Polychlorinated biphenyl mixtures PCBs

Kubo T, Matsumoto H, Shiraishi E, Nomachi M, Nemoto K, Hosoya K, Kaya K (2007) Selective separation of hydroxy polychlorinated biphenyls (HO-PCBs) by the structural recognition on the molecularly imprinted polymers Direct separation of the thyroid hormone active analogues from mixtures. Anal Chim Acta 589 180... 

Synonym(s) PCB-1016 Polychlorinated biphenyl mixture with 41.5% chlorine PCB-1221 Polychlorinated biphenyl mixture with 21% chlorine PCB-1232 Polychlorinated biphenyl mixture with 32% chlorine PCB-1242 Polychlorinated biphenyl mixture with 41.5% chlorine PCB-1248 Polychlorinated biphenyl mixture with 48% chlorine... 

Another example of industrially useful polychlorinated molecules that have been found to have long-term deleterious environmental and health effects are the polychlorinated biphenyls or PCBs Aroclor, Clophen, Fenclor, Kanechlor, Phenoclor, Pyralene, and Santotherm. (Commercial PCBs are mixtures.) These substances have been listed as carcinogens by the U.S. Environmental Protection Agency, but they were once widely used as hydraulic fluids, plasticizers, adhesives, Are retardants, lubricants, and in carbonless reproducing paper. They are still found in older electrical capacitors and electrical transformers and are widely identified in the environment and chemical dump sites. Newer transformers and capacitors use alternative fluids. 

Many commercial products are complex chemical or physical mixtures. In some cases the use of the type of search scheme described above is not always useful. Sometimes, all that is required is a broad based characterization or a generic identity in terms of a product type. A good example is a polychlorinated biphenyl (a PCB), such as the Arochlor 1254 shown in Figure 8. This time the identification of the individual component polychlorinated compounds would not be useful. Therefore in this case a normal absolute scoring scheme is preferred where the material is treated as a single entity. The computer interpretation (Table 6) accurately classifies the sample as an aromatic material with multiple halogen (ring) substituents. 

The values of n and the corresponding N which are necessary to resolve 50-90% of the constituents of a mixture of 100 compounds are listed in Table 1.5, thus making clear the limitations of one-dimensional chromatography. For example, to resolve over 80 % of the 100 compounds by GC would require a column generating 2.4 million plates, which would be approximately 500 m long for a conventional internal diameter of 250 p.m. For real mixtures, the situation is even less favourable to resolve, for example, 80 % the components of a mixture containing all possible 209 polychlorinated biphenyls (PCBS) would require over lO plates. 

PCDFs are similar in many respects to PCDDs but have been less well studied, and will be mentioned only briefly here. Their chemical structure is shown in Figure 7.1. Like PCDDs, they can be formed by the interaction of chlorophenols, and are found in commercial preparations of chlorinated phenols and in products derived from phenols (e.g., 2,4,5-T and related phenoxyalkanoic herbicides). They are also present in commercial polychlorinated biphenyl (PCB) mixtures, and can be formed... 

Valnes of have been measnred for a number of polychlorinated biphenyl (PCB) congeners and applied to a nnmber of commercial PCB mixtures. Both the number and the position of the chlorine snbstitnents affected the depletion of C, and this reflected the mannfacturing procednres that involved kinetic isotope effects as well as the source of the biphenyl starting material (Jarman et al. 1998). It was snggested that this could be applied to determine the source of PCBs in the environment. 

The most critical decision to be made is the choice of the best solvent to facilitate extraction of the drug residue while minimizing interference. A review of available solubility, logP, and pK /pKb data for the marker residue can become an important first step in the selection of the best extraction solvents to try. A selected list of solvents from the literature methods include individual solvents (n-hexane, " dichloromethane, ethyl acetate, acetone, acetonitrile, methanol, and water ) mixtures of solvents (dichloromethane-methanol-acetic acid, isooctane-ethyl acetate, methanol-water, and acetonitrile-water ), and aqueous buffer solutions (phosphate and sodium sulfate ). Hexane is a very nonpolar solvent and could be chosen as an extraction solvent if the analyte is also very nonpolar. For example, Serrano et al used n-hexane to extract the very nonpolar polychlorinated biphenyls (PCBs) from fat, liver, and kidney of whale. One advantage of using n-hexane as an extraction solvent for fat tissue is that the fat itself will be completely dissolved, but this will necessitate an additional cleanup step to remove the substantial fat matrix. The choice of chlorinated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride should be avoided owing to safety and environmental concerns with these solvents. Diethyl ether and ethyl acetate are other relatively nonpolar solvents that are appropriate for extraction of nonpolar analytes. Diethyl ether or ethyl acetate may also be combined with hexane (or other hydrocarbon solvent) to create an extraction solvent that has a polarity intermediate between the two solvents. For example, Gerhardt et a/. used a combination of isooctane and ethyl acetate for the extraction of several ionophores from various animal tissues. 

Chemicals degraded by WRF include pesticides such as organochlorines DDT and its very toxic metabolite DDE [8, 9] and organophosphate pesticides such as chlorpyrifos, fonofos and terbufos [10] polychlorinated biphenyls (PCBs) of different degrees of chlorine substitution [11-13], some even to mineralization [14, 15] diverse polycyclic aromatic hydrocarbons (PAHs) in liquid media and from contaminated soils or in complex mixtures such as creosote [16-18] components of munition wastes including TNT and its metabolites DNT [19-23], nitroglycerin [24] and RDX [25]. 

The quantitative environmental analysis of surfactants, such as alcohol ethoxylates, alkylphenol ethoxylates (APEOs) and linear alkylbenzene sulfonates (LASs), is complicated by the presence of a multitude of isomers and oligomers in the source mixtures (see Chapter 2). This issue bears many similarities to the quantitation problems that have occurred with halogenated aromatic compound mixtures, e.g. polychlorinated biphenyls (PCBs) [1]. 

Polychlorinated biphenyls (PCBs) were manufactured by catalytic chlorination of biphenyl to produce complex mixtures, each containing 60-90 different PCB molecular species or congeners (see Chaps. 1 and 4). In the United States, PCB mixtures were manufactured by Monsanto under the trade name Aroclor and were widely used as dielectric fluids in capacitors and transformers from 1929 to 1978. PCBs are widespread contaminants of aquatic sediments and continue to be a focus of environmental concern because they tend to accumulate in biota and are potentially toxic. The following sections show the most effective bioremediation techniques applied to various PCB contaminated environments ... 

GC-EI-MS permits the direct analysis of mixtures, e.g., to analyze synthetic byproducts an advantage that made GC-EI-MS benchtop instruments become widespread in modem synthetic laboratories. The GC-EI-MS combination is especially successful in monitoring environmental pollutants such as polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), polychlorinated dibenzo-dioxins (PCDDs), polychlorinated dibenzofuranes (PCDFs), or other volatile organic compounds (VOCs). 

A principal components multivariate statistical approach (SIMCA) was evaluated and applied to interpretation of isomer specific analysis of polychlorinated biphenyls (PCBs) using both a microcomputer and a main frame computer. Capillary column gas chromatography was employed for separation and detection of 69 individual PCB isomers. Computer programs were written in AMSII MUMPS to provide a laboratory data base for data manipulation. This data base greatly assisted the analysts in calculating isomer concentrations and data management. Applications of SIMCA for quality control, classification, and estimation of the composition of multi-Aroclor mixtures are described for characterization and study of complex environmental residues. 

Biological. Reported degradation products by the microorganism Alcaligenes BM-2 for a mixture of polychlorinated biphenyls include monohydroxychlorobiphenyl, 2-hydroxy-6-oxochlorophenylhexa-2,4-dieonic acid, chlorobenzoic acid, chlorobenzoylpropionic acid, chlorophenylacetic acid, and 3-chlorophenyl-2-chloropropenic acid (Yagi and Sudo, 1980). When PCB-1016 was statically incubated in the dark at 25 °C with yeast extract and settled domestic wastewater inoculum, no significant biodegradation was observed. At a concentration of 5 mg/L, percent losses after 7, 14, 21, and 28-d incubation periods were 44, 47, 46, and 48, respectively. At a concentration of 10 mg/L, only 22, 46, 20, and 13% losses were observed after the 7, 14, 21, and 28-d incubation periods, respectively (Tabak et al., 1981). 

The potential of modern chemical instrumentation to detect and measure the conposition of coirplex mixtures has made it necessary to consider the use of methods of multivariable data analysis in the overall evaluation of environmental measurements. In a number of instances, the category (chemical class) of the compound that has given rise to a series of signals may be known but the specific entity responsible for a given signal may not be. This is true, for example, for the polychlorinated biphenyls (PCB s) in which the clean-up procedure and use of specific detectors eliminates most possibilities except PCB s. Such hierarchical procedures simplify the problem somewhat but it is still advantageous to apply data reduction methods during the course of the interpretation process. 

Clearly, humans are exposed to a complex mixture of CDDs and other halogenated aromatic hydrocarbons such as chlorinated diben-zofurans (CDF) and polychlorinated biphenyls (PCBs). The toxicological concerns resulting from exposure to mixtures, as well as the gaps... 

The polychlorinated biphenyls (PCBs, coplanar biphenyls) have been used in a large variety of applications as dielectric and heat transfer fluids, lubricating oils, plasticizers, wax extenders, and flame retardants. Their industrial use and manufacture in the USA were terminated by 1977. Unfortunately, PCBs persist in the environment. The products used commercially were actually mixtures of PCB isomers and homologs containing 12-68% chlorine. These chemicals are highly stable and highly lipophilic, poorly metabolized, and very resistant to environmental degradation they bioaccumulate in food chains. Food is the major source of PCB residues in humans. 

Borlakoglu JT, Wilkins JP. 1993. Metabolism of di-, tri- and tetrabromobiphenyls by hepatic microsomes isolated from control animals and animals treated with Aroclor 1254, a commercial mixture of polychlorinated biphenyls (PCBs). Comp Biochem Physiol C 105(1) 107-112. 

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