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Congress; Brasser, L. J., Mulder, W. C., E&.; Elsevier: The Hague, 1989; Vol. 2, p 87. (14) McLachlan, M.S.;Hutzinger, 0. In Organohdogen Compounds; Hutzinger, O., Fiedler, H., E&.; Eco-Informs Press: Bayreuth, Germany, 1990; Vol. 1, p 441.
(15) Umlauf, G.; Reischl, A.; Reissinger, M.; Richartz, H.;
Hutzinger, 0.;WeiBflog, L.i, Wenzel, K.-D.; Martinez, D. UWSF-Z. Umweltchem. Okotoxikol. 1990,2, 193. Received for review September 3, 1991. Revised manuscript received April 2, 1992. Accepted April 3, 1992.
Profile and Pattern of Monochloro- through Octachlorodibenzodioxins and -dibenzofurans in Chimney Deposits from Wood Burning Relner Bacher, Max Swerev, and Karlhelnz Ballschmlter*
Department of Analytical and Environmental Chemistry, University of Ulm, Albert-Einstein-Allee 11, D-7900 Ulm-Donau, Germany Chimney deposits from wood burning exhibit a homologue profile for the 135 chlorodibenzofurans (C1,DF) ( x = 1-8) and the 75 chlorodibenzodioxins(C1,DD) ( x = 1-8) close to that from flue gas from municipal waste incineration. The C1,DF dominate the C1,DD by the factor of 5-10 as do the lower chlorinated Cl,DD/Cl,DF ( x = 1-3) over the higher chlorinated ( x = 4-8). The content of Cl,DD/Cl,DF ( x = 4-8) in soot from wood burning was for the sum of chloro isomers in nanograms per kilogram in the range of 70-13400 (Cl,DF/Cl,DF) for the chlorodibenzofurans and 90-3900 (Cl,DD/Cl,DD) for the chlorodibenzodioxins. The C1,DD exhibit for the chloro isomers the typical "2,3"-pattern indicative of low-temperature burning. The widely used approach of analyzing environmental samples only for the tetra- through octachloro congeners omits valuable information given by the mono through trichloro congeners, particularly when the sources of the so-called baseline levels of dioxin pollution are under discussion. ~
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Introduction The formation of chlorodibenzodioxins (C1,DD) and -dibenzofurans (C1,DF) as part of the chemistry of incomplete combustion of wood, straw, gasoline, or oil has found little attention considering the extensive work concerning their formation in waste combustion. The contribution of the former source to the general pollution of dioxins is still an open question (1-4). Only recently has the contribution to the general pollution of halogenated dioxins and furans connected with automobile exhausts as a further incineration source been analyzed in detail, covering the full spectrum of halogenated dibenzodioxins (Ha1,DD) and dibenzofurans (Ha1,DF) ( x = 1-8) (5). The possibility of chlorodibenzodioxin formation in wood burning was first reported about a decade ago by Bumb et al. (I), who analyzed soot from a home fireplace. These results have been expanded in detail by Nestrick and Lamparski (2), analyzing for the tetrachloro- to octachlorodibenzodioxins. Their survey of chimney deposita from residential wood combustion in three different rural regions of the United States gave clear experimental evidence for the isomer pattern and the homologue profile for the tetra- to octachlorodibenzodioxins (Cl,DD, x = 4, 6-8). They found a typical exponential increase to the higher chlorinated dioxins, with octachlorodibenzodioxin as the most abundant congener. No data for C1,DF were 0013-936X/92/0926-1649$03.00/0
reported. Later Thoma (3) reported on the occurrence of both C1,DD and C1,DF as the sum of chloro isomers in ash from wood and oil burning. In his samples, the C1,DF dominated over the Cl,DD, which had a maximum for the pentachloro and hexachloro congeners. More recently Swerev (6) reported the homologue profile and the isomer pattern of C1,DD (x = 4-8) and C1,DF ( x = 4-8) from deposits in the upper part of a chimney which carried the smoke from an oven fed with wood and brown coal in a ratio 1:l. The C1,DD profile showed an exponential increase from the C14DD to the Cl,DD, while the C1,DF ( x = 4-8) had a maximum at x = 6, 7. Samples of coal soot from UK domestic coal fires have been analyzed for C1,DD and C1,DF ( x = 4-8) by Harrad et al. (7). The results indicate that domestic coal combustion is among the major sources of dioxins in the United Kingdom. Here we report the full spectrum of chloro homologue profiles and chloro isomer patterns of both the C1,DD ( x = 1-8) and C1,DF ( x = 1-8) of deposits in the upper part of a chimney of an old Suebian farmhouse in southern Germany. The chimney carries only the smoke from the oven to the outside. Only untreated wood has been used in the oven at a rate of about 5 m3per year over more than 10 years. Experimental Section
Sampling. The sample was taken from the inner surface of the chimney during the annual cleaning and inspection by the chimney sweep. Sample Preparation-Cleanup. See Scheme I. Gas chromatography with mass selective detection: equipment GC H P 5890, MSD 5970; column SP 2331,60 m, 0.32 mm id., 0.2 pm df; type of injection splitless/split; solvent n-nonane; injection port temperature 260 "C; temperature program 120 "C/3 min, 20 "C/min/l80 "C, 2 OC/min to 250 "C, 20 min. Masses monitored by MSD. C1,DF CllDF 202.0,204.0; ClzDF 236.0, 238.0; C13DF 270.0, 272.0; C1,DF 303.9, 305.9; C15DF 339.85, 341.85; C16DF 373.8, 375.8; C17DF 407.8, 409.8; C1,DF 441.75, 443.75. C1,DD: CllDD 218.0, 220.0; Cl2DD 252.0, 254.0; C13DD 286, 288.0; Cl4DD 319.9, 321.9; C15DD 355.85, 357.85'; C16DD 389.8, 391.8; C17DD 423.8, 425.8; C&DD 457.75, 459.75; [13C6]C14DD 325.9, 327.9; [13C12]C16DD 401.8, 403.8. Br,DF: Br,DF 245.95, 297.95; Br,DF 323-329, 325.9; Br,DF 403.8, 405.8. Br,Cl,DF:
0 1992 American Chemical Society
Environ. Sci. Technol., Vol. 26,
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