Chlordecone

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Chlordecone
Chlordecone.png
Chlordecone Kepone 3D.png
Names
IUPAC name
decachloropentacyclo[5.3.0.02.6.03.9.04.8]decan-5-one [1]
Other names
Chlordecone
Clordecone
Merex
CAS name: 1,1a,3,3a,4,5,5,5a,5b,6-decachlorooctahydro-1,3,4-metheno-2H-cyclobuta[cd]pentalen-2-one
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.005.093 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 205-601-3
KEGG
PubChem CID
UNII
  • InChI=1S/C10Cl10O/c11-2-1(21)3(12)6(15)4(2,13)8(17)5(2,14)7(3,16)9(6,18)10(8,19)20 Yes check.svgY
    Key: LHHGDZSESBACKH-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/C10Cl10O/c11-2-1(21)3(12)6(15)4(2,13)8(17)5(2,14)7(3,16)9(6,18)10(8,19)20
    Key: LHHGDZSESBACKH-UHFFFAOYAM
  • ClC54C(=O)C1(Cl)C2(Cl)C5(Cl)C3(Cl)C4(Cl)C1(Cl)C2(Cl)C3(Cl)Cl
Properties
C10Cl10O
Molar mass 490.633 g/mol
Appearancetan to white crystalline solid
Odor odorless
Density 1.6 g/cm3
Melting point 349 °C (660 °F; 622 K) (decomposes)
0.27 g/100 mL
Solubility soluble in acetone, ketone, acetic acid
slightly soluble in benzene, hexane
log P 5.41
Vapor pressure 3.10−7 kPa
Thermochemistry
Std molar
entropy (S⦵298)
764 J/K mol
-225.9 kJ/mol
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
carcinogen [2]
Flash point Non-flammable [2]
Lethal dose or concentration (LD, LC):
95 mg/kg (rat, oral)
NIOSH (US health exposure limits):
PEL (Permissible)
none [2]
REL (Recommended)
Ca TWA 0.001 mg/m3 [2]
IDLH (Immediate danger)
N.D. [2]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

Chlordecone, better known in the United States under the brand name Kepone, is an organochlorine compound and a colourless solid. It is an obsolete insecticide, now prohibited in the western world, but only after many thousands of tonnes had been produced and used. [3] Chlordecone is a known persistent organic pollutant that was banned globally by the Stockholm Convention on Persistent Organic Pollutants in 2009. [4]

Contents

Synthesis

Chlordecone is made by dimerizing hexachlorocyclopentadiene and hydrolyzing to a ketone. [5]

It is also the main degradation product of mirex. [3]

History

In the U.S., chlordecone, commercialized under the brand name "Kepone", was produced by Allied Signal Company and LifeSciences Product Company in Hopewell, Virginia. The improper handling and dumping of the substance (including the waste materials generated in its manufacturing process) into the nearby James River (U.S.) in the 1960s and 1970s drew national attention to its toxic effects on humans and wildlife. After two physicians, Dr. Yi-nan Chou and Dr. Robert S. Jackson of the Virginia Health Department, notified the Centers for Disease Control that employees of the company had been found to have toxic chemical poisoning, LifeSciences voluntarily closed its plant on July 4, 1975, and cleanup of the contamination began and a 100-mile section of the James River was closed to fishing while state health officials looked for other persons who might have been injured. [6] At least 29 people in the area were hospitalized as a result of their exposure to Kepone. [6]

The product is made in a Diels-Alder reaction shared with pesticides like chlordane and endosulfan. [3] Chlordecone is cited amongst a handful of other noxious substances as the driver for Gerald Ford's half-hearted approval in 1976 of the Toxic Substances Control Act, which "remains one of the most controversial regulatory bills ever passed". [7]

Regulation

In the US, Chlordecone was not federally regulated until after the Hopewell disaster, in which 29 factory workers were hospitalized with various ailments, including neurological. [8]

In France it was banned on the mainland only, in 1993. [9]

In 2009, chlordecone was included in the Stockholm Convention on Persistent Organic Pollutants, which bans its production and use worldwide. [4]

On March 14, 2024, the French National Assembly assumed responsibility for the chlordecone contamination affecting populations in Martinique and Guadeloupe. [10]

Toxicology

Chlordecone can accumulate in the liver and the distribution in the human body is regulated by binding of the pollutant or its metabolites to lipoproteins like LDL and HDL. [11] The LC50 (LC = lethal concentration) is 35 μg/ L for Etroplus maculatus , [12] 22–95 μg/kg for blue gill and trout. Chlordecone bioaccumulates in animals by factors up to a million-fold.

Workers with repeated exposure suffer severe convulsions resulting from degradation of the synaptic junctions. [3]

Chronic low level exposure appears to cause prostate cancer in men, [13] and "significant excesses of deaths were observed for stomach cancer in women and pancreatic cancer in women". [14]

Chlordecone has been found to act as an agonist of the GPER (GPR30), which interacts strongly with the estrogen sex hormone estradiol. [15]

Incidents

The history of chlordecone incidents are reviewed in Who's Poisoning America?: Corporate Polluters and Their Victims in the Chemical Age (1982).

James River estuary

In July 1975, [16] Virginia Governor Mills Godwin Jr. shut down the James River to fishing for 100 miles, from Richmond to the Chesapeake Bay. [8] This ban remained in effect for 13 years, until efforts to clean up the river began to show results. [17]

Due to the pollution risks, many fishermen, marinas, seafood businesses, and restaurants, along with their employees along the river suffered economic losses. In 1981, a large group of these entities sued Allied Chemical in federal district court (Eastern District of Virginia), claiming special economic damages from Allied's negligent damage to the fish and wildlife. [18] In a case that sometimes appears in law school courses on Remedies, the court rejected the traditional "economic-loss rule", which requires physical impact causing personal injury or property damage to receive economic damages, and instead allowed a limited group of the plaintiffs—the fishing boat owners, the marinas, and the bait and tackle shops—to recover economic damages from Allied Chemical.

French Antilles

The French islands of Martinique and Guadeloupe are heavily contaminated with chlordecone, [19] following years of its massive and unrestricted use on banana plantations. [20] [21] Despite a 1990 ban on the substance in mainland France, the economically powerful banana planters lobbied intensively to obtain a waiver to keep using Kepone until 1993. They argued that no alternative pesticide was available, which has since been disputed. After the 1993 ban, the banana planters were discreetly granted derogations to use their remaining stocks, and a 2005 report prepared by the French National Assembly states that after the 1993 ban was imposed, the chemical was illegally imported to the islands under the name Curlone, and continued to be used for many years. [9] Since 2003, local authorities in the two islands have restricted the cultivation of various food crops because the soil is badly contaminated by chlordecone. A 2018 large-scale study by the French public health agency, Santé publique France, shows that 95% of the inhabitants of Guadeloupe and 92% of those of Martinique are contaminated by the chemical. [22] Guadeloupe has one of the highest prostate cancer diagnosis rates in the world. [23]

Related Research Articles

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<span class="mw-page-title-main">Dichloromethane</span> Chemical compound

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<span class="mw-page-title-main">Lindane</span> Organochlorine chemical and an isomer of hexachlorocyclohexane

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<span class="mw-page-title-main">Chlorpyrifos</span> Chemical compound

In organic chemistry, chlorpyrifos (CPS), also known as chlorpyrifos ethyl, is an organophosphate pesticide that has been used on crops, animals, and buildings, and in other settings, to kill several pests, including insects and worms. It acts on the nervous systems of insects by inhibiting the acetylcholinesterase enzyme. Chlorpyrifos was patented in 1966 by Dow Chemical Company.

<span class="mw-page-title-main">Endocrine disruptor</span> Chemicals that can interfere with endocrine or hormonal systems

Endocrine disruptors, sometimes also referred to as hormonally active agents, endocrine disrupting chemicals, or endocrine disrupting compounds are chemicals that can interfere with endocrine systems. These disruptions can cause numerous adverse human health outcomes including, alterations in sperm quality and fertility, abnormalities in sex organs, endometriosis, early puberty, altered nervous system function, immune function, certain cancers, respiratory problems, metabolic issues, diabetes, obesity, cardiovascular problems, growth, neurological and learning disabilities, and more. Found in many household and industrial products, endocrine disruptors "interfere with the synthesis, secretion, transport, binding, action, or elimination of natural hormones in the body that are responsible for development, behavior, fertility, and maintenance of homeostasis ."

<span class="mw-page-title-main">Chemical hazard</span> Non-biological hazards of hazardous materials

Chemical hazards are hazards present in hazardous chemicals and hazardous materials. Exposure to certain chemicals can cause acute or long-term adverse health effects. Chemical hazards are usually classified separately from biological hazards (biohazards). Chemical hazards are classified into groups that include asphyxiants, corrosives, irritants, sensitizers, carcinogens, mutagens, teratogens, reactants, and flammables. In the workplace, exposure to chemical hazards is a type of occupational hazard. The use of personal protective equipment may substantially reduce the risk of adverse health effects from contact with hazardous materials.

<span class="mw-page-title-main">Pentachlorophenol</span> Chemical compound

Pentachlorophenol (PCP) is an organochlorine compound used as a pesticide and a disinfectant. First produced in the 1930s, it is marketed under many trade names. It can be found as pure PCP, or as the sodium salt of PCP, the latter of which dissolves easily in water. It can be biodegraded by some bacteria, including Sphingobium chlorophenolicum.

<span class="mw-page-title-main">Persistent organic pollutant</span> Organic compounds that are resistant to environmental degradation

Persistent organic pollutants (POPs) are organic compounds that are resistant to degradation through chemical, biological, and photolytic processes. They are toxic and adversely affect human health and the environment around the world. Because they can be transported by wind and water, most POPs generated in one country can and do affect people and wildlife far from where they are used and released.

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<span class="mw-page-title-main">Atrazine</span> Herbicide

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<span class="mw-page-title-main">Dieldrin</span> Chemical compound

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<span class="mw-page-title-main">Toxaphene</span> Chemical compound

Toxaphene was an insecticide used primarily for cotton in the southern United States during the late 1960s and the 1970s. Toxaphene is a mixture of over 670 different chemicals and is produced by reacting chlorine gas with camphene. It can be most commonly found as a yellow to amber waxy solid.

<span class="mw-page-title-main">Aldrin</span> Chemical compound

Aldrin is an organochlorine insecticide that was widely used until the 1990s, when it was banned in most countries. Aldrin is a member of the so-called "classic organochlorines" (COC) group of pesticides. COCs enjoyed a very sharp rise in popularity during and after World War II. Other noteworthy examples of COCs include dieldrin and DDT. After research showed that organochlorines can be highly toxic to the ecosystem through bioaccumulation, most were banned from use. Before the ban, it was heavily used as a pesticide to treat seed and soil. Aldrin and related "cyclodiene" pesticides became notorious as persistent organic pollutants.

<span class="mw-page-title-main">Endosulfan</span> Chemical compound

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<span class="mw-page-title-main">Mirex</span> Chemical compound

Mirex is an organochloride that was commercialized as an insecticide and later banned because of its impact on the environment. This white crystalline odorless solid is a derivative of cyclopentadiene. It was popularized to control fire ants but by virtue of its chemical robustness and lipophilicity it was recognized as a bioaccumulative pollutant. The spread of the red imported fire ant was encouraged by the use of mirex, which also kills native ants that are highly competitive with the fire ants. The United States Environmental Protection Agency prohibited its use in 1976. It is prohibited by the Stockholm Convention on Persistent Organic Pollutants.

<span class="mw-page-title-main">Soil contamination</span> Pollution of land by human-made chemicals or other alteration

Soil contamination, soil pollution, or land pollution as a part of land degradation is caused by the presence of xenobiotic (human-made) chemicals or other alteration in the natural soil environment. It is typically caused by industrial activity, agricultural chemicals or improper disposal of waste. The most common chemicals involved are petroleum hydrocarbons, polynuclear aromatic hydrocarbons, solvents, pesticides, lead, and other heavy metals. Contamination is correlated with the degree of industrialization and intensity of chemical substance. The concern over soil contamination stems primarily from health risks, from direct contact with the contaminated soil, vapour from the contaminants, or from secondary contamination of water supplies within and underlying the soil. Mapping of contaminated soil sites and the resulting clean ups are time-consuming and expensive tasks, and require expertise in geology, hydrology, chemistry, computer modelling, and GIS in Environmental Contamination, as well as an appreciation of the history of industrial chemistry.

<span class="mw-page-title-main">Methoxychlor</span> Synthetic organochloride insecticide, now obsolete.

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<span class="mw-page-title-main">Dichlorvos</span> Insect killing chemical, organophosphate

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Xenohormones or environmental hormones are compounds produced outside of the human body which exhibit endocrine hormone-like properties. They may be either of natural origin, such as phytoestrogens, which are derived from plants, or of synthetic origin. These compounds can cause endocrine disruption by multiple mechanisms including acting directly on hormone receptors, affecting the levels of natural hormones in the body, and by altering the expression of hormone receptors. The most commonly occurring xenohormones are xenoestrogens, which mimic the effects of estrogen. Other xenohormones include xenoandrogens and xenoprogesterones. Xenohormones are used for a variety of purposes including contraceptive & hormonal therapies, and agriculture. However, exposure to certain xenohormones early in childhood development can lead to a host of developmental issues including infertility, thyroid complications, and early onset of puberty. Exposure to others later in life has been linked to increased risks of testicular, prostate, ovarian, and uterine cancers.

References

  1. ↑ IUPAC Agrochemical information.
  2. 1 2 3 4 5 NIOSH Pocket Guide to Chemical Hazards. "#0365". National Institute for Occupational Safety and Health (NIOSH).
  3. 1 2 3 4 Robert L. Metcalf "Insect Control" in Ullmann's Encyclopedia of Industrial Chemistry Wiley-VCH, Wienheim, 2002. doi : 10.1002/14356007.a14_263
  4. 1 2 Press Release – COP4 – Geneva, 8 May 2009: Governments unite to step-up reduction on global DDT reliance and add nine new chemicals under international treaty, 2009.
  5. ↑ Survey of Industrial Chemistry by Philip J. Chenier (2002), p. 484.
  6. 1 2 "Two young doctors stopped the spread of Kepone poisoning", by Bill McAllister, L.A. Times-Washington Post Service, reprinted in Courier-Journal (Louisville KY), January 5, 1976, p. 1
  7. ↑ Hanson, David J. (15 January 2007). "Those Were The Days". Chemical & Engineering News. 85 (3). American Chemical Society. doi:10.1021/cen-v085n003.p044.
  8. 1 2 Richard Foster, Kepone: The 'Flour' Factory, Richmond Magazine (July 8, 2005).
  9. 1 2 "N° 2430 - Rapport d'information sur l'utilisation du chlordécone et des autres pesticides dans l'agriculture martiniquaise et guadeloupéenne (M. Philippe-Edmond Mariette, Président, et M. Joël Beaugendre, Rapporteur)". www.assemblee-nationale.fr. Retrieved 7 June 2024. Rapport d'information (...) sur l'utilisation du chlordécone et des autres pesticides dans l'agriculture martiniquaise et guadeloupéenne.
  10. ↑ Resiere, Dabor; Lapostolle, Fréderic; Florentin, Jonathan; Banydeen, Rishika; Gueye, Papa; Pujo, Jean; Mégarbane, Bruno; Kallel, Hatem; Névière, Rémi (June 2024). "A health strategy for chlordecone (Kepone) exposure in the French Territories of America". The Lancet. 403 (10443): 2481–2482. doi:10.1016/s0140-6736(24)00883-3. ISSN   0140-6736.
  11. ↑ Delannoy, Matthieu; Girardet, Jean-Michel; Djelti, Fathia; Yen, Frances T.; Cakir-Kiefer, Céline (1 November 2020). "Affinity of chlordecone and chlordecol for human serum lipoproteins" (PDF). Environmental Toxicology and Pharmacology. 80: 103486. doi:10.1016/j.etap.2020.103486. PMID   32891758. S2CID   221523766.
  12. ↑ Asifa, K. P.; Chitra, K. C. (2013). "Determination of median lethal concentration (LC50) and behavioral effects of chlordecone in the cichlid fish, Etroplus maculatus" (PDF). International Journal of Science and Research. 4 (3): 1473–1475.
  13. ↑ Brureau, L.; Emeville, E.; Ferdinand, S.; Thome, J.; Romana, M.; Blanchet, P.; Multigner, L. (2015). "Exposition au chlordécone et cancer de la prostate. Interactions avec les gènes codants pour les œstrogènes". Progrès en Urologie. 25 (13): 755. doi:10.1016/j.purol.2015.08.080. PMID   26544275.
  14. ↑ Luce, Danièle; Dugas, Julien; Vaidie, Amandine; Michineau, Léah; El-Yamani, Mounia; Multigner, Luc (2020). "A cohort study of banana plantation workers in the French West Indies: First mortality analysis (2000–2015)" (PDF). Environmental Science and Pollution Research. 27 (33): 41014–41022. doi:10.1007/s11356-019-06481-4. PMID   31621027. S2CID   204707528.
  15. ↑ Prossnitz, Eric R.; Barton, Matthias (May 2014). "Estrogen biology: New insights into GPER function and clinical opportunities". Molecular and Cellular Endocrinology. 389 (1–2): 71–83. doi:10.1016/j.mce.2014.02.002. PMC   4040308 . PMID   24530924.
  16. ↑ SUGAWARA, SANDRA (25 October 1985). "Virginia's James River Still Is Choked With Pesticide Contamination". Los Angeles Times. Washington Post.
  17. ↑ Jack Cooksey, "What's in the Water?", Richmond Magazine, June 2007. Retrieved 13 June 2012.
  18. ↑ Pruitt v. Allied Chemical Corp., 523 F. Supp. 975 (E.D. Va. 1981).
  19. ↑ Durimel A.; et al. (2013). "pH dependence of chlordecone adsorption on activated carbons and role of adsorbent physico-chemical properties". Chemical Engineering Journal. 229: 239–349. doi:10.1016/j.cej.2013.03.036.
  20. ↑ Wong, Alfred; Ribero, Christine (26 March 2014). "Alternative Agricultural Cropping Options for Chlordecone-Polluted Martinique". Études Caribéennes (26). doi: 10.4000/etudescaribeennes.6710 . Open Access logo PLoS transparent.svg
  21. ↑ Agard-Jones, Vanessa (1 November 2013). "Bodies in the System". Small Axe . 17 (3(42)): 182–192. doi:10.1215/07990537-2378991. S2CID   145642259.
  22. ↑ Chlordécone : les Antilles empoisonnées pour des générations, Le Monde, 6 June 2018.
  23. ↑ "France: Island Paradise With Contaminated Drinking Water". European Journal. Deutsche Welle. 26 May 2010. Archived from the original on 27 May 2010.
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