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691.
Mohammednoor Altarawneh Daniel Carrizo Artur Ziolkowski Eric M. Kennedy Bogdan Z. Dlugogorski John C. Mackie 《Chemosphere》2009,74(11):1435-1443
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. 相似文献
692.
The herbicide paraquat induces alterations in the elemental and biochemical composition of non-target microalgal species 总被引:1,自引:0,他引:1
Huge quantities of pesticides are dispersed in the environment, affecting non-target organisms. Since paraquat affects the photosynthetic process, the biochemical composition of affected species should be altered. The effect of paraquat on Chlamydomonas moewusii, a freshwater non-target species, was studied. After 48 h of herbicide exposure, growth rate, dry weight, and chlorophyll a and protein content were affected by paraquat concentrations above 0.05 μM. C/N ratio was also affected due to a decrease in nitrogen content in the dry biomass, while the carbon content remained constant for all paraquat concentrations assayed. Enzymes involved in nitrogen assimilation were affected by paraquat, being nitrate reductase activity more sensitive to paraquat than nitrite reductase. Based on the results obtained in the present study, paraquat exerts adverse effects upon a common freshwater green microalga, thus the application of this herbicide for weed control must be carried out very carefully, so that any disturbance affecting algae will have severe repercussions on higher trophic levels and on the elemental biogeochemical cycles. 相似文献
693.
Influence of titanium dioxide nanoparticles on speciation and bioavailability of arsenite 总被引:2,自引:0,他引:2
Sun H Zhang X Zhang Z Chen Y Crittenden JC 《Environmental pollution (Barking, Essex : 1987)》2009,157(4):1165-1170
In this study, the influence of the co-existence of TiO2 nanoparticles on the speciation of arsenite [As(III)] was studied by observing its adsorption and valence changing. Moreover, the influence of TiO2 nanoparticles on the bioavailability of As(III) was examined by bioaccumulation test using carp (Cyprinus carpio). The results showed that TiO2 nanoparticles have a significant adsorption capacity for As (III). Equilibrium was established within 30 min, with about 30% of the initial As (III) being adsorbed onto TiO2 nanoparticles. Most of aqueous As (III) was oxidized to As(V) in the presence of TiO2 nanoparticles under sunlight. The carp accumulated considerably more As in the presence of TiO2 nanoparticles than in the absence of TiO2 nanoparticles, and after 25-day exposure, As concentration in carp increased by 44%. Accumulation of As in viscera, gills and muscle of the carp was significantly enhanced by the presence of TiO2 nanoparticles. 相似文献
694.
Sorption of alkylphenols on Ebro River sediments: comparing isotherms with field observations in river water and sediments 总被引:1,自引:0,他引:1
Navarro A Endo S Gocht T Barth JA Lacorte S Barceló D Grathwohl P 《Environmental pollution (Barking, Essex : 1987)》2009,157(2):698-703
This study reports sorption isotherms of the endocrine disruptors nonylphenol (NP) and octylphenol (OP) in three sediment samples from the Ebro River basin (NE Spain), with organic carbon fractions (fOC) ranging from 0.0035 to 0.082 gOC g−1. All isotherms were fitted to the Freundlich model with slightly nonlinear exponents ranging from 0.80 to 0.94. The solubility of the compounds as well as the organic carbon (OC) content had the strongest influences on the sorption behavior of these compounds. Comparison of the laboratory-spiked samples with the native contamination of NP of 45 water and concurrent sediment samples resulted in reasonable matches between both data sets, even though the lowest concentrations in the field were not completely reached in laboratory tests. This good agreement indicates that sorption laboratory data can be extrapolated to environmental levels and therefore the distribution of nonylphenol between sediments and water can be predicted with a precision of one order of magnitude. Furthermore, laboratory experiments with simultaneous loading of NP and OP revealed negligible competition for sorption sites at low concentrations. 相似文献
695.
Study of lead phytoavailability for atmospheric industrial micronic and sub-micronic particles in relation with lead speciation 总被引:1,自引:0,他引:1
Particles from channelled emissions of a battery recycling facility were size-segregated and investigated to correlate their speciation and morphology with their transfer towards lettuce. Microculture experiments carried out with various calcareous soils spiked with micronic and sub-micronic particles (1650 ± 20 mg Pb kg−1) highlighted a greater transfer in soils mixed with the finest particles. According to XRD and Raman spectroscopy results, the two fractions presented differences in the amount of minor lead compounds like carbonates, but their speciation was quite similar, in decreasing order of abundance: PbS, PbSO4, PbSO4·PbO, α-PbO and Pb0. Morphology investigations revealed that PM2.5 (i.e. Particulate Matter 2.5 composed of particles suspended in air with aerodynamic diameters of 2.5 μm or less) contained many Pb nanoballs and nanocrystals which could influence lead availability. The soil-plant transfer of lead was mainly influenced by size and was very well estimated by 0.01 M CaCl2 extraction. 相似文献
696.
Spohn P Hirsch C Hasler F Bruinink A Krug HF Wick P 《Environmental pollution (Barking, Essex : 1987)》2009,157(4):1134-1139
Since the discovery of fullerenes in 1985, these carbon nanospheres have attracted attention regarding their physico/chemical properties. Despite little knowledge about their impact on the environment and human health, the production of fullerenes has already reached an industrial scale. However, the toxicity of C60 is still controversially discussed.The aim of this study was to clarify the biological effects of tetrahydrofuran (THF) suspended C60 fullerene in comparison to water stirred C60 fullerene suspensions. Beyond that, we analyzed the effects on the Crustacea Daphnia magna an indicator for ecotoxicological effects and the human lung epithelial cell line A549 as a simplified model for the respiratory tract.We could demonstrate that water-soluble side products which were formed in THF nC60 suspension were responsible for the observed acute toxic effects, whereas fullerenes themselves had no negative effect regardless of the preparative route on either A549 cell in vitro or D. magna in vivo. 相似文献
697.
Identifying natural and anthropogenic sources of metals in urban and rural soils using GIS-based data,PCA, and spatial interpolation 总被引:2,自引:0,他引:2
Harley T. Davis C. Marjorie Aelion Suzanne McDermott Andrew B. Lawson 《Environmental pollution (Barking, Essex : 1987)》2009,157(8-9):2378-2385
Determining sources of neurotoxic metals in rural and urban soils is important for mitigating human exposure. Surface soil from four areas with significant clusters of mental retardation and developmental delay (MR/DD) in children, and one control site were analyzed for nine metals and characterized by soil type, climate, ecological region, land use and industrial facilities using readily available GIS-based data. Kriging, principal component analysis (PCA) and cluster analysis (CA) were used to identify commonalities of metal distribution. Three MR/DD areas (one rural and two urban) had similar soil types and significantly higher soil metal concentrations. PCA and CA results suggested that Ba, Be and Mn were consistently from natural sources; Pb and Hg from anthropogenic sources; and As, Cr, Cu, and Ni from both sources. Arsenic had low commonality estimates, was highly associated with a third PCA factor, and had a complex distribution, complicating mitigation strategies to minimize concentrations and exposures. 相似文献
698.
Cristiano V.M. Araújo Fernando R. Diz Irene Laiz Luís M. Lubián Julián Blasco Ignacio Moreno-Garrido 《Environment international》2009,35(6):831-841
This study consisted of the sediment toxicity assessment of the Bay of Cádiz based on two endpoints: growth inhibition for Cylindrotheca closterium (benthic microalgae) and fecundity inhibition for Tisbe battagliai (harpacticoid copepod). A new methodology to eliminate (but not as storage technique) the autochthonous biota present in the sediment samples by immersing them in liquid nitrogen (? 196 °C) was also assessed. Sediment toxicity data showed different toxicity levels for both organisms. In general, T. battagliai was more sensitive; however a good correlation (r = 0.75; p < 0.05) between sediment toxicity results for both species was found. Data in pore water (pH, redox potential, and toxicity for microalgae and copepod) and sediment (pH, redox potential, organic carbon, and metal concentrations) demonstrated that ultra-freezing did not alter sample characteristics; thus, this technique can be adopted as a pre-treatment in whole-sediment toxicity tests in order to avoid misleading results due to presence of autochthonous biota. Multivariate statistical analysis such as cluster and principal component analysis using chemical and ecotoxicological data were employed. Silt and organic matter percentage and lead concentration were found to be the factors that explain about 77% of sediment toxicity in the Bay of Cádiz. Assay methodology determined in this study for both assayed species is considered adequate to be used in sediment toxicity monitoring programs. Results obtained using both species show that the Bay of Cádiz can be considered a moderately polluted zone. 相似文献
699.
The Almaraz nuclear power plant (Spain) uses the water of Arrocampo reservoir for cooling, and consequently raises the radioactive levels of the aquatic ecosystem of this reservoir. From July 2002 to June 2005, monthly samples of surface water, bulrushes (Typha latifolia) and carp (Cyprinus carpio) were collected from this reservoir. They were analyzed to determine the temporal evolution of the levels of 3H in surface water and of its transfer from the surface water to free-water in the tissues (TFWT) of the aforementioned two organisms. The tritium levels in the surface water oscillate with a biannual period, with their values in the study period ranging between 53 and 433 Bq/L. The incorporation of tritium to bulrushes and carp was fairly similar, the respective mean concentration factors being 0.74 and 0.8 (unitless, as Bq/L tissue water per Bq/L reservoir water). The temporal evolution of the levels fairly closely followed that observed for the surface water tritium, although detailed analysis showed the dominant periodicity for the bulrushes to be annual. This difference reflects the influence on the incorporation of tritium to bulrushes of diverse environmental and metabolic factors, especially evapotranspiration and the seasonal growth of this plant. 相似文献
700.
New best estimates for the solid–liquid distribution coefficient (Kd) for a set of radionuclides are proposed, based on a selective data search and subsequent calculation of geometric means. The Kd best estimates are calculated for soils grouped according to the texture and organic matter content. For a limited number of radionuclides this is extended to consider soil cofactors affecting soil–radionuclide interaction, such as pH, organic matter content, and radionuclide chemical speciation. Correlations between main soil properties and radionuclide Kd are examined to complete the information derived from the best estimates with a rough prediction of Kd based on soil parameters. Although there are still gaps for many radionuclides, new data from recent studies improve the calculation of Kd best estimates for a number of radionuclides, such as selenium, antimony, and iodine. 相似文献