Mirex

Mirex
IUPAC name 1,1a,2,2,3,3a,4,5,5,5a,5b,6-dodecachlorooctahydro-1H-1,3,4-(methanetriyl)cyclobuta[cd]pentalene
Identifiers
CAS number	2385-85-5 Y
KEGG	C14184 N
Jmol-3D images	Image 1
SMILES ClC12C(C3(Cl)Cl)(Cl)C4(Cl)C1(Cl)C(Cl)(Cl)C5(Cl)C4(Cl)C3(Cl)C52Cl
Properties
Molecular formula	C10Cl12
Molar mass	545.54 g mol−1
Melting point	485 °C, 758 K, 905 °F
N (verify) (what is: Y/N?) Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)
Infobox references

Mirex is a chlorinated hydrocarbon 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. Ironically, the spread of the red imported fire ant was actually 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.^[1]

Production and applications

Mirex was first reported in 1946 by Prins^[2] but was not used in pesticide formulations until 1955. Mirex was produced by the dimerization of hexachlorocyclopentadiene in the presence of aluminium chloride.

Mirex is a stomach insecticide. The insecticidal use was focused on Southeastern United States to control the imported fire ants Solenopsis saevissima richteri and Solenopsis invicta. Approximately 250,000 kg of mirex was applied to fields between 1962-75 (US NRC, 1978). Most of the mirex was in the form of "4X mirex bait," which consists of 0.3% mirex in 14.7% soybean oil mixed with 85% corncob grits. Application of the 4X bait was designed to give a coverage of 4.2 g mirex/ha and was delivered by aircraft, helicopter or tractor. 1x and 2x bait were also used. Use of mirex as a pesticide was banned in 1978. The Stockholm Convention banned production and use of several persistent organic pollutant and Mirex was one of the "dirty dozen."^[3]

Degradation

Characteristic of chlorocarbons, mirex does not burn easily; combustion products are expected to include carbon dioxide, carbon monoxide, hydrogen chloride, chlorine, phosgene, and other organochlorine species. Slow oxidation produces chlordecone ("Kepone"), a related insecticide that is also banned in most of the western world. but more readily degraded. Sunlight degrades mirex to photomirex.^[1]

Mirex is highly resistant to microbiological degradation. It only slowly dechlorinates to a monohydro derivative by anaerobic microbial action in sewage sludge and by enteric bacteria. Degradation by soil microorganisms has not been described.

Bioaccumulation and biomagnification

Mirex is highly cumulative and amount depends upon the concentration and duration of exposure. There is evidence of accumulation of mirex in aquatic and terrestrial food chains to harmful levels. After 6 applications of mirex bait at 1.4 kg/ha, high mirex levels were found in some species; turtle fat contained 24.8 mg mirex/kg, kingfishers, 1.9 mg/kg, coyote fat, 6 mg/kg, opossum fat, 9.5 mg/kg, and racoon fat, 73.9 mg/kg. In a model ecosystem with a terrestrial-aquatic interface, sorgum seedlings were treated with mirex at 1.1 kg/ha. Caterpillars fed on these seedlings and their faeces contaminated the water which contained algae, snails, Daphnia, mosquito larvae, and fish. After 33 days, the ecological magnification value was 219 for fish and 1165 for snails.

Although general environmental levels are low, it is widespread in the biotic and abiotic environment. Being lipophilic, Mirex is strongly adsorbed on sediments.

Safety

Mirex is only moderately toxic in single-dose animal studies (oral LD₅₀ values range from 365–3000 mg/kg body weight).^[4] It can enter the body via inhalation, ingestion, and via the skin. The most sensitive effects of repeated exposure in animals are principally associated with the liver, and these effects have been observed with doses as low as 1.0 mg/kg diet (0.05 mg/kg body weight per day), the lowest dose tested. At higher dose levels, it is fetotoxic (25 mg/kg in diet) and teratogenic (6.0 mg/kg per day). Mirex was not generally active in short-term tests for genetic activity. There is sufficient evidence of its carcinogenicity in mice and rats.^{[citation needed]} Delayed onset of toxic effects and mortality is typical of mirex poisoning.^{[citation needed]} Mirex is toxic for a range of aquatic organisms, with crustacea being particularly sensitive.

Mirex induces pervasive chronic physiological and biochemical disorders in various vertebrates. No acceptable daily intake (ADI) for Mirex has been advised by FAO/WHO. IARC (1979) evaluated the carcinogenic hazard resulting from exposure to mirex and concluded that "there is sufficient evidence for its carcinogenicity to mice and rats. In the absence of adequate data in humans, based on above result it can be said that it has carcinogenic risk to humans”. Data on human health effects do not exist.

References

1. ^ ^{a b} Robert L. Metcalf “Insect Control” in Ullmann’s Encyclopedia of Industrial Chemistry” Wiley-VCH, Wienheim, 2002. doi:10.1002/14356007.a14_263
2. ^ H. J. Prins (1946). "Synthesis of Polychloro Combounds with Aluminium Chloride .XI.The Elimination of Hydrogen Chloride from Polychloro Combounds and the Formation of Cyclic Compounds -The Synthesis of Perchlorocyclopentadien". Rec. Trav. Chim. 65 (7-8): 455–467. doi:10.1002/recl.19460650607. 
3. ^ Kaiser KL, The rise and fall of Mirex. Environ.Sci.Technol.1978, 12, 520-528
4. ^ EL-Bayomey AA, IW Somak, and S. Branch. Embryotoxicity of the pesticide Mirex In vitro. Teratogenesis, Carcinogenesis, and Mutagenesis 2002, 22:239-249.

See also

• International Organization for the Management of Chemicals (IOMC), 1995, POPs Assessment Report, December.1995.
• Lambrych KL, and JP Hassett. Wavelength-Dependent Photoreactivity of Mirex in Lake Ontario. Environ. Sci. Technol. 2006, 40, 858-863
• Mirex Health and Safety Guide. IPCS International Program on Chemical Safety. Health and Safety Guide No.39. 1990
• Toxicological Review of Mirex. In support of summary information on the Integrated Risk Information System (IRIS) 2003. U.S. Environmental Protection Agency, Washington DC.