Chlorinated insecticides, determination

Work on the determination of chlorinated insecticides has been almost exclusively in the area of gas chromatography using different types of detection systems, although a limited amount of work has been carried out using liquid chromatography and thin-layer chromatography. 

Aspila et al. [338] reported the results of an interlaboratory quality control study in five laboratories on the electron capture gas chromatographic determination of ten chlorinated insecticides in standards and spiked and unspiked seawater samples (lindane, heptachlor, aldrin, 5-chlordane, a-chlordane, dield-rin, endrin, p, p -DDT, methoxychlor, and mirex). The methods of analyses used by these workers were not discussed, although it is mentioned that the methods were quite similar to those described in the water quality Branch Analytical Methods Manual [339]. Both hexane and benzene were used for the initial extraction of the water samples. 

In actual practice, environmental samples which are contaminated with PCB are also highly likely to be contaminated with chlorinated insecticides. Many reports have appeared discussing co-interference effects of chlorinated insecticides in the determination of PCB and vice versa, and much of the more recent published work takes account of this fact by dealing with the analysis of both types of compounds. This work is discussed below. 

This technique has been applied to the determination of chlorinated insecticides, carbamate insecticides and substituted urea type herbicides in soil and chloroaliphatic hydrocarbons in non-saline sediments. Separation is usually achieved on thin layers of silica gel or alumina. 

This technique has been used for the determination of polychlorobiphenyls, polychlorodibenzo-p-dioxins, polychlorodibenzofurans, alkyl phosphates, chlorinated insecticides, organophosphorus insecticides, triazine herbicides. Dacthal insecticide, insecticide/herbicide mixtures, mixtures of organic compounds and organotin compounds in soils, and polyaromatic compounds, polychlorobiphenyls, chlorinated insecticides and organotin compounds in non-saline sediments and anionic surfactants in sludges. 

This technique has been used to determine the following types of organic compounds in soil polychlorobiphenyls, chlorinated insecticides, triazine herbicides, paraquat and diquat. 

Goerlitz and Law [59] determined chlorinated insecticides in sediment and bottom material samples, which also contained polychlorobiphenyls by extracting the sample with acetone and hexane. The combined extracts were passed down an alumina column. The first fraction (containing most of the insecticides and some polychlorinated biphenyls and polychlorinated naphthalenes) was eluted with hexane and treated with mercury to precipitate sulphur. If the polychlorinated hydrocarbons interfered with the subsequent gas chromatographic analysis, further purification on a silica gel column was necessary. 

Von Bavel et al. [55] have developed a solid phase carbon trap (PX-21 active carbon) for the simultaneous determination of polychlorodibenzo-p-dioxins and polychlorodibenzofurans also polychlorobiphenyls and chlorinated insecticides in soils using superfluid extraction liquid chromatography for the final determination. Supercritical fluid extraction with carbon dioxide has been applied to the determination of dioxins in soil [114],... 

Mangani et al. [13] have described a method for determining extract chlorinated insecticides in soil. In this procedure a short column is packed with the soil sample. The insecticides in the soil are desorbed by a suitable solvent mixture chosen for its polarity characteristics. 

Sackmauereva et al. [30, 42] have described the method, given below, for the determination of chlorinated insecticides (BHC isomers, DDE, DDT and hexachlorobenzene) in water, fish and sediments. 

Using the gas chromatography methods Sackmayereva et al. [30] obtained from spiked samples the four BHC isomers at 93-103.5% recovery. Both DDT and DDE were yielded in 85.6-94%, 90-93.2%, 90-102.4% and 92-105.8% from sediment. Purification on a Florisil column was used in determining chlorinated insecticides unstable at low pH (Aldrin, Dieldrin). The type and activity of Florisil influence the yield and accuracy of the method. Therefore, the activity of this adsorbent had to be verified and adjusted [36, 37],... 

The procedure described by Suzuki et al. [11, 12], discussed in section 9.1.1.1 for the determination of chlorinated insecticides in soils has also been applied to hexane extracts of river sediments using high-resolution gas chromatography with glass capillary columns. Minimum detectable levels of a-BHC, fs-BHC, -BHC, P-BHC, Heptachlor, Heptachlor epoxide, Aldrin, Dieldrin, Endrin, p,p -DDE, p,p -TDE and p,p -DDT in lOOg samples of bottom sediment were 0.0005, 0.0032, 0.0014, 0.0040, 0.0012, 0.0020, 0.0014, 0.0020, 0.0056, 0.0032, 0.0080 and 0.0120mg kgr1 respectively. 

The method described by Teichman et al. [15] and discussed in section 9.1.1.2 for the determination of chlorinated insecticides and PCBs in soils has also been applied to sediments. The procedure involves adsorption chromatography on alumina and charcoal, elution with increasing fractional amounts of hexane on alumina columns, and with acetonediethyl ether and benzene on charcoal columns. The polychlorobiphenyl and pesticides are then determined by gas chromatography on the separate elutes without interference. 

Mattson and Nygren [57] have described the chromatographic procedure for the determination of polychlorobiphenyls and some chlorinated insecticides in sewage sludge. The capillary column is coated with silicone oil SF 96. 

McIntyre et al. [58, 59] described a method for the analysis of polychlorobiphenyls and chlorinated insecticides in sewage sludges in which homogenized samples are extracted with hexane, concentrated and cleaned up on an alumina/alumina plus silver nitrate column and eluted with hexane. After concentration of the eluent, polychlorobiphenyl and organochlorine compounds were determined by a silica gel chromatographic procedure and gas chromatography. 

Japenga et al. [56] determined polychlorinated biphenyls and chlorinated insecticides in River Elbe estuary sediments by a procedure in which the sediments were pretreated with acetic acid, mixed with silica and Soxhlet-extracted with benzene/hexane. Humic material and elemental sulphur were removed by passing the extract through a chromatographic column containing basic alumina, on which sodium sulphite and sodium hydroxide were adsorbed. Silica fractionation was followed by gas chromatography to analyse chlorinated pesticides, polychlorinated biphenyls and polyaromatic hydrocarbons. Recovery experiments with standard solutions gave recoveries of 90-102%. 

Table 4.2. Application of supercritical fluid extraction to the determination of chlorinated insecticides in soil (from author s own files)...

Again, as in the case of chlorinated insecticides, gas chromatography is the method of choice for the determination of carbamate insecticides (Table 4.4). High-performance liquid chromatography has been used more recently. 

By its nature, gas chromatography is able to handle the analysis of complex mixtures of chlorinated insecticides. It is not surprising therefore, that much of the published work discussed in this section is concerned with the analyses of mixtures of different types of chlorinated insecticides as found in environmental samples. Work on the determination of individual insecticides is reported at the end of this section. 

The American Public Health Association [97,98] published an early gas chromatographic method for the solvent extraction and gas chromatographic determination of 11 chlorinated insecticides in water samples in amounts, down to 0.005mg L 1 p,p -DT)E, p,p -DDT, Aldrin, Dieldrin, Endrin, Heptachlor, Heptachlor epoxide, Lindane, Isodrin and Methoxychlor. The insecticides Carbophenothion, Chlordane, Dioxathion, Diazinon, Ethion, Malathion, Parathion methyl, methyl Trithion, Parathion, Toxaphene and VC-13 may be determined when present at higher levels. Also, the chemicals chlordane, hexachlorobicycloheptadiene and hexachlorocyclopentadiene, which are pesticide manufacturing precursors, may be analysed by this method. 

Suzuki et al. [819] studied the determination of chlorinated insecticides in river and surface waters using high resolution electron capture gas chromatography with glass capillary columns. They compared resolution efficiencies of organochlorine insecticides and their related compounds with wall-coated open tubular (WCOT) and support-coated open tubular (SCOT) glass capillary columns with those of conventional... 

Dolan and Hall [148] have described a Coulson electrolytic conductivity detector of enhanced sensitivity for the gas chromatographic determination of chlorinated insecticides in the presence of PCBs. The detector was modified by the replacement of the silicone-rubber septum and stainless steel fitting at the exit of the pyrolysis furnace with PTFE fitting, by the reduction in diameter of the PTFE transfer tube, and by the... 

Other applications of gas chromatography to the determination of chlorinated insecticides and polychlorobiphenyls in non saline waters are discussed in Table 15.9. 

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