Environmental Science and Pollution Research

, Volume 23, Issue 1, pp 81–97 | Cite as

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

  • Damien A. DevaultEmail author
  • Christophe Laplanche
  • Hélène Pascaline
  • Sébastien Bristeau
  • Christophe Mouvet
  • Hervé Macarie
Crop protection and environmental health: legacy management and new concepts


Chlordecone (CLD) was an organochlorine insecticide whose previous use resulted in an extensive pollution of the environment with severe health effects and social consequences. A closely related compound, 5b-hydrochlordecone (5b-hydroCLD), has been searched for and often detected in environmental matrices from the geographical area where CLD was applied. The current consensus considered that its presence was not the result of a biotic or abiotic dechlorination of CLD in these matrices but rather the consequence of its presence as impurity (synthesis by-product) in the CLD released into the environment. The aim of the present study was to determine if and to what extent degradation of CLD into 5b-hydroCLD occurred in the field. To test this hypothesis, the ratios of 5b-hydroCLD and CLD concentrations in a dataset of 810 soils collected between 2006 and 2012 in Martinique were compared to the ratios measured in 3 samples of the CLD dust commercial formulations applied in the banana fields of French West Indies (FWI) and 1 sample of the technical-grade CLD corresponding to the active ingredient used in such formulations. Soil data were processed with a hierarchical Bayesian model to account for random measurement errors and data censoring. Any pathway of CLD transformation into 5b-hydroCLD occurring over the long term in FWI soils would indeed change the ratio of 5b-hydroCLD/CLD compared to what it was in the initially applied formulations. Results showed a significant increase of the 5b-hydroCLD/CLD ratio in the soils—25 times greater in soil than in commercial formulations—which suggested that natural CLD transformation into 5b-hydroCLD over the long term occurred in these soils. Results from this study may impact future decisions for the remediation of the polluted areas.


Kepone Curlone Pesticides Banana Martinique Hierarchical Bayesian modelling Data censoring 



The authors thank the SIG 972 and the Direction de l’Agriculture, de l’Alimentation et de la Forêt (Agriculture, Food and Forest Agency) of Martinique (Jean Iotti) for having allowed the access to the DAAF database and their help for data mining (Valentine Troesch and Mathilde Guéné). This work would not have been possible without the samples of Curlone® preserved from destruction by Alain Soler and Christian Chabrier from Cirad, Soizig Lemoine from French West Indies University and Hélène Marie-Nely from Martinique Agricultural Council and the sample of technical grade Kepone® conserved by Michael Unger (Virginia Institute of Marine Science). H.M. thanks Alain Archelas for his help in the correct naming of the bishomocubane compounds according to the CAS nomenclature and Yoan Labrousse for useful discussions. BRGM contribution was financed by the ABACHLOR project (Mouvet et al. 2013) within the DEMICHLORD programme set up by INRA with funds from the French Ministry of Research and by the DEVCHLORDECONE project conducted on BRGM research funds


In his 73rd year, this article is dedicated to Dr. G. Wayne Sovocool for his contributions to the use of mass spectral tools for the identification of organic pollutants. 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. We also thank Wayne for his advice in order to improve the English of the present article.

Supplementary material

11356_2015_4865_MOESM1_ESM.doc (334 kb)
Fig. S1 Point (circles) and 95 % confidence interval (horizontal lines: CLD; vertical lines: 5b-hydroCLD) estimates for latent 5b-hydroCLD and CLD concentrations in soil computed by the HBM. Concentrations for uncensored data (green) as well as rounded data (orange) and soil samples which measured 5b-hydroCLD concentration were lower than the LOQ (DAAF: red; BRGM: blue) are represented. Oblique black lines are lines of constant 5bhydroCLD/CLD mass ratio. LOQ for CLD and 5b-hydroCLD are plotted as horizontal and vertical dashed lines (DAAF: violet; BRGM: pink). (DOC 334 kb).
11356_2015_4865_MOESM2_ESM.doc (442 kb)
Fig. S2 Point estimates for latent 5b-hydroCLD and CLD concentrations (circles) and 95 % confidence interval estimates for 5b-hydroCLD/CLD mass ratio (colored oblique lines) in soil computed by the HBM. 5b-hydroCLD/CLD mass ratio for uncensored data (green) as well as rounded data (orange) and soil samples which measured 5b-hydroCLD concentration were lower than the LOQ (DAAF: red; BRGM: blue) are represented. Oblique black lines are lines of constant 5bhydroCLD/CLD mass ratio. LOQ for CLD and 5b-hydroCLD are plotted as horizontal and vertical dashed lines (DAAF: violet; BRGM: pink). (DOC 441 kb).
11356_2015_4865_MOESM3_ESM.doc (127 kb)
Fig. S3 Extraction yields plotted as box-and-whisker plots. (for the explanation of the letter significance above the box see appendix B). (DOC 127 kb).
11356_2015_4865_MOESM4_ESM.doc (54 kb)
Appendix A (DOC 54 kb)
11356_2015_4865_MOESM5_ESM.doc (48 kb)
Appendix B (DOC 48 kb)


  1. Alley EG, Layton BR, Minyard JP (1974) Identification of the photoproducts of the insecticides Mirex and Kepone. J Agric Food Chem 22:442–445CrossRefGoogle Scholar
  2. Beaugendre MJ, Edmond-Mariette P, Le Guen MM, Mnascour LJ, Sauvadet F, Vialatte JS (2005) Information report on the use of chlordecone and other organochlorine pesticides in the agriculture of Martinique and Guadeloupe. Assemblée Nationale (French Parliament), report no 2430, 170 pp. Observatoire des Résidus de Pesticides. Accessed 30 April 2015 (in French)
  3. Belghit H, Cola C, Bristeau S, Mouvet C, Maunit B (2015) Liquid chromatography-high resolution mass spectrometry for identifying aqueous chlordecone hydrate dechlorinated products formed by reaction with zero-valent iron. Int J Environ Anal Chem 95:93–105CrossRefGoogle Scholar
  4. Bellec S, Godard E (2002) Contamination by organochlorine phytosanitary products in Martinique – characterization of the population exposition. Report established for the French Ministry of Employment and Solidarity. 37 pp. Observatoire des Résidus de Pesticides. Accessed 30 April 2015 (in French)
  5. Bettina H, Hermann F, Wolfgang V, Mehmet C (2011) Effects of chain length, chlorination degree, and structure on the octanol-water partition coefficients of polychlorinated n-alkanes. Environ Sci Technol 45:2842–2849CrossRefGoogle Scholar
  6. Bocquené G, Franco A (2005) Pesticide contamination of the coastline of Martinique. Mar Pollut Bull 51:612–619CrossRefGoogle Scholar
  7. Borsetti AP, Roach JAG (1978) Identification of Kepone alteration products in soil and mullet. Bull Environ Contam Toxicol 20:211–247CrossRefGoogle Scholar
  8. Bristeau S, Amalric L, Mouvet C (2014) Validation of chlordecone analysis for native and remediated French West Indies soils with high organic matter content. Anal Bioanal Chem 406:1073–1080CrossRefGoogle Scholar
  9. Bro-Rasmussen F (1996) Contamination by persistent chemicals in food chain and human health. Sci Total Environ 188:S45–S60CrossRefGoogle Scholar
  10. Cabidoche Y-M, Achard R, Cattan P, Clermont-Dauphin C, Massat F, Sansoulet J (2009) Long-term pollution by chlordecone of tropical volcanic soils in the French West Indies: a simple leaching model accounts for current residue. Environ Pollut 157:1697–1705CrossRefGoogle Scholar
  11. Cabidoche Y-M, Lesueur-Jannoyer M (2012) Contamination of harvested organs in root crops grown on chlordecone-polluted soils. Pedosphere 22:562–571CrossRefGoogle Scholar
  12. Carlson DA, Konyha KD, Wheeler WB, Marshall GP, Zaylskie RG (1976) Mirex in the environment: its degradation to Kepone and related compounds. Science 194:939–941CrossRefGoogle Scholar
  13. Carver RA, Griffith FD (1979) Determination of Kepone dechlorination products in finfish, oysters and crustaceans. J Agric Food Chem 27:1035–1037CrossRefGoogle Scholar
  14. Cavelier N (1980) Contamination of fauna by organochlorine pesticides. In: Kermarrec A. (ed) Actual level of the contamination of biological chains in Guadeloupe by pesticides and heavy metals: 1979-1980. Report established for the French Ministry of Environment. pp 114-128. Observatoire des Résidus de Pesticides. Accessed 30 April 2015 (in French)
  15. Chevallier T, Woignier T, Toucet J, Blanchart E (2010) Organic carbon stabilization in the fractal pore structure of andosols. Geoderma 159:182–188CrossRefGoogle Scholar
  16. Clostre F, Lesueur-Jannoyer M, Achard R, Letourmy P, Cabidoche Y-M, Cattan P (2014a) Decision support tool for soil sampling of heterogeneous pesticide (chlordecone) pollution. Environ Sci Pollut Res 21:1980–1992CrossRefGoogle Scholar
  17. Clostre F, Letourmy P, Thuriès L, Lesueur-Jannoyer M (2014b) Effect of home food processing on chlordecone (organochlorine) content in vegetables. Sci Total Environ 490:1044–1050CrossRefGoogle Scholar
  18. Coat S, Bocquené G, Godard E (2006) Contamination of some aquatic species with the organochlorine pesticide chlordecone in Martinique. Aquat Living Resour 19:181–187CrossRefGoogle Scholar
  19. Coat S, Monti D, Legendre P, Bouchon C, Massat F, Lepoint G (2011) Organochlorine pollution in tropical rivers (Guadeloupe): role of ecological factors in food web bioaccumulation. Environ Pollut 159:1692–1701CrossRefGoogle Scholar
  20. Cornish AS, Ng WC, Ho VCM, Wong HL, Lam JCW, Lam PKS, Leung KMY (2007) Trace metal and organochlorines in the bamboo shark Chiloscyllium plagiosum from the southern waters of Hong Kong, China. Sci Total Environ 376:335–345CrossRefGoogle Scholar
  21. Dallaire R, Muckle G, Rouge F, Kadhel P, Bataille H, Guldner L, Seurin S, Chajès V, Monfort C, Boucher O, Pierre Thomé J, Jacobson SW, Multigner L, Cordier S (2012) Cognitive, visual, and motor development of 7-month-old Guadeloupean infants exposed to chlordecone. Environ Res 118:79–85CrossRefGoogle Scholar
  22. Dolfing J, Novak I, Archelas A, Macarie H (2012) Gibbs free energy of formation of chlordecone and potential degradation products: implications for remediation strategies and environmental fate. Environ Sci Technol 46:8131–8139CrossRefGoogle Scholar
  23. Dolfing J, Van Eekert M, Seech A, Vogan J, Mueller J (2008) In situ chemical reduction (ISCR) technologies: significance of low Eh reactions. Soil Sediment Contam 17:63–74CrossRefGoogle Scholar
  24. Dubuisson C, Héraud F, Leblanc J-C, Gallotti S, Flamand C, Blateau A, Quenel P, Volatier J-L (2007) Impact of subsistence production on the management options to reduce the food exposure of the Martinican population to chlordecone. Regul Toxicol Pharmacol 49:5–16CrossRefGoogle Scholar
  25. Faroon O, Kueberuwa S, Smith L, DeRosa C (1995) ATSDR evaluation of health effects of chemicals 2. Mirex and chlordecone: health effects, toxicokinetics, human exposure, and environmental fate. Toxicol Ind Health 11:1–203CrossRefGoogle Scholar
  26. Fernández-Bayo JD, Saison C, Voltz M, Disko U, Hofmann D, Berns AE (2013) Chlordecone fate and mineralisation in a tropical soil (andosol) microcosm under aerobic conditions. Sci Total Environ 463–464:395–403CrossRefGoogle Scholar
  27. Galuszka A, Migaszewski ZM, Manecki P (2011) Pesticide burial grounds in Poland: a review. Environ Int 37:1265–1272CrossRefGoogle Scholar
  28. George SE, King LC, Claxton LD (1986) High performance liquid chromatography separation of chlordecone and its metabolites. Chromatographia 22:165–167CrossRefGoogle Scholar
  29. Gewurtz SB, Lega R, Crozier PW, Whittle DM, Fayez L, Reiner EJ, Helm PA, Marvin CH, Tomy GT (2009) Factors influencing trends of polychlorinated naphthalenes and other dioxin-like compounds in lake trout (Salvelinus namaycush) from lake Ontario, North America (1979-2004). Environ Toxicol Chem 28:921–930CrossRefGoogle Scholar
  30. Gourcy L, Baran N, Vittecoq B (2009) Improving the knowledge of pesticide transfer processes using age-dating tools (CFC, SF6, 3H) in a volcanic island (Martinique, French West Indies). J Contam Hydrol 108:107–117CrossRefGoogle Scholar
  31. Harless RL, Haris DE, Sovocool GW, Zehr RD, Wilson NK, Oswald EO (1978) Mass spectrometric analyses and characterization of Kepone in environmental and human samples. Biol Mass Spectrom 5:232–237CrossRefGoogle Scholar
  32. Hodgson E (1998) Toxicology of environmentally persistent chemicals: Mirex and chlordecone. Rev Toxicol 2:477–499Google Scholar
  33. Houdart M, Tixier P, Lassoudière A, Saudubray F (2009) Assessing pesticide pollution risk: from field to watershed. Agron Sustain Dev 29:321–327CrossRefGoogle Scholar
  34. Hugget RJ (1989) Kepone and the James River. In: Contaminated marine sediments: assessments and remediation. National Academic Press, Washington DC, pp 417–424Google Scholar
  35. Ivie GW, Dorough HW, Alley EG (1974) Photodecomposition of Mirex on silica gel chromatoplates exposed to natural and artificial light. J Agric Food Chem 22:933–935CrossRefGoogle Scholar
  36. Joly P-B (2010) Chlordecone saga in French West Indies – chronological reconstruction 1968-2008. 82 pp. Observatoire des Résidus de Pesticides. Accessed 30 April 2015 (in French)
  37. Jondreville C, Lavigne A, Jurjanz S, Dalibard C, Liabeuf JM, Clostre F, Lesueur-Jannoyer M (2014) Contamination of free-range ducks by chlordecone in Martinique (French West Indies): a field study. Sci Total Environ 493:336–341CrossRefGoogle Scholar
  38. Kadhel P, Monfort C, Costet N, Rouget F, Thomé JP, Multigner L, Cordier S (2014) Chlordecone exposure, length of gestation and risk of preterm birth. Am J Epidemiol 179:536–544CrossRefGoogle Scholar
  39. Kaiser KLE (1978) Pesticide report: the rise and fall of Mirex. Environ Sci Technol 12:520–528CrossRefGoogle Scholar
  40. Kuramochi H, Maeda K, Kawamoto K (2004a) Water solubility and partitioning behavior of brominated phenols. Environ Toxicol Chem 23:1386–1393CrossRefGoogle Scholar
  41. Kuramochi H, Maeda K, Kawamoto K (2004b) Measurements of water solubilities and 1-octanol/water partition coefficients and estimations of Henry’s Law constants for brominated benzenes. J Chem Eng Data 49:720–724CrossRefGoogle Scholar
  42. Le Déaut J-Y, Procaccia C (2009) Pesticide use in the Antilles: current situation and perspectives for change. OPECST report n° 487 (2008-2009). French Senat. ISBN: 9782111267688,, 223 pp (in French)
  43. Li XM, Li YT, Li FB, Zhou SG, Feng CH, Liu TX (2009) Interactively interfacial reaction of iron-reducing bacterium and goethite for reductive dechlorination of chlorinated organic compounds. Chin Sci Bull 54:2800–2804Google Scholar
  44. Li XM, Zhou SG, Li FB, Wu CY, Zhuang L, Xu W, Liu L (2008) FeIII oxide reduction and carbon tetrachloride dechlorination by a newly isolated Klebsiella pneumoniae strain L1. J Appl Microbiol 106:130–139CrossRefGoogle Scholar
  45. Lunn D, Jackson C, Best N, Thomas A, Spiegelhalter D (2012) The BUGS book: a practical introduction to Bayesian analysis. Chapman and Hall/CRC, LondonGoogle Scholar
  46. Maejima Y, Nagatsuka S, Higashi T (2000) Mineralogical composition of iron oxides in red-and yellow-colored soils from Southern Japan and Yunnan, China. Soil Sci Plant Nutr 46:571–580CrossRefGoogle Scholar
  47. Maier-Bode H (1976) The insecticide “Kelevan”. Residue Rev 63:45–76Google Scholar
  48. Majzlan J (2013) Minerals and aqueous species of iron and manganese as reactants and products of microbial metal respiration. In: Gesher J, Kappler A (eds) Microbial metal respiration: from geochemistry to potential applications. Springer Verlag, Berlin, pp 1–28CrossRefGoogle Scholar
  49. Martin-Laurent F, Sahnoun MM, Merlin C, Volmer G, Lübke M (2014) Detection and quantification of chlordecone in contaminated soils from the French West Indies by GC-MS using the 13C10-chlordecone stable isotope as a tracer. Environ Sci Pollut Res 21:4928–4933CrossRefGoogle Scholar
  50. Mercier A, Dictor M-C, Harris-Hellal J, Breeze D, Mouvet C (2013) Distinct bacterial community structure of 3 tropical volcanic soils from banana plantations contaminated with chlordecone in Guadeloupe (French West Indies). Chemosphere 92:787–794CrossRefGoogle Scholar
  51. Merlin C, Devers M, Crouzet O, Heraud C, Steinberg C, Mougin C, Martin-Laurent F (2014) Characterization of chlordecone-tolerant fungal populations isolated from long-term polluted tropical volcanic soil in the French West Indies. Environ Sci Pollut Res 21(7):4914–27CrossRefGoogle Scholar
  52. Moore WP, Hundtofte VA (1976) Process for producing decachlorooctahydro-1,3,4-metheno-2H-cyclobuta-(C, D)-pentalen-2-one. US Patent 3:937,734, 5 pp Google Scholar
  53. Mouvet C, Bristeau S, Amalric L, Dossman H, Maunit B, Belghit H, Ollivier B, Archelas A, Macarie H (2013) ABAChlor final report. BRGM/RP-62769-FR,, 153 pp (in French)
  54. Mouvet C, Dictor M-C, Mercier A, Bristeau S, Amalric L, Mueller J (2012) In situ chemical reduction (ISCR) for removal of Kepone from tropical soils. In: “Eighth international conference on remediation of chlorinated and recalcitrant compounds”, Monterey, CA, ISBN 978-0-9819730-5-0. ©2012 Battelle Memorial Institute, Columbus, OH,
  55. Mrema EJ, Rubino FM, Colosio C (2013) Obsolete pesticides – a threat to environment, biodiversity and human health. In: Simeonov LI, Macaev FZ, Simeonova BG (eds) Environmental security assessment and management of obsolete pesticides in southeast Europe, NATO Science for Peace and Security, Series C: Environmental Security. Springer, Dordrecht, pp 1–21Google Scholar
  56. Multigner L, Ndong JR, Giusti A, Romana M, Delacroix-Maillard H, Cordier S, Jégou B, Thome JP, Blanchet P (2010) Chlordecone exposure and risk of prostate cancer. J Clin Oncol 28:3457–3462CrossRefGoogle Scholar
  57. Nguyen TH, Goss K-U, Ball WP (2005) Polyparameter linear free energy relationships for estimating the equilibrium partition of organic compounds between water and the natural organic matter in soils and sediments. Environ Sci Technol 39:913–924CrossRefGoogle Scholar
  58. Orndorff SA, Colwell RR (1980) Microbial transformation of Kepone. Appl Environ Microbiol 39:398–406Google Scholar
  59. Parfitt RL, Childs CW, Eden DN (1988) Ferrihydrite and allophane in four Andepts from Hawaii and implications for their classification. Geoderma 41:223–241CrossRefGoogle Scholar
  60. R Core Team (2014). R: a language and environment for statistical computing. R Foundation for Statistical Computing, Vienna, Austria.
  61. Roche H, Salvat B, Ramade F (2011) Assessment of the pesticides pollution of coral reefs communities from French Polynesia. Rev Ecol 66:3–10Google Scholar
  62. Schaefer CEGR, Fabris JD, Ker JC (2008) Minerals in the clay fraction of Brazilian Latosols (Oxisols): a review. Clay Miner 43:137–154CrossRefGoogle Scholar
  63. Schrauzer GN, Katz RN (1978) Reductive dechlorination and degradation of Mirex and Kepone with vitamin B12s. Bioinorg Chem 9:123–143CrossRefGoogle Scholar
  64. Sexstone AJ, Revsbech N, Parkin TB, Tideje JM (1985) Direct measurement of oxygen profile and denitrification rates in soil aggregates. Soil Sci Soc Am J 49:645–651CrossRefGoogle Scholar
  65. Smidt H, de Vos WM (2004) Anaerobic microbial dehalogenation. Annu Rev Microbiol 58:43–73CrossRefGoogle Scholar
  66. Stafford CJ, Reichel WL, Swineford DM, Prouty RM, Gay ML (1978) Gas-liquid chromatographic determination of Kepone in field-collected avian tissues and eggs. J Assoc Official Anal Chem 61:8–14Google Scholar
  67. Stockholm Convention website (2015). The 12 initial POPs under the Stockholm Convention. Accessed 4 May 2015
  68. van Noort PCM (2009) Estimation of amorphous organic carbon/water partition coefficients, subcooled liquid aqueous solubilities, and n-octanol/water partition coefficients of nonpolar chlorinated aromatic compounds from chlorine fragment constants. Chemosphere 74:1024–1030CrossRefGoogle Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2015

Authors and Affiliations

  • Damien A. Devault
    • 1
    • 2
    Email author
  • Christophe Laplanche
    • 3
  • Hélène Pascaline
    • 1
  • Sébastien Bristeau
    • 4
  • Christophe Mouvet
    • 5
  • Hervé Macarie
    • 6
    • 7
  1. 1.EA 929 AIHP-GEODE, Groupe BiospheresUniversité des AntillesSchœlcher CedexFrance
  2. 2.Faculté de Pharmacie, UMR 8079, CNRS AgroParisTechUniv. Paris SudParisFrance
  3. 3.INP, UPS, CNRS, ECOLAB (Laboratoire Ecologie Fonctionnelle et Environnement), ENSATUniversité de ToulouseCastanet TolosanFrance
  4. 4.Division LaboratoiresBRGMOrléans CedexFrance
  5. 5.Division Eau, Environnement et EcotechnologiesBRGMOrléans CedexFrance
  6. 6.IRD, UMR IMBELamentinFrance
  7. 7.Aix Marseille Université, CNRS, IRD, Avignon Université, IMBE, UMR 7263 – IRD 237MarseilleFrance

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