Identification of the photoproducts of the insecticides mirex and Kepone

Alley, Earl G.; Layton, Blake; Minyard, J. P.

doi:10.1021/jf60193a054

Cited by 38 publications

(14 citation statements)

References 5 publications

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“…Assuming that the higher isotopic pattern centered at m/z 507.8 contained the molecular ion, we hypothesized two possible neutral formulae for F1, C 10 Cl 10 O 2 H 2 and C 10 Cl 10 SH 2 . In-source fragments were highly similar to those observed in polychlorinated bishomocubane-based structures including chlordecone, hydrochlordecones, chlordecol and mirex 5 , 6 , 24 . Indeed, the isotopic patterns at m/z 201.0, 235.9 and 271.9 presumably arose from the known in-source bishomocubane retrocyclodimerization and corresponded to positively charged C 5 -fragments.…”

Section: Resultssupporting

confidence: 56%

Transformation of the recalcitrant pesticide chlordecone by Desulfovibrio sp.86 with a switch from ring-opening dechlorination to reductive sulfidation activity

Della-Negra

Chaussonnerie

Fonknechten

et al. 2020

Sci Rep

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The insecticide chlordecone has been used in the French West Indies for decades, resulting in long term pollution, human health problems and social crisis. In addition to bacterial consortia and Citrobacter sp.86 previously described to transform chlordecone into three families of transformation products (A: hydrochlordecones, B: polychloroindenes and C: polychloroindenecarboxylic acids), another bacterium Desulfovibrio sp.86, showing the same abilities has been isolated and its genome was sequenced. Ring-opening dechlorination, leading to A, B and C families, was observed as previously described. changing operating conditions in the presence of chlordecone gave rise to the formation of an unknown sulfur-containing transformation product instead of the aforementioned ones. Its structural elucidation enabled to conclude to a thiol derivative, which corresponds to an undocumented bacterial reductive sulfidation. Microbial experiments pointed out that the chlordecone thiol derivative was observed in anaerobiosis, and required the presence of an electron acceptor containing sulfur or hydrogen sulfide, in a confined atmosphere. It seems that this new reaction is also active on hydrochlordecones, as the 10-monohydrochlordecone A1 was transformed the same way. Moreover, the chlordecone thiol derivative called F1 was detected in several chlordecone contaminated mangrove bed sediments from Martinique Island, highlighting the environmental relevance of these results. Chlordecone is a highly recalcitrant organochlorine pesticide that has been added to the Stockholm convention list of persistent organic pollutants in 2009. Several pest control products containing chlordecone (Kepone, Curlone) or a functionalized derivative (Kelevan) have been manufactured in the US, Brazil and France and applied in the Caribbean, Central America, West Africa, and Europe over an extended period of forty years 1. To date, chlordecone has caused two major environmental disasters: (1) acute exposure of workers at the Hopewell (US) chlordecone production plant in 1975 and massive pollution of the James River, extending over 100 miles that lasted for decades 2 , (2) ongoing impregnation of the French West Indies (FWI) population due to extensive agricultural use of chlordecone from 1972 to 1993 that has resulted in long-term pollution of environmental compartments (soils, water resources, coastal areas) and subsequently of some local food production (vegetables, farmed animals, and seafood). Until now, no remediation strategy has been proven satisfactory in the FWI environment whereas the population has to deal with health troubles (increased risk of cancer, motor and cognitive development disorders in young children, premature births) and social difficulties (disappearance of local economy activities) 1 .

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Section: Resultssupporting

confidence: 56%

Transformation of the recalcitrant pesticide chlordecone by Desulfovibrio sp.86 with a switch from ring-opening dechlorination to reductive sulfidation activity

Della-Negra

Chaussonnerie

Fonknechten

et al. 2020

Sci Rep

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“…MS data were interpreted using the extensive fragmentation work previously published for polychlorinated bishomocubanes including mirex, chlordecone and its two known partially dechlorinated derivatives (Uk et al, 1972; Alley et al, 1974; Harless et al, 1978). Finally, a chemical formula was postulated for 14 metabolites divided into two families: C 10 -compounds Ai (1 ≤ i ≤ 11) and C 9 -compounds Bi (1 ≤ i ≤ 3) (Figure 3 and Table 2).…”

Section: Resultsmentioning

confidence: 99%

Microbial Degradation of a Recalcitrant Pesticide: Chlordecone

et al. 2016

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Chlordecone (Kepone®) is a synthetic organochlorine insecticide (C10Cl10O) used worldwide mostly during the 1970 and 1980s. Its intensive application in the French West Indies to control the banana black weevil Cosmopolites sordidus led to a massive environmental pollution. Persistence of chlordecone in soils and water for numerous decades even centuries causes global public health and socio-economic concerns. In order to investigate the biodegradability of chlordecone, microbial enrichment cultures from soils contaminated by chlordecone or other organochlorines and from sludge of a wastewater treatment plant have been conducted. Different experimental procedures including original microcosms were carried out anaerobically over long periods of time. GC-MS monitoring resulted in the detection of chlorinated derivatives in several cultures, consistent with chlordecone biotransformation. More interestingly, disappearance of chlordecone (50 μg/mL) in two bacterial consortia was concomitant with the accumulation of a major metabolite of formula C9Cl5H3 (named B1) as well as two minor metabolites C10Cl9HO (named A1) and C9Cl4H4 (named B3). Finally, we report the isolation and the complete genomic sequences of two new Citrobacter isolates, closely related to Citrobacter amalonaticus, and that were capable of reproducing chlordecone transformation. Further characterization of these Citrobacter strains should yield deeper insights into the mechanisms involved in this transformation process.

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“…Chlordecone is a perchlorinated synthetic pesticide with a bis-homocubane structure (anhydrous form: C 10 Cl 10 O) that can be hydrated in the presence of water to a gem-diol form in place of the ketone moiety (Figure ). − Between the 1960s and 1990s, chlordecone was the active ingredient of pesticide formulations in many countries, including the French West Indies, among them Kepone which was introduced in 1958. Chlordecone toxicity was demonstrated in 1975 at the Hopewell chlordecone production plant (U.S.), where a lack of safety controls led to poisoning of workers and environmental pollution. − This disaster prompted the U.S. to prohibit the production and use of chlordecone in 1978.…”

Section: Introductionmentioning

confidence: 99%

Distinct Carbon Isotope Fractionation Signatures during Biotic and Abiotic Reductive Transformation of Chlordecone

Chevallier

Cooper

Kümmel

et al. 2018

Environ. Sci. Technol.

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Chlordecone is a synthetic organochlorine pesticide, extensively used in banana plantations of the French West Indies from 1972 to 1993. Due to its environmental persistence and bioaccumulation, it has dramatic public health and socio-economic impact. Here we describe a method for carbon-directed compound specific isotope analysis (CSIA) for chlordecone and apply it to monitor biotic and abiotic reductive transformation reactions, selected on the basis of their distinct product profiles (polychloroindenes versus lower chlorinated hydrochlordecones). Significant carbon isotopic enrichments were observed for all microbially mediated transformations (ε = -6.8‰ with a Citrobacter strain and ε = -4.6‰ with a bacterial consortium) and for two abiotic transformations (ε = -4.1‰ with zerovalent iron and ε = -2.6‰ with sodium sulfide and vitamin B). The reaction with titanium(III) citrate and vitamin B, which shows the product profile most similar to that observed in biotic transformation, led to low carbon isotope enrichment (ε =-0.8‰). The CSIA protocol was also applied on representative chlordecone formulations previously used in the French West Indies, giving similar chlordecone δC values from -31.1 ± 0.2‰ to -34.2 ± 0.2‰ for all studied samples. This allows the in situ application of CSIA for the assessment of chlordecone persistence.

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Identification of the photoproducts of the insecticides mirex and Kepone

Cited by 38 publications

References 5 publications

Transformation of the recalcitrant pesticide chlordecone by Desulfovibrio sp.86 with a switch from ring-opening dechlorination to reductive sulfidation activity

Transformation of the recalcitrant pesticide chlordecone by Desulfovibrio sp.86 with a switch from ring-opening dechlorination to reductive sulfidation activity

Microbial Degradation of a Recalcitrant Pesticide: Chlordecone

Distinct Carbon Isotope Fractionation Signatures during Biotic and Abiotic Reductive Transformation of Chlordecone

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