Chlordane

Production, composition and uses

Technical chlordane development was by chance at Velsicol Chemical Corporation by Julius Hyman in 1948, during a search for possible uses of a by-product of synthetic rubber manufacturing. By chlorinating this by-product, persistent and potent insecticides were easily and cheaply produced. The chlorine atoms, 7 in the case of heptachlor, 8 in chlordane, and 9 in the case of nonachlor, surround and stabilize the cyclodiene ring and thus these compounds are referred to as cyclodienes. Other members of the cyclodiene family of organochlorine insecticides are aldrin and its epoxide, dieldrin, as well as endrin, which is a stereoisomer of dieldrin. Cyclodiene derives its name from hexachlorocyclopentadiene, a precursor in its production.

Hexachlorocyclopentadiene forms a Diels-Alder adduct with cyclopentadiene to give chlordene intermediate [3734-48-3]; chlorination of this adduct gives predominantly two chlordane isomers, α and β, in addition to other products such as trans-nonachlor and heptachlor. The β-isomer is popularly known as gamma and is more bioactive.

Cis-chlordane.svg|cis-chlordane (also known as α-chlordane (CAS=5103-71-9)) Trans-chlordane.svg|trans-chlordane (also known as γ-chlordane and gamma-chlordane (CAS=5103-74-2)) Trans-nonachlor.svg|trans-nonachlor (+)-Heptachlor.svg|(+)-heptachlor

Chlordane appears as a white or off-white crystals when synthesized, but it was more commonly sold in various formulations as oil solutions, emulsions, sprays, dusts, and powders. These products were sold in the United States from 1948 to 1988.

Because of concern for harm to human health and to the environment, the United States Environmental Protection Agency (EPA) banned all uses of chlordane in 1983, except termite control in wooden structures (e.g. houses). After many reports of chlordane in the indoor air of treated homes, EPA banned the remaining use of chlordane in 1988.Pesticides and Breast Cancer Risk: Chlordane , Fact Sheet #11, March 1998, Program on Breast Cancer and Environmental Risk Factors Cornell University The EPA recommends that children should not drink water with more than 60 parts of chlordane per billion parts of drinking water (60 ppb) for longer than 1 day. EPA has set a limit in drinking water of 2 ppb.

Chlordane is very persistent in the environment because it does not break down easily. Tests of the air in the residence of U.S. government housing, 32 years after chlordane treatment, showed levels of chlordane and heptachlor 10-15 times the Minimal Risk Levels (20 nanograms/cubic meter of air) published by the Centers for Disease Control. It has an environmental half-life of 10 to 20 years.

Origin, pathways of exposure, and processes of excretion

Environmental impact

Being hydrophobic, chlordane adheres to soil particles and enters groundwater only slowly, owing to its low solubility (0.009 ppm). It requires many years to degrade. Chlordane bioaccumulates in animals. It is highly toxic to fish, with an of 0.022–0.095 mg/kg (oral).

Oxychlordane (C10H4Cl8O), the primary metabolite of chlordane, and heptachlor epoxide, the primary metabolite of heptachlor, along with the two other main components of the chlordane mixture, cis-nonachlor and trans-nonachlor, are the main bioaccumulating constituents. trans-Nonachlor is more toxic than technical chlordane and cis-nonachlor is less toxic.

Chlordane and heptachlor are known as persistent organic pollutants (POP), classified among the "dirty dozen" and banned by the 2001 Stockholm Convention on Persistent Organic Pollutants.

Health effects

Exposure to chlordane/heptachlor and/or its metabolites (oxychlordane, heptachlor epoxide) are risk factors for type-2 diabetes, for lymphoma, for prostate cancer, for obesity, for testicular cancer, for breast cancer.

An epidemiological study conducted by the National Cancer Institute reported that higher levels of chlordane in dust on the floors of homes were associated with higher rates of non-Hodgkin lymphoma in occupants. Breathing chlordane in indoor air is the main route of exposure for these levels in human tissues. Currently, EPA has defined a concentration of 24 nanogram per cubic meter of air (ng/M3) for chlordane compounds over a 20-year exposure period as the concentration that will increase the probability of cancer by 1 in 1,000,000 persons. This probability of developing cancer increases to 10 in 1,000,000 persons with an exposure of 100 ng/m3 and 100 in 1,000,000 with an exposure of 1000 ng/m3.

The non-cancer health effects of chlordane compounds, which include diabetes, insulin resistance, migraines, respiratory infections, immune-system activation, anxiety, depression, blurry vision, confusion, intractable seizures as well as permanent neurological damage, probably affects more people than cancer. Trans-nonachlor and oxychlordane in serum of mothers during gestation has been linked with behaviors associated with autism in offspring at age 4–5. The Agency for Toxic Substances and Disease Registry (ATSDR) has defined a concentration of chlordane compounds of 20 ng/m3 as the Minimal Risk Level (MRLs). ATSDR defines Minimal Risk Level as an estimate of daily human exposure to a dose of a chemical that is likely to be without an appreciable risk of adverse non-cancerous effects over a specific duration of exposure.

Remediation

Chlordane was applied under the home/building during treatment for termites and the half-life can be up to 30 years. Chlordane has a low vapor pressure and volatilizes slowly into the air of home/building above. To remove chlordane from indoor air requires either ventilation (Heat Exchange Ventilation) or activated carbon filtration. Chemical remediation of chlordane in soils was attempted by the US Army Corps of Engineers by mixing chlordane with aqueous lime and persulfate. In a phytoremediation study, Kentucky bluegrass and Perennial ryegrass were found to be minimally affected by chlordane, and both were found to take it up into their roots and shoots. Mycoremediation of chlordane in soil have found that contamination levels were reduced. The fungus Phanerochaete chrysosporium has been found to reduce concentrations of chlordane by 21% in water in 30 days and in solids in 60 days.

References

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