Compositions of Particles from Selected Sources in

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Compositions of Particles from Selected Sources in Philadelphia for Receptor Modeling Applications I. Olmez , A. E. Sheffield , G. E. Gordon , J. E. Houck , L. C. Pritchett , J. A. Cooper , T. G. Dzubay & R. L. Bennett To cite this article: I. Olmez , A. E. Sheffield , G. E. Gordon , J. E. Houck , L. C. Pritchett , J. A. Cooper , T. G. Dzubay & R. L. Bennett (1988) Compositions of Particles from Selected Sources in Philadelphia for Receptor Modeling Applications, JAPCA, 38:11, 1392-1402, DOI: 10.1080/08940630.1988.10466479 To link to this article: http://dx.doi.org/10.1080/08940630.1988.10466479

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•JAPCA 38:1392-1402 (1988)

Compositions of Particles from Selected Sources in Philadelphia for Receptor Modeling Applications I. Olmez, A. E. Sheffield, and G. E. Gordon University of Maryland College Park, Maryland

J. E. Houck, L. C. Pritchett, and J. A. Cooper NEA, Inc. Beaverton, Oregon

T. G. Dzubay and R. L. Bennett

Downloaded by [196.40.112.53] at 23:07 29 January 2016

U.S. Environmental Protection Agency Research Triangle Park, North Carolina

As a part of a receptor model study of the Philadelphia, PA atmosphere, particulate samples were collected from seven air pollution sources In the area: two oil-fired power plants, a coalfired power plant, a fluidized catalytic cracker, a refuse incinerator, a secondary aluminum smelter and an antimony ore roaster. Samples were collected In two size fractions with a dilution source sampler connected to a modified dichotomous sampler. Masses of collected material were determined gravlmetrlcally. Samples were analyzed for elements by x-ray fluorescence followed by Instrumental neutron activation analysis of some samples. Other samples were analyzed by chemical methods for volatile and nonvolatile carbon, SO42~ and NH 4 + . Data are presented for up to 46 elements and species on fine (42~ from oilfired plants could, thus, account for about 4 percent of ambient SCV", and a greater fraction in winter, when ambient concentrations are lower. Multiple linear regressions of ambient SC>42~ vs. Se and V or Ni indicate that about 16 percent of the SO42~ is from oil combustion20; however, this figure includes secondary SO42~ mostly formed during long transport times from distant plants. Refuse Incinerator

Enrichment factors for selected elements on fine and coarse particles from the incinerator are compared with those from three and two other U.S. incinerators, respectively, in Figure 4. Only a few of the elements shown (Si, Ca, V, Fe) plus a number of lithophile elements not shown are essentially unenriched on particles released by incinerators. Many elements have enormous EF values, especially S, Cl, Zn, Br, Ag, Cd, Sn, Sb and Pb. As discussed by Greenberg et al.,21 EFs of Zn, Ag, Cd, Sn, In and Sb are so large that a small mass contribution from incineration can supply major fractions of their urban airborne concentrations. Emissions from incinerators are dominated by Cl (mainly from combustion of plastics) and metals that form volatile chloJAPCA


rides. Some of the metals probably originate from the cans and other metallic objects, e.g., Zn, Cd, Ni, Cr, Sn, etc. Some metals such as Zn and Cd are also additives in plastics or rubber. Before incinerators had been studied, it was generally assumed that, because of variations of the composition of refuse, there would be large variations of composition of emitted particles versus time at a particular incinerator, and from one incinerator to another. However, studies of three incinerators, two in the Washington, D.C. area and one in Chicago, by Greenberg et al., revealed that there is generally less variability of composition of particles from refuse combustion than of that from other major sources such as coal- and oil-fired power plants.21-22 Comparisons of EF values in Figure 4 show that the Philadelphia incinerator releases particles of composition quite similar to those of the other U.S. incinerators previously studied. In Table VI we compare absolute compositions of particles of all sizes released by the Philadelphia incinerator with those from three other U.S. incinerators21-22 and seven in Japan.23 The agreement is remarkable for many of these elements and there is also agreement that the major elements released are Na, Cl, K, S, Ca, Zn and Pb. Presumably because of differences in composition of discardible consumer products in Japan, there are some significant differences for their incinerator emissions: greater amounts of S, K, Co and Cu and smaller amounts of Zn, Cd, Sn, Sb and Pb are released in Japan. Secondary Aluminum Plant

The only comparable study of which we are aware are measurements on four Al melting furnaces by Mamuro et al.,23 which are listed in Table VII, along with our results. While there is general agreement on the orders of magnitude of concentrations of various elements, there is not detailed agreement as for incinerators. Japanese plants use oil heat to melt the Al, accounting for the greater concentrations of V and Ni. As secondary Al smelters employ cryolite baths (NaCl, KC1 and NasAlFe) as a flux to prevent oxidation, it is not surprising that the emissions consist largely of Na, K and Cl and, probably F, although the latter was not measured. Other metals may arise as impurities in the scrap Al used at the plants, which would account for the substantial disagreements with the Japanese data for minor and trace elements. We also show the composition of baghouse dust from a U.S. West Coast secondary Al smelter.24 In general, the composition is in agreement November 1988

Volume 38, No. 11

with our measurements at the Philadelphia plant, but the baghouse data confirm the expected high F concentration. Antimony Roaster

We are aware of no other data on emissions from Sb roasters. Assuming that the emitted Sb is in the form of Sb2C>3, the oxide would account for about 90 percent of the particulate material released. Small amounts of C and S account for much of the balance. Conclusions

Composition profiles of particles from the seven sources studied have been used in CMB treatments of ambient concentrations of the same species determined simultaneously with these studies.20 However, the data reported here should have much wider applicability to receptor model studies in other areas that have some of the same sources. By combining XRF, INAA, thermal carbon analysis, wet chemical methods (including ion chromatography and the indophenol blue method), we obtained data for up to 46 species on fine and coarse particles, which are often chemically quite different. The size separation plus the measurement of so many species increased the chances of identifying some which are good markers for certain sources, e.g., the rare earths for the catalytic cracker. The use of so many species in research on source apportionment does not necessarily mean that all of them will need to be measured in field applications when these approaches are fully developed, as many of them may provide little useful information. The use of the dilution sampler should yield samples more appropriate for field use than those collected directly from hot stacks. However, except for S on fine particles from the coal-fired plant, differences from previous studies were not obvious, perhaps because pollution controls at some sources studied were not operating properly. Further studies of changes during dilution and cooling of plumes should be made by airplane collections in plumes or wind-trajectory analysis.25 Acknowledgments

We thank the operators of the sources studied for their permission to conduct the study and for cooperation of their staffs during sample collection. We are grateful to Robert K. Stevens and Kenneth T. Knapp of EPA for their help in planning the Philadelphia project and for their enthusiastic encouragement. We thank James E. Howes, Jr. and William Baytos of Bat-

telle-Columbus Laboratory for coordination of field tests and arrangements with plant operators, and Mark Mason and Margaret Beaman for performing carbon and ion analyses. The University of Maryland group thank the staff of the National Bureau of Standards reactor for their help during irradiations. Computer time at the University of Maryland was provided (in part) by the Maryland Computer Science Center. The work at Maryland was supported in part by the U.S. Environmental Protection Agency through Cooperative Agreement No. CR-806263. Although some of the research described in this article has been conducted at the U.S. Environmental Protection Agency, it has not been subjected to Agency review and, therefore, does not necessarily reflect the views of the Agency, and no official endorsement should be inferred. Mention of commercial products and company names does not constitute endorsement by the Agency. References

1. J. E. Houck, J. A. Cooper, E. R. Larson, "Dilution Sampling for Chemical Receptor Source Fingerprinting," in Proceedings of the 1982 APCA Annual Meeting, New Orleans, LA, Paper No. 82-61M.2. 2. J. D. McCain, A. D. Williamson, "Development and Evaluation of Dilution Probes Used for Sampling to Determine Source Signatures," Southern Research Institute Report No. SORI-EAS-83201,1983. 3. W. H. Zoller, G. E. Gordon, "Instrumental neutron activation analysis of atmospheric pollutants utilizing Ge(Li) yray detectors," Anal. Chem. 42: 257 (1970). 4. J. M. Ondov, W. H. Zoller, I. Olmez, N. K. Aras, G. E. Gordon, L. A. Rancitelli, K. H. Abel, R. H. Filby, K. R. Shah, R. C. Ragaini, "Elemental concentrations in the National Bureau of Standards' environmental coal and fly ash Standard Reference Materials," Anal. Chem. 47:1102 (1975). 5. M. S. Germani, I. Gokmen, A. C. Sigleo, G. S. Kowalczyk, I. Olmez, A. Small, D. L. Anderson, M. P. Failey, M. C. Gulovali, C. E. Choquette, E. A. Lepel, G. E. Gordon, W. H. Zoller, "Concentrations of elements in the National Bureau of Standards Bituminous and Subbituminous Coal Standard Reference Materials," Anal. Chem. 52: 240 (1980). 6. E. S. Gladney, C. E. Burns, D. R. Perrin, I. Roelandts, T. E. Gills, "1982 compilation of elemental concentration data for NBS biological, geological and environmental Standard Reference Materials," NBS Special Publ. No. 260-88, National Bureau of Standards, Gaithersburg, MD, March, 1984. 7. R. K. Stevens, W. A. McClenny, T. G. Dzubay, M. A. Mason, W. J. Courtney, "Analytical methods to measure the carbonaceous content of aerosols," in Particulate Carbon: Atmospheric Life Cycle, G. T. Wolff, R. L. Klimish, eds., Plenum Publ. Co., New York, 1982, pp. 111-129. 8. P. R. Bevington, Data Reduction and Error Analysis for the Physical Sciences, McGraw-Hill, New York, 1969, p. 73. 1401


9. P. K. Hopke, Receptor Modeling in Environmental Chemistry, Wiley-Interscience, New York, 1985. 10. G. E. Gordon, W. H. Zoller, G. S. Kowalczyk and S. W. Rheingrover, "Composition of source components needed for aerosol receptor models," in Atmospheric Aerosol: Source/Air Quality Relationships, E. S. Macias and P. K. Hopke, eds., Amer. Chem. Soc. Symp. Ser. #167,1981, pp. 51-74. 11. K. H. Wedepohl, "Chemical fractionation in the sedimentary environment," in Origin and Distribution of the Elements, L. H. Ahrens, ed., Pergamon Press, London, 1968, pp. 999-1016. 12. D. F. S. Natusch, J. R. Wallace, C. A. Evans, Jr., "Toxic trace elements: Preferential concentration in respirable particles," Science, 183:202 (1974). 13. A. E. Sheffield, G. E. Gordon, "Variability of particle composition from ubiquitous sources: results from a new source composition library," in Receptor Methods, Apportionment: Real World Issues and Applications, T. G. Pace, ed., APCA, Pittsburgh, PA, 1985, pp. 922. 14. D. N. Wallace, in Industrial Applications of Rare Earth Elements, K. A. Gschneidner, American Chemical Society Symposium Series # 164, Washington, DC, 1981, p. 101. 15. I. Olmez, G. E. Gordon, "Rare earths: atmospheric signatures for oil-fired power plants and refineries," Science 229:966(1985).

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16. M. E. Kitto, private communication, Univ. of Maryland, College Park, MD (1987). 17. A. Mizohata, "Rare earth elements in atmospheric aerosol particles and their sources," J. Aerosol Res. (Japan) 1: 274 (1986). 18. R. A. Cahill, "A Study of the Trace Element Distribution in Petroleum," M. S. Dissertation, Dept. of Chemistry, University of Maryland, College Park, MD, 1974. 19. K. R. Shah, R. H. Filby, W. A. Haller, "Determination of trace elements in petroleum by neutron activation analysis," J. Radioanal. Chem. 6: 185-192 (1970); ibid. 6,413-422 (1970). 20. T. G. Dzubay, R. K. Stevens, G. E. Gordon, I. Olmez, A. E. Sheffield, W. Courtney, "A composite receptor method applied to Philadelphia aerosol," Environ. Sci. Technol. 22:46 (1988). 21. R. R. Greenberg, W. H. Zoller, G. E. Gordon, "Composition and size distributions of particles released in refuse incineration," Environ. Sci. Technol. 12:566(1978). 22. R. R. Greenberg, G. E. Gordon, W. H. Zoller, R. B. Jacko, D. W. Neuendorf, K. J. Yost, "Composition of particles emitted from the Nicosia municipal incinerator," Environ. Sci. Technol. 12: 1329 (1978). 23. T. Mamuro, A. Mizohata, T. Matsunami, Y. Matsuda, "Non-destructive Multielement Analysis of Airborne Particles by Means of Instrumental Neu-

tron Activation Method," Report of the Radiation Center of Osaka Prefecture, Osaka, Japan, March 1981. 24. J. E. Houck, unpublished data, 1985. 25. S. W. Rheingrover, G. E. Gordon, "Wind-trajectory method for determining compositions of particles from major air-pollution sources," Aerosol Sci. Technol. 8: 29 (1988).

I. Olmez is now with the Massachusetts Institute of Technology, Nuclear Reactor Laboratory, Cambridge, MA 02139. A. E. Sheffield is now with Allegheny College, Department of Chemistry, Meadville, PA 16325. G. E. Gordon is with the Department of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742. J. E. Houck, and L. C. Pritchett are now with Omni Environmental Services, Inc., 10950 S.W. 5th Street, Suite 160, Beaverton, OR 97005. J. A. Cooper is with NEA, Inc., 10950 S.W. 5th Street, Suite 380, Beaverton, OR 97005. T. G. Dzubay and R. L. Bennett are with the U.S. Environmental Protection Agency, Research Triangle Park, NC 27711. This paper was submitted for peer review October 9, 1986; the revised manuscript was received May 4, 1988.

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