedings of the Fifth International Conference on Fluidized Bed Combustion, 111”; Bliss, C., Williams, B. M., Eds.; Mitre Corp.: McLean VA, 1977; 379. (25) Vogel, G. J.; Cunningham, P. T.; Hubble, W.; Lee, S.; Lenc, J.; Montagna, J.; Saxena, S.; Siegel, S.; Snyder, R.; Swift, W. M.; Jonke, A. A. “A Development Program on Pressurized Fluidized-Bed Combustion”; ANL/ES-CEN-1010, Argonne National Laboratory, Argonne, IL, 1975. (26) Stone, R.; Kahle, R. L. “Environmental Assessment of Solid Residues from Fluidized-Bed Fuel Processing”; Final Report, EPA-600/7-7&107 (or PB-282-940),NTIS, Springfield, VA, 1978. (27) Lyon, W. S. “Trace Elemental Measurements at the Coal-Fired Steam Plant”; CRC Press: Cleveland, OH, 1977. (28) Gladney, E. S.; Small, J. A.; Gordon, G. E.; Zoller, W. H. Atmos. Environ. 1976, 10, 1071. (29) Kaakinen,,J. W.; Jordon, R. M.; Lawasani, M. H.; West, R. E. Environ. Sei. Technol. 1975, 9, 862. (30) Swaine, D. J. In “Proceedings of the International Clean Air Conference: Clean Air-The Continuing Challenge”; White, E. T., Hetherington, P., Thiele, B. R., Eds.; Ann Arbor, MI, 1978, p 519. (31) Fisher, G. L.; Prentice, B. A.; Silberman, D.; Ondov, J. M.; Biermann, A. H.; Ragaini, R. C.; McFarland, A. R. Environ. Sei. Technol. 1978, 12, 447. (32) Murthy, K. S.; Howes, J. E.; Nack, H.; Hoke, R. C. Environ. Sci. Technol. 1979, 13, 197. (33) Smith, R. D.; Campbell, J. A.; Nielson, K. K. Environ. Sei. Technol. 1979, 13, 553. (34) Ondov, J. M.; Ragaini, R. C.; Biermann, A. H. Environ. Sei. Technol. 1979, 13, 598. (35) Ondov, J. M.; Ragaini, R. C.; Biermann, A. H. Environ. Sei. Technol. 1979, 13, 946.
Received for review December 15, 1980. Revised manuscript received March 8, 1982. Accepted August 23, 1982. Research performed under U.S. Department of Energy Contract No. DE-ACO4- 76EV01013.
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