Mass spectrometric analyses and characterization of Kepone in environmental and human samples

Abstract

A specific portion of our environment has been contaminated with Kepone, or chlordecone. Additionally, some specific human exposures to high concentrations of Kepone have been confirmed. Gas chromatography mass spectrometry involving chemical ionization and high resolution mass spectrometry were used to detect, identify and confirm the presence of Kepone, Kepone photoproducts and a reduction product of Kepone in environmental and human samples. Field desorption, field ionization and electron impact mass spectrometric methods, as well as infrared and nuclear magnetic resonance techniques were used to characterize and identify Kepone hydrate and hemiketal in benzene and methanol solutions, respectively.

Natural transformation of chlordecone into 5b-hydrochlordecone in French West Indies soils: statistical evidence for investigating long-term persistence of organic pollutants

“…5b-Hydrochlordecone 4 (5b-hydroCLD), whose structure is identical to CLD except that one chlorine atom is replaced by a hydrogen at position 5b (Chemical Abstracts Service (CAS) numbering) and which is commercially available as an analytical standard, has been searched for and often detected in environmental matrices (soil, surface water and groundwater, sediments, plants, avian tissues and eggs, crustaceans, molluscs and fishes) from the geographical areas where CLD was applied (FWI) or unintentionally released during its manufacture (USA) (Borsetti and Roach 1978;Harless et al 1978;Stafford et al 1978;Carver and Griffith 1979;Orndorff and Colwell 1980;Coat et al 2011;Martin-Laurent et al 2014;Clostre et al 2014a, b). The current tacit assumption is that the presence of this compound is not the result of a biotic or abiotic dechlorination of CLD in these matrices but rather the consequence of its presence as an impurity, a by-product of its preparation, in the CLD released in the environment (Borsetti and Roach 1978;Cabidoche et al 2009;Coat et al 2011;Martin-Laurent et al 2014).…”

“…Among his achievements, he was a member of the US EPA team who 37 years ago made a breakthrough in the GC/MS analysis of chlordecone and of its mono-, di-hydro and chlordecol derivatives (see reference of Harless et al 1978). Since then, this work remains a source of key information for those who are involved in chlordecone environmental studies.…”

Determination of Kepone and Its Metabolite in Water and Soil by High-Performance Liquid Chromatography–Mass Spectrometry

“…Unexpectedly, in addition to the ion at m=z 507 [M þ H 2 O-H] - (Moriwaki and Hasegawa 2004;Fariss et al 1982), an ion at m=z 521 [M þ MeOH-H] -( Figure S1, Supplemental Content) was also observed by HPLC-MS when kepone was eluted in methanol=water. The methanolic adduct was also reported by Harless et al (1978). Therefore, the reported HPLC-ESI-MS method needed improvement.…”

“…Methods for kepone determination are primarily based on gas chromatography (GC) (Amalric et al 2006;Caplan, Thompson, and Hebb 1979;Carver, Borsetti, and Kamps 1978;Dabrowski and Waliszewski 1979;Deleon et al 1980;Meus and Ernst 1979;Moseman et al 1977;Stafford et al 1978). George, King, and Claxton (1986) reported that kepone may be determined by high-performace liquid chromatography (HPLC), which tolerates higher sample loading and may avoid sample degradation (Harless et al 1978;Cairns, Siegmund, and Doose 1982). In addition, HPLC-mass spectrometry (MS) typically exhibited higher sensitivity than GC-MS (Moriwaki and Hasegawa 2004), although the analysis may be affected by formation of a methanolic hemiketal.…”

“…Kepone alcohol, which has been mistakenly recognized as an artifact in kepone analysis (Harless et al 1978), has been considered to be a kepone metabolite (Fariss et al 1982;Houston et al 1981;Molowa eet al 1986;Dilling and Dilling 1967). However, to our knowledge, no method is available for the determination of kepone and kepone alcohol in environmental samples.…”