Insecticide chlorinated cyclodiene

Below-grade bioremediation is an ex situ technology designed to treat soil, sludge, and sediment impacted with chlorinated cyclodiene insecticides such as chlordane and heptachlor. Naturally occurring fungi are added to pesticide-contaminated soil, which is then treated in a below-grade actively aerated bioremediation cell. 

Manclus, J.J., A. Abad, M.Y. Lebedev, et al. 2004. Development of a monoclonal immunoassay selective for chlorinated cyclodiene insecticides. J. Agric. Food Chem. 52 2776-2784. 

Heptachloronorbornene (l,2,3,4,5,7,8-heptachlorobicyclo[2,2,l]hept-2-ene) is produced by the Diels-Alder reaction by addition of vinylchloride to cyclopen-tadiene. This product is converted by dehydrochlorination to hexachloronor-bornadiene (l,2,3,4,7,7-hexachlorobicyclo[2,2,l]hepta-2,5-diene) which is an intermediate in the syntheses of the stable chlorinated cyclodiene insecticides. Hexachloronorbornadiene (HCND) and heptachloronorbornene are very hydrophobic chemical intermediates with very high log Kqw values of 5.15... 

Chemical/Pharmaceutical/Other Class Organo-chlorine cyclodiene insecticide... 

Epoxidation or the insertion of an oxygen atom into a carbon-carbon double bond can frequently result in the formation of products with greater environmental toxicity. Various microorganisms can catalyze the reaction of the chlorinated cyclodiene insecticides aldrin, isodrin, and heptachlor to their more toxic epoxide derivatives. 

A rapid, competition immunoassay has been developed that detects chlorinated cyclodiene insecticides in meat, fish and milk products. The assay, a competition enzyme-linked inununosorbent assay, employs a monoclonal antibody that recognized all of the cyclodiene insecticides it was tested against. A simple method to extract heptachlor and related cyclodiene insecticides that is compatable with the immunoassay is described. The sensitivity of the immunoassay is sufficent to detect cyclodienes at the tolerance level in beef. We anticipate initial application of this assay as a screening aid. 

The use of chlorinated, cyclodiene insecticides in agricultgure production by and large has been phased out with the exception of endosulfan. 

A cELISA using LLNL-Hept-2. capable of detection heptachlor and other related chlorinated cyclodiene insecticides in spiked meat, fish and dairy samples was developed. Our cleanup method did not remove all of the substance(s) that interfered with the cELlSA. Such substances were observed in the hexane extracted material from all three matrixes investigated. Our data suggests that the beef fat has the highest level of interfering substances and heavy dairy cream the lowest level. The exact nature of these substances are not known. 

Since LLNL-Hept-2 binds all of the chlorinated cyclodiene insecticides tested, a positive response in the cELISA represents an integrated value and does not identify a specific insecticide. Uncertainty about the exact composition of the contamination is a result of cross-reactivity with related chemicals and occurs even with monoclonal antibodies. However, monoclonal antibodies are invariant reagents that need to be extensively characterized only once to determine the range of compounds detected and their relative sensitivities. In contrast, polyclonal antibodies need to be... 

Further studies of spiked and incurred tissues using both the cELISA and a more traditional chemical assay for chlorinated cyclodiene insecticides are needed to demonstrate the reliability of the cELISA. Such studies also will permit an evaluation of the level of false negatives and/or false positives detected by the immunoassay. This latter point is of key importance for defining a useful screening method. 

After examination of 106 chlorinated cyclodiene insecticides on six selected types of insect. Soloway (1965) concluded that a strict geometry governs ability to react with insect receptors. Two electron-rich sites are required (Cl, O, N, S, or double bond) for electrostatic adsorption (dihydro-aldrin has only one such site, and has only a low toxicity to insects). Aldrin 6.46) is a typical example. Chemically it is efo- wrf(9-l,2,3,4,10,10-hexachloro-l,4 5,8-dimethano-hexa-hydronaphthalene. The critical outline which these nearly spherical molecules require for activity is shown in 6,47), it was produced by viewing molecular models along a line joining the bridgehead (methano) atoms. Lindane, which has a similar mode of action, has a similar outline. For further details of structure—action relationships, see Brooks (1974). 

The chlorinated cyclodiene insecticides act in a biologically different way from the DDT—pyrethrin group of insecticides and have different steric requirements. Soloway (1965) examined 106 cyclodienes and concluded that, for high activity, they should be nearly spherical. Proceeding to detail, he projected a model of aldrin on to a plane and obtained the outline of a highly modulated circle. Molecules which could just traverse through an aperture of these dimensions, see 6.47), scored well as insecticides. In addition, the presence of two electron-attracting substituents (usually chlorine atoms) was necessary. 

Technical chlordane is a mixture of chlorinated hydrocarbons that has been used as an insecticide since its introduction in 1947. Chlordane was the first cyclodiene insecticide to be used in agriculture and was the second most important organochlorine insecticide in the United States in 1976/1977, behind toxaphene, with an estimated annual production of 9 million kg (Nomeir and Hajjar 1987). Chlordane is a leading insecticide in controlling termites, with about 1.2 million homes in the United States alone treated annually for this purpose (Nomeir and Hajjar 1987). 

A second organochlorine pesticide, heptachlor (HEP), a chlorinated cyclodiene that was used primarily as an agricultural and domestic insecticide, was evaluated for its potential to suppress the immune system of rats. Rats were exposed to HEP pre-and postnatally, as described above for MXC. The IgM antibody response to SRBCs was suppressed at all doses in males but not females at 8 weeks of age. At 26 weeks of age, the IgG anti-SRBC response was suppressed in all of the HEP-exposed males, but not females.131... 

Folmar LC. 1978. In vitro inhibition of rat brain ATPase, pNPPase, and ATP-32Pi exchange by chlorinated-diphenyl ethanes and cyclodiene insecticides. Bull Environ Contam Toxicol 19(4) 481-488. 

Ivie, G.W. and Casida, J.E. Photosensitizers for the accelerated degradation of chlorinated cyclodienes and other insecticide chemicals exposed to sunlight on bean leaves, / Agric. Food Chem., 19(3) 410-416, 1971a. 

As seen from the structural formulas in Figure 16.4, the organochlorine insecticides are of intermediate molecular mass and contain at least one aromatic or nonaromatic ring. They can be placed in four major chemical classes. The first of these consists of the chloroethylene derivatives, of which DDT and methoxychlor are the prime examples. The second major class is composed of chlorinated cyclodiene compounds, including aldrin, dieldrin, and heptachlor. The most highly chlorinated members of this class, such as chloredecone, are manufactured from hexachlorocyclo-pentadiene (see Section 16.3). The benzene hexachloride stereoisomers make up a third class of organochlorine insecticides, and the third group, known collectively as toxaphene, constitutes a fourth. 

Chlorinated ring systems, such as cyclodiene insecticides dieldrin and aldrin react to CO2 and HCl during irradiation with UVdight (X > 290 nm). By using... 

Cyclodienes are chlorinated hydrocarbon insecticides with a polycyclic structure and, as the name implies, two unsaturated bonds. Not all of the insecticides in this class meet these criteria. Chlordane, for example, contains only one double bond in its polycyclic structure. Endrin and dieldrin are epoxides of the cyclodienes isodrin and aldrin, respectively. 

Researchers were also able to establish the link between declines of other predatory species such as the European sparrowhawk and the use of organo-chlorine pesticides other than DDT. For instance, the cyclodiene insecticides aldrin, dieldrin, and he-ptachlor used as seed treatments caused massive mortality of both seed-eating species and their predators. All of the insecticides had the following points in common they were highly soluble in fats and refractory to metabolism. The impacts on the predatory species typically take place in periods of food stress when fat soluble residues are released from fat stores and returned into general circulation. In a food-stressed individual, the brain remains as the most lipid rich tissue and this is where contaminants move to. Toxicity results when threshold values in brain tissue are exceeded. At sublethal levels, documented effects of cyclodiene insecticides in birds have included changes in their reproductive, social, and avoidance behaviors. 

CABA receptors - antagonists Active plant alkaloids, mainly convulsants, include bicuculline and picrotoxin (active principle is picrotoxinin). Important synthetic agents include the synthetic chlorinated hydrocarbon (cyclodiene) insecticide dieldrin, which is similar to many other insecticides, including aldrin, heptachlor and chlordane. In mammals they cause central stimulation and convulsions. 

Halogeno-alkenes.- The photochemical behaviour of AJdrm (30a) is complex. A reinvestigation of the irradiation of this cyclodiene insecticide in hexane has isolated two new photo products (30b) and (31). Irradiation in acetone also provides surprises and the two new adducts (32) and (33) have been identified. The influence of triethylamine on photodehalogenation of cyclodiene insecticides has also been evaluated. Irradiation appears to bring about selective dehalogenation at C-11 in (30a) yielding a 9 1 mixture of the products (34a) and (34b). This stereoselective loss of chlorine is also seen with Dieldrin (35) and Endrin (36). ... 

Heptachlor [76-44-8], another cyclodiene insecticide of chemical structure similar to chlordane is a chlorination product of chlordane. Technical grade heptachlor contains about 73% heptachlor, 22% fran -chlordane and 5% nonachlor. This pesticide was extensively used until 1970s for the control of soil insects, cotton insects, grasshoppers and termite control. The use of this pesticide for underground termite control was banned in the United States in 1988. Its application after that was restricted to controlling fire ant in power transformers. The U.S. EPA has classified heptachlor as a Group B2 probable human carcinogen. 

Their presence in these products is not surprising since as a group the cyclodienes are apolar, lipophilic compounds. Acceptable daily intake for cyclodienes has been established by the World Health Organization and tolerance limits in meats and poultry set by the US-EPA. Development of an immunoassay for these compounds would greatly facilitate improved monitoring for cyciodienes in foods and environmental samples. We have isolated a monoclonal antibody, LLNL-Hept-2. that detects cyclodiene insecticides and have used this antibody to develop an immunoassay that is able to detect heptachlor (and related chlorinated cyciodienes) in meat, flsh and dairy products. 

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