title: Formation of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F) in fires of arsenic-free treated wood: role of organic preservatives.
abstract: This article demonstrates that biocidal organochlorines such as tebuconazole and permethrin, employed in formulations of wood preservatives, produce significant quantities of polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran (PCDD/F) when subjected to thermal decomposition under oxidative conditions. Both tebuconazole and permethrin form PCDD/F during gas-phase oxidation, but much greater yields occurred in the presence of surrogate ash corresponding to wood treated with copper-based fungicides. The significant yields have implications for the increased toxicity of PCDD/F emissions during fires of wood impregnated by combination of organic and copper-based preservatives. The oxidative pyrolysis of tebuconazole and permethrin over simulated wood ash generated amounts of PCDD/F exceeding those of untreated wood by 3 orders of magnitude. We obtained yields of 1000 ng WHO97-TEQ/g tebuconazole and 5500 ng WHO97-TEQ/g permethrin when reacting the organochlorines in an oxidizing atmosphere over surrogate wood ash. Gas-phase oxidation also produce measurable quantities of PCDD/F, corresponding to 1 ng WH097-TEQ/g tebuconazole and 36 ng WHO97-TEQ/g permethrin. In the case of tebuconazole, the present measurements correlate well with those obtained from oxidative pyrolysis of CBA-treated wood in the cone calorimeter. It appears that permethrin and tebuconazole provide phenyl and diphenyl precursors to formation of PCDD/F and both constitute a source of chlorine upon fragmentation.
authors.affiliation: Process Safety and Environment Protection Research Group, School of Engineering, The University of Newcastle, Callaghan, NSW 2308, Australia.
authors.forename: Nigel W
authors.initials: NW
authors.lastname: Tame
authors.forename: Bogdan Z
authors.initials: BZ
authors.lastname: Dlugogorski
authors.forename: Eric M
authors.initials: EM
authors.lastname: Kennedy
mesh_terms: D001151:Arsenic / Q000737:chemistry*; D001572:Benzofurans / Q000737:chemistry*; D000072338:Dibenzofurans, Polychlorinated; D017745:Incineration / Q000295:instrumentation / Q000379:methods*; D015394:Molecular Structure; D010084:Oxidation-Reduction; D000072317:Polychlorinated Dibenzodioxins / Q000737:chemistry*; D014934:Wood / Q000737:chemistry*
chemical_list: D001572:Benzofurans; D000072338:Dibenzofurans, Polychlorinated; D000072317:Polychlorinated Dibenzodioxins; D001151:Arsenic