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.     

Structural-functional organization of lower vegetation layers in tree communities of the upper timberline ecotone in the Polar Urals

Typologically identical (dwarf birch-herb-dwarf shrub-moss) open and closed larch forests growing on the same altitudinal transect have proved to differ in the structural-functional organization of lower vegetation layers. Coverage, general species composition, and species richness of the herb-dwarf shrub layer are higher in the open forest than in the closed forest. Correlations between individual species of vascular plants weaken upon transition from the open to the closed forest. Conversely, the coverage of the lichen-moss layer increases in the closed forest, which contributes to its role as a factor of selection of vascular plant species against the background of the prevailing influence of the tree layer.     

Ecogenetic features and functions of solods in transural forest-steppes (within Sverdlovsk Oblast)

Specific ecogenetic features of solods in the forest-steppe zone has been studied, and the role of biotic and abiotic factors of soil formation has been estimated. Differentiation of soil horizons with respect to the physical clay fraction accounts for specific features of their moistening, which is reflected in the ratio of strongly and weakly crystallized forms of iron. Periodic changes in redox conditions results in iron segregation, and a high content of fulvic acids accounts for its eluvial migration. These processes are controlled by soil geochemical barriers.     

Reproductive parameters and disturbances of embryonic development in the fieldfare (<Emphasis Type="Italic">Turdus pilaris</Emphasis> L.) in the zone of impact from the nuclear fuel industry

The impact of emissions from the Siberian Chemical Plant (Tomsk oblast) on reproduction and embryonic development of the fieldfare was studied. Bird abundance, clutch size, and egg volume in the impact and background (control) zones were similar, but partial brood mortality in the impact zone proved to be significantly higher, and the frequency of embryonic pathologies (including developmental abnormalities) was also several times higher than in the control.     

Analysis of long-term changes in the dates of seasonal phenomena in plants and insects of the Il’men Reserve as related to climatic factors

The results of monitoring the dates of the onset of flowering and leaf budding in eight herbaceous and woody plant species and the first appearance of three insect species in the Il’men Reserve (1972–2005) were processed by means of regression and correlation analyses. No significant changes in test parameters were revealed in the majority of these species. Only two early spring plants, coltsfoot (Tussilago farfara L.) and goat willow (Salix caprea L.), showed a weak tendency toward earlier flowering in the 1980s and 1990s. This is explained primarily by the absence of any significant trends in spring and summer air temperatures in the study region over the observation period. On the other hand, interannual fluctuations in the dates of plant flowering and insect appearance were well manifested not only in early spring but also in late-spring species. These fluctuations proved to depend largely on spring temperatures: in years with early and warm springs, flowering and leaf budding in plants and the appearance of first individuals in insects were recorded on significantly earlier dates.     

Composition of pied flycatcher (<Emphasis Type="Italic">Ficedula hypoleuca</Emphasis> Pall.) nestling diet in industrially polluted area

The composition of pied flycatcher (Ficedula hypoleuca Pall.) nestling diet was studied in the zone of strong pollution with emissions from the Middle Ural Copper Smelter (Revda, Sverdlovsk oblast) and in the background area from 2005 to 2007. The results show that diversity of the diet decreases and prevalence in it of one insect taxon (Lepidoptera) increases near the source of emissions. The proportion of uncharacteristic food objects (orthopterans, herpetobiont invertebrates) and variation in the size of invertebrates brought by parents to their nestlings increase, which is explained by degradation of forest habitats in the polluted area. Pied flycatchers provide nestlings with sufficient quantities of food, but its quality in the polluted zone is lower than in the background area.     

Specific features of early stages of progressive succession in an anthropogenic landscape: An example from southeastern Belarus

Specific features of progressive succession in the vegetation of anthropogenically transformed landscapes in southeastern Belarus have been studied in permanent test plots. Using phytoindication scales proposed by Ellenberg (1974) and Tsyganov (1983), trends of changes in ecological conditions in the first years of succession have been revealed.     

On causes of gigantism in herbaceous plants

Landscape-geochemical features providing for manifestation of gigantism in herbaceous plants have been revealed in natural habitats in the south of Sakhalin and Kunashir islands. Tall herb assemblages have proved to be associated with geochemical landscapes characterized by reducing (gley or hydrogen sulfide) conditions and increased contents of petroleum hydrocarbons and some trace elements (total and movable forms). A hypothesis is put forward that gigantism in herbaceous plants is manifested in zones of active faults, which serve as a kind of conduits supplying endogenous heat, matter, and water to the root systems.