Development and validation of an HPLC-MS/MS method with QuEChERS extraction using isotopic dilution to simultaneously analyze chlordecone and chlordecol in animal livers.

A QuEChERS extraction method followed by HPLC-MS/MS analysis was developed to simultaneously analyze chlordecone and its metabolite chlordecol in animal livers. The overall method was validated with accuracy profiles according to the French Standard NF V03-110 and European Union guidelines. The validation was performed on bovine, ovine and porcine liver samples. Linearity, matrix effect, accuracy, within-laboratory repeatability, specificity, LOQ, Q/q relative ion intensities, and uncertainty were reported. Recoveries were between 70% and 120%. LOQs of 1.36 µg chlordecone kg-1 and 2.50 µg chlordecol kg-1 of fresh liver were found. Twelve contaminated livers of bovine, ovine and porcine origin from the French West Indies or samples from in vivo studies were analyzed. In these liver samples from contaminated animals, chlordecone was quantified at concentrations higher than the maximum residue limit and chlordecol in very low amounts in all the samples. In addition, these results confirm that chlordecone can be metabolized in ruminant species.

Theoretical study of chlordecone and surface groups interaction in an activated carbon model under acidic and neutral conditions.

Activated carbons (ACs) are widely used in the purification of drinking water without almost any knowledge about the adsorption mechanisms of the persistent organic pollutants. Chlordecone (CLD, Kepone) is an organochlorinated synthetic compound that has been used mainly as agricultural insecticide. CLD has been identified and listed as a persistent organic pollutant by the Stockholm Convention. The selection of the best suited AC for this type of contaminants is mainly an empirical and costly process. A theoretical study of the influence of AC surface groups (SGs) on CLD adsorption is done in order to help understanding the process. This may provide a first selection criteria for the preparation of AC with suitable surface properties. A model of AC consisting of a seven membered ring graphene sheet (coronene) with a functional group on the edge was used to evaluate the influence of the SGs over the adsorption. Multiple Minima Hypersurface methodology (MMH) coupled with PM7 semiempirical Hamiltonian was employed in order to study the interactions of the chlordecone with SGs (hydroxyl and carboxyl) at acidic and neutral pH and different hydration conditions. Selected structures were re-optimized using CAM-B3LYP to achieve a well-defined electron density to characterize the interactions by the Quantum Theory of Atoms in Molecules approach. The deprotonated form of surface carboxyl and hydroxyl groups of AC models show the strongest interactions, suggesting a chemical adsorption. An increase in carboxylic SGs content is proposed to enhance CLD adsorption onto AC at neutral pH conditions.

Soil microstructure and organic matter: keys for chlordecone sequestration.

Past applications of chlordecone, a persistent organochlorine pesticide, have resulted in diffuse pollution of agricultural soils, and these have become sources of contamination of cultivated crops as well as terrestrial and marine ecosystems. Chlordecone is a very stable and recalcitrant molecule, mainly present in the solid phase, and has a strong affinity for organic matter. To prevent consumer and ecosystem exposure, factors that influence chlordecone migration in the environment need to be evaluated. In this study, we measured the impact of incorporating compost on chlordecone sequestration in andosols as a possible way to reduce plant contamination. We first characterized the transfer of chlordecone from soil to plants (radish, cucumber, and lettuce). Two months after incorporation of the compost, soil-plant transfers were reduced by a factor of 1.9-15 depending on the crop. Our results showed that adding compost modified the fractal microstructure of allophane clays thus favoring chlordecone retention in andosols. The complex structure of allophane and the associated low accessibility are important characteristics governing the fate of chlordecone. These results support our proposal for an alternative strategy that is quite the opposite of total soil decontamination: chlordecone sequestration.

A preliminary communication. Isolation and positive confirmation of chlordecone in rabbit oviductal fluid.

Chlordecone (10 mg/kg, sc in corn oil) was administered to mature female rabbits once daily for five days. Analysis of oviductal fluid collected from these rabbits over the course of this experiment confirmed the presence of chlordecone. It is reasonable to suggest that chlordecone may reduce mammalian fertility during the preimplantation period by producing deleterious effects on respective gametes and/or the embryo. The mechanisms by which chlordecone may interfere with fertilization and reproduction is discussed.