title: Pyrolysis of permethrin and formation of precursors of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) under non-oxidative conditions.
abstract: This article reports the computational and experimental results of the thermal decomposition of permethrin, a potential source of dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF). We have performed a quantum chemical analysis by applying density functional theory to obtain the decomposition pathways of permethrin and the formation mechanism of dibenzofuran. We have conducted the pyrolysis experiments in a tubular reactor and identified the pyrolysis products to demonstrate the agreement between the experimental measurements and quantum chemical calculations. The initiation of the decomposition of permethrin involves principally the aromatisation of permethrin into 3-phenoxyphenylacetic acid, 2-methylphenyl ester (J) and concomitant loss of 2HCl. This rearrangement is followed by the rupture of the O-CH2 linkage in J, with a rate constant derived from the quantum chemical results of 1 x 10(15) exp(-68 kcal/mol/RT)s(-1) for temperatures between 700 and 1300 K. This is confirmed by finding that the rate constant for unimolecular rearrangement of permethrin into J is 1.2 x 10(12) exp(-53 kcal/mol/RT)s(-1) over the same range of temperatures and exceeds the direct fission rate constant at all temperatures up to 850+/-120 degrees C as well as by the experimental detection of J prior to the detection of the initial products incorporating diphenyl ether, 1-methyl-3-phenoxybenzene, 3-phenoxybenzaldehyde and 1-chloromethyl-3-phenoxybenzene. As the temperature increases, we observe a rise in secondary products formed directly or indirectly (via phenol/phenoxy) including aromatics (naphthalene), biphenyls (biphenyl, 4-methyl-1,1'-biphenyl) and dibenzofuran (DF). In particular, we discover by means of quantum chemistry a direct route from 2-phenoxyphenoxy to naphthalene. We detect no polychlorinated dibenzo-p-dioxins and dibenzofurans. Unlike the case of oxidative pyrolysis [Tame, N.W., Dlugogorski, B.Z., Kennedy, E.M., 2007b. Formation of dioxins in fires of arsenic-free treated wood: Role of organic preservatives. Environ. Sci. Technol. 41, 6425-6432] where significant yields of both PCDD and PCDF were obtained, under non-oxidative conditions the thermal decomposition of permethrin does not form appreciable amounts of PCDD or PCDF and the presence of oxygen (and/or a sizable radical pool) appears necessary for the formation of dibenzo-p-dioxin itself or PCDD/F from phenol/phenoxy.
authors.affiliation: Process Safety and Environment Protection Research Group, School of Engineering, The University of Newcastle, Callaghan, New South Wales 2308, Australia.
authors.forename: Mohammednoor
authors.initials: M
authors.lastname: Altarawneh
authors.forename: Daniel
authors.initials: D
authors.lastname: Carrizo
authors.forename: Artur
authors.initials: A
authors.lastname: Ziolkowski
authors.forename: Eric M
authors.initials: EM
authors.lastname: Kennedy
authors.forename: Bogdan Z
authors.initials: BZ
authors.lastname: Dlugogorski
authors.forename: John C
authors.initials: JC
authors.lastname: Mackie
mesh_terms: D001572:Benzofurans / Q000138:chemical synthesis*; D008401:Gas Chromatography-Mass Spectrometry; D006358:Hot Temperature; D010084:Oxidation-Reduction; D026023:Permethrin / Q000737:chemistry*; D000072317:Polychlorinated Dibenzodioxins / Q000031:analogs & derivatives* / Q000138:chemical synthesis; D011789:Quantum Theory; D013816:Thermodynamics
chemical_list: D001572:Benzofurans; D000072317:Polychlorinated Dibenzodioxins; D026023:Permethrin; C023614:dibenzofuran