Pyrolysis of permethrin and formation of precursors of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) under non-oxidative conditions

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 × 10¹⁵ 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 × 10¹² 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 °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.     

Simultaneous conversion of CHClF(2) and CH(3)Br to CH(2)CF(2)

Gas phase reaction of CHClF(2) with CH(3)Br in an alumina tube reactor at 773-1123 K as a function of various input ratios of CH(3)Br to CHClF(2) is presented. The major products detected include C(2)F(4), CH(2)CF(2), and CH(4). Minor products include CH(3)Cl, CHF(3), C(2)H(4), C(2)H(2), CH(2)CF-CF(3), and C(2)H(3)F. The reaction produces a high yield of CH(2)CF(2) (53% based on CHClF(2) feed) at 1123 K and an input molar ratio of CH(3)Br to CHClF(2) of 1.8, suggesting that the reaction potentially can be developed as a process to convert two ozone depleting substances (CHClF(2) and CH(3)Br) to a highly valuable chemical, CH(2)CF(2). The reaction of CHClF(2) with CH(3)Cl and CH(3)I was also investigated under similar reaction conditions, to assist in understanding the reaction chemistry involved in the reaction of CHClF(2) with CH(3)Br.     

The chemical basis of food detection in the lobster Homarus gammarus

A synthetic mixture of chemicals, based on the composition of an extract of squid muscle, has been developed, which is highly attractive for the lobster Homarus gammarus (L.). None of the components of this mixture was as attractive as the complete mixture, and substitution of D-amino acids for the natural L-forms also greatly reduced the attractiveness. This would indicate that several different types of chemosensory cell must be simultaneously stimulated to initiate exploratory feeding behaviour, and that a high degree of stereospecificity is involved. The results are discussed in the context of the wide range of food materials known to attract lobsters.     

Invasion patterns inferred from cytochrome oxidase I sequences in three bryozoans, Bugula neritina, Watersipora subtorquata, and Watersipora arcuata

Nucleotide variation in cytochrome c oxidase subunit I (COI) was used to examine population structure in three invasive bryozoans: Bugula neritina (Linnaeus, 1758), Watersipora subtorquata (d’Orbigny, 1852), and W. arcuata (Banta, 1969). These species are found on ship hulls and have a short (≤2 days) larval phase. Samples were collected from 1998–2001 at multiple sites in Australia, and in Hong Kong, New Zealand, Hawaii, California, Curaçao, and England. B. neritina is known to include three cryptic species, including species Type S (Davidson and Haygood in Biol Bull 196:273–280, 1999) which occurs on the east and west coasts of the USA. One haplotype recorded previously in the USA, S1, was found to be widespread, occurring throughout Australia and in Hong Kong, Curaçao, Hawaii, and England. W. subtorquata, a Caribbean–Atlantic species which has invaded southern Australia, New Zealand, and California, had low nucleotide diversity in these areas (π=0.0016±0.0014), consisting of three haplotypes connected by one or two nucleotide mutations. W. arcuata, an Eastern-Pacific native, had comparatively high diversity (π=0.0221±0.0115) in introduced populations from Australia and Hawaii. In each species, identical haplotypes were identified on separate coastlines providing evidence of widespread, rather than genetically independent, introductions. The major contrast in nucleotide diversity suggests that different propagule-source models explain introductions.     

Formation of toxic species and precursors of PCDD/F in thermal decomposition of alpha-cypermethrin

This article examines the thermal decomposition of alpha-cypermethrin, one of the most common pyrethroid pesticides. The objective was to identify its decomposition pathways and to gain an understanding into the formation of toxic species in the environment, including those that may behave in combustion systems, especially in fires in the environment, as precursors for PCDD/F (polychlorinated dibenzo-p-dioxins and dibenzofurans). The experiments were conducted under non-oxidative conditions using a tubular reactor housed in a three-zone heating furnace and operated with a dilute stream of alpha-cypermethrin in 99.999% nitrogen. The condensable products were identified and quantitated, after being collected in a cold solvent trap and in an activated charcoal cartridge. The study revealed the formation of pollutants including precursors of toxic PCDD/F such as diphenyl ether and phenol. It was also found that the decomposition of alpha-cypermethrin involved parallel pathways of an unusual vinylcyclopropane rearrangement-cum-aromatisation reaction transforming alpha-cypermethrin and a rupture of the C(O)OC(CN) linkage. The former is similar to that occurring in the decomposition of permethrin pesticide, whereas the latter constitutes a newly discovered channel for the formation of pollutants. Density functional theory (DFT) calculations allowed us to attribute the occurrence of the second pathway to the effect of the cyanide group in significantly weakening the OC bond.     

Geographic variation in tissue accumulation of endocrine disrupting compounds (EDCs) in grazing sheep

Muscle tissue was collected from ewes and lambs derived from farms throughout Scotland and sample concentrations of five endocrine disrupting compound groups were determined. Farms of origin were categorised according to geographic region. There were few statistically-significant differences with region or distance from cities. However, the magnitude of the difference between the highest and lowest mean values in ewe muscle from different regions exceeded 30% for 13 of the 15 compounds that were consistently detected in muscle, with animals derived from the industrialised region having the highest mean values for 11 of the 13 compounds. A less marked trend was apparent in the lamb muscle (8 of 13 highest were in the industrialised region). The physiological effects of such small differences in exposure to mixtures of pollutants remain to be determined.