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- Bidleman, TF, et al.
(författare)
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Air-soil and air-water exchange of chiral pesticides
- 2003
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Ingår i: ENVIRONMENTAL FATE AND EFFECTS OF PESTICIDES Book Series: ACS SYMPOSIUM SERIES. - 0097-6156. ; 853, s. 196-225
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Tidskriftsartikel (refereegranskat)abstract
- The enantiomers of chiral pesticides are often metabolized at different rates in soil and water, leading to non-racemic residues. This paper reviews enantioselective metabolism of organochlorine pesticides (OCPs) in soil and water, and the use of enantiomers to follow transport and fate processes. Residues of chiral OCPs and their metabolites are frequently non-racemic in soil, although exceptions occur in which the OCPs are racemic. In soils where enantioselective degradation and/or metabolite formation has taken place, some OCPs usually show the same degradation preference; e.g. depletion of (+)trans-chlordane (TC) and (-)cis-chlordane (TC), and enrichment of the metabolite (+)heptachlor exo-epoxide (HEPX). The selectivity is ambivalent for other chemicals; preferential loss of either (+) or (-)o,p'-DDT and enrichment of either (+) or (-)oxychlordane (OXY) occurs in different soils.Non-racemic OCPs are found in air samples collected above soil which contains non-racemic residues. The enantiomer profiles of chlordanes in ambient air suggests that most chlordane in northern Alabama air comes from racemic sources (e.g. termiticide emissions), whereas a mixture of racemic and non-racemic (volatilization from soil) sources supplies chlordane to air in the Great Lakes region. Chlordanes and heptachlor exo-epoxide (HEPX) are also non-racemic in arctic air, probably the result of soil emissions from lower latitudes.The (+) enantiomer of alpha-hexachlorocyclohexane (alpha-HCH) is preferentially metabolized in the Arctic Ocean, arctic lakes and watersheds, the North American Great Lakes and the Baltic Sea. In some marine regions (Bering and Chukchi seas, parts of the North Sea) the preference is reversed and (-)alpha-HCH is depleted. Volatilization from seas and large lakes can be traced by the appearance of non-racemic alpha-HCH in the air boundary layer above the water. Estimates of microbial degradation rates for alpha-HCH in the eastern Arctic Ocean and an arctic lake have been made from the enantiomer fractions (EFs) and mass balance in the water column. Apparent pseudo first-order rate constants in the eastern Arctic Ocean are 0.12 y(-1) for (+)alpha-HCH 0.030 y(-1) for (-)alpha-HCH, and 0.037 y(-1) for achiral gamma-HCH. These rate constants are 3-10 times greater than those for basic hydrolysis in seawater. Microbial breakdown may compete with advective outflow for long-term removal of HCHs from the Arctic Ocean. Rate constants estimated for the arctic lake are about 3-8 times greater than those in the ocean.
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| 3. |
- Bidleman, TF, et al.
(författare)
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Chiral pesticides as tracers of air-surface exchange
- 1998
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Ingår i: Environmental Pollution. - 0269-7491 .- 1873-6424. ; 102:1, s. 43-49
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Tidskriftsartikel (refereegranskat)abstract
- The enantiomers of chiral pesticides are selectively broken down in soil and water to yield residues and metabolites, which are non-racemic. The distinctive enantiomer signatures of residues are preserved upon volatilization, providing site-specific tracers for air-soil and air-water exchange. Applications of enantiomeric tracers include distinguishing the atmospheric transport of freshly applied pesticides from those which are 'recycled' from lakes, oceans and soil, and investigating biotic vs abiotic degradation pathways. Examples are given of using pesticide enantiomers to follow volatilization from the Great Lakes and arctic waters and as indicators of pesticide emissions from agricultural soils.
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| 4. |
- Bidleman, TF, et al.
(författare)
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Chiral signatures of chlordanes indicate changing sources to the atmosphere over the past 30 years
- 2004
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Ingår i: Atmospheric Environment. - : Elsevier BV. - 1352-2310. ; 38:35, s. 5963-5970
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Tidskriftsartikel (refereegranskat)abstract
- Chlordane was used as an insecticide for half a century until its withdrawal from the world market in 1997. Trans- and cis-chlordane (TC, CC) are racemic in the technical product, but undergo enantio selective degradation in soil to leave nonracemic residues. In most cases, the (+) enantiomer of TC and the (-) enantiomer of CC are depleted, leading to enantiomer fractions, EF = (+)/[(+) + (-)], that are < 0.500 for TC and > 0.500 for CC. Nonracemic EFs of TC and CC, showing the same degradation preference as soils, were found in 1998-2001 air samples from stations in Arctic Canada and Finland, and on the west coast of Sweden. Environmental samples representing different time periods of chlordane history were also examined in: (a) archived atmospheric deposition samples collected in Sweden, Slovakia and Iceland in 1971-1973, (b) soils from southern Sweden sampled in 2001 and (c) a laminated lake sediment core from the Canadian Arctic representing similar to50 years of accumulation. TC and CC were racemic or nearly so in the historical atmospheric deposition samples and nonracemic in the Swedish soils. The EF of TC in the dated take sediment core decreased from nearly racemic in the past to nonracemic in recent times. These observations suggest that sources of chlordane to the atmosphere have changed over time and are now influenced to a greater extent by emission from soils.
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| 5. |
- Bidleman, TF, et al.
(författare)
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Soil as a source of atmospheric heptachlor epoxide
- 1998
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Ingår i: Environmental Science and Technology. - : American Chemical Society (ACS). - 0013-936X .- 1520-5851. ; 32:10, s. 1546-1548
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Tidskriftsartikel (refereegranskat)abstract
- The chiral pesticide heptachlor can undergo photolysis to yield the racemic products heptachlor-exo-epoxide (HEPX) and photoheptachlor. Heptachlor is also metabolized to nonracemic HEPX in biological systems and soils. HEPX in ambient air samples from the southern United States and Lakes Ontario and Superior was nonracemic and enriched in the (+) enantiomer. Average enantiomer ratios (ER = areas of (+)/(-) HEPX) in these locations ranged from 1.51 to 2.02, and were similar to ER values of HEPX reported for agricultural soils. Airborne heptachlor was racemic, with ERs of 0.98-1.02. These results suggest that the main source of HEPX in ambient air is not photolysis of heptachlor, hut rather metabolism of heptachlor in soils followed by volatilization of HEPX. The study exemplifies the use of chiral analysis for investigating the environmental fate of pesticides.
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