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Zimmerman, P. R.; Greenberg, J. P.; Westberg, C. E. J . Geophys. Res., D 1988,93,1407-1416. Juttner, F. Chemosphere 1988,17,309-317. Petersson, G. Atmos. Environ. 1988,22,2617-2619. Arey, J.; Winer, A. M.; Atkinson, R.; Aschmann, S.M.; Long, W. D.; Morrison, C. L.; Olszyk, D. M. J. Geophys. Res., D, to be submitted for publication. Zimmerman, P. R.; Chatfield, R. B.; Fishman, J.; Crutzen, P. J.; Hanst, P. L. Geophys. Res. Lett. 1978,5,679-682. Lamb, B.;Guenther, A.; Gay, D.; Westberg, H. Atmos. Environ. 1987,21, 1695-1705. Chameides, W. L.; Lindsay, R. W.; Richardson, J.; Kiang, C. S. Science 1988,241, 1473-1475. Trainer, M.; Williams, E. J.; Parrish, D. D.; Buhr, M. P.; Allwine, E. J.; Westberg, H. H.; Fehsenfeld, F. C.; Liu, S. C. Nature 1987,329,705-707. Trainer, M.; Hsie, E. Y.; McKeen, S. A,; Tallamraju, R.; Parrish, D. D.; Fehsenfeld, F. C.; Liu, S.C. J. Geophys. Res., D 1987,92,11879-11894. Jacob, D. J.; Wofsy, S.C. J . Geophys. Res., D 1988,93, 1477-1486. Atkinson, R. J . Phys. Chem. Ref. Data, 1989,Monograph 1, 1-246.
Atkinson, R.; Aschmann, S.M.; Arey, J. Atmos. Environ., in press. Atkinson, R.; Aschmann, S. M.; Pitts, J. N., Jr. J . Phys. Chem. 1988,92,3454-3457. Dlugokencky, E.J.; Howard, C. J. J. Phys. Chem. 1989,93, 1091-1096. Atkinson, R.; Carter, W. P. L. Chem. Rev. 1984,84,437-470. Nolting, F.; Behnke, W.; Zetzsch, C. J. Atmos. Chem. 1988, 6, 47-59. Atkinson, R.; Hasegawa, D.; Aschmann, S.M. Znt. J. Chem. Kinet., in press.
Atkinson, R.; Aschmann, S. M.; Pitts, J. N., Jr. Znt. J. Chem. Kinet. 1986,18,287-299. Atkinson, R. Znt. J . Chem. Kinet. 1987,19,799-828. Atkinson, R.; Aschmann, S. M.; Carter, W. P. L. Znt. J. Chem. Kinet. 1983,15,1161-1177. Taylor, W. D.; Allston, T. D.; Moscato, M. J.; Fazekas, G. B.; Kozlowski, R.; Takacs, G. A. Znt. J . Chem. Kinet. 1980, 12,231-240. Atkinson, R.; Plum, C. N.; Carter, W. P. L.; Winer, A. M.; Pitts, J. N., Jr. J . Phys. Chem. 1984,88, 1210-1215. Ravishankara, A. R.; Mauldin, R. L., I11 J . Phys. Chem. 1985,89,3144-3147. Atkinson, R.; Aschmann, S. M.; Winer, A. M.; Pitts, J. N., Jr. Environ. Sci. Technol. 1985,19,159-163. Atkinson, R.; Plum, C. N.; Carter, W. P. L.; Winer, A. M.; Pitts, J. N., Jr. J. Phys. Chem. 1984,88, 2361-2364. Atkinson, R.; Aschmann, S.M. Znt. J . Chem. Kinet. 1988, 20,513-539. Atkinson, R.; Winer, A. M.; Pitts, J. N., Jr. Atmos. Environ. 1986,20,331-339. Logan, J. A. J. Geophys. Res., D 1985,90,10463-10482. Prinn, R.; Cunnold, D.; Rasmussen, R.; Simmonds, P.; Alyea, F.; Crawford, A.; Fraser, P.; Rosen, R. Science 1987, 238,945-950. Received for review January 29,1990.Revised manuscript received May 1, 1990. Accepted May 22, 1990. We gratefully acknowledge the National Science Foundation f o r support o f this research through Grant ATM8617884 (Project Monitor, Dr. Jarvis L. Moyers) and thank Ms. Sara M. Aschmann for her generous advice. This research was carried out as part of an undergraduate research project (S.B.C.)through the Department of Chemistry, University of California, Riverside.
Chlorinated Dibenzofurans and Dioxins in Atmospheric Samples from Cities in New York Robert M. Smith,' Patrick W. O'Keefe, Kenneth M. Aldous, Herman Valente, Stephen P. Connor, and Robert J. Donnelly Wadsworth Center for Laboratories and Research, New York State Department of Health, Box 509, Albany, New York 12201-0509
Chlorinated dibenzofurans and chlorinated dibenzo-pdioxins were detected in air samples from Albany, Binghamton, Utica, and Niagara Falls, NY, in concentrations ranging up to 8.8 pg/m3. The air results showed a variety of homologue distributions including a previously unreported one dominated by lower chlorinated CDFs, which may result following particulate fallout. Other results were more typical of urban and suburban air that is subject to the processes of atmospheric "aging" as reported in the literature. Introduction
Few studies have been conducted on chlorinated dibenzofurans (CDFs) and chlorinated dibenzo-p-dioxins (CDDs) in the atmosphere. These compounds are relatively stable global pollutants. They are emitted from many industrial and combustion sources (1-4) into the environment where they are transported by air (5-7), water, or the food chain (8) to sediments (5, 9-11), soils (12), and humans (13, 14). Municipal waste combustion (MWC) (15-18), hospital waste combustion (19),and automobile emissions (20, 21) have been shown to be significant sources of these compounds to the atmosphere. However, little progress has been made in evaluating the 1502
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relative contribution to the atmosphere from each of these sources since combustion processes produce similar isomer and homologue distributions (22-24) and even a given source may exhibit considerable pattern variability. The principal source of atmospheric contamination, if one exists, is still the subject of controversy. The search for other sources presently continues in an attempt to account for the quantities of these compounds that have been observed in the environment. Studies in 1986 showed that collecting air particles was inadequate for the more volatile lower chlorinated CDFs and CDDs (6, 25). Recent atmospheric studies in both Europe and North America used glass fiber filters followed by polyurethane foam (PUF) to collect particulate-bound and vapor-phase CDFs/CDDs respectively (7,26-33). In a long-term study, Eitzer and Hites found that temperature and vapor pressure were two key parameters that determined the phase in which a CDF/CDD congener was found in the atmosphere (34). Further, they presented data to support the hypothesis that an urban air mass with relatively uniform CDD/CDF concentrations is subject to wet and dry deposition processes that "age" it as it travels from an urban center, resulting ultimately in an altered congener pattern and deposition of CDFs/CDDs to sediments (35). On the basis of laboratory experiments, other
0013-936X/90/0924-1502$02.50/0
0 1990 American Chemical Society
Table I. Literature Comparison Data: CDF and CDD Results for Air, MWC Emissions, NBS Dust, and Sediment
Niagara Falls, NY, air," pg/m3 Niagara Falls, NY, air,* pg/m3 Bloomington, IN, air: pg/m3 tunnel air, FRG, pg/m3 MWC emissions? ng/dnm3 Siskiwit sediment, ppt NBS dust 1648; ng/g
ref
homologue group total concentration chlorinated dibenzo-p-dioxins chlorinated dibenzofurans tetrapenta- hexa- heptaoctatetra- penta- hexa- hepta-
7 7 6 26 15 10 40
0.02 0.98 0.006 0.22 36 26
