Chlorine PCBs and

Measurements of POCs in the snow and glacial ice of mountains have revealed that anthropogenic contaminants are not only present in these media, but that some occur at higher concentrations at higher elevations than at lower elevations [3,40], Specifically, the HCHs, lower chlorinated PCBs and endosulfan showed this trend in the mountains of Western Canada [3], while p, p -DDT and p, p -DDD did so in snow collected from four elevations on Mt. Everest [40],... 

Recently, the PCB-biodegradative capabilities of methanotrophs have been demonstrated (Adriaens, 1994). In this study, 2-CB was oxidized by a methanotrophic culture (CSC1) to a hydroxylated chlorobiphenyl intermediate identified as 2-hydroxy-3-chlorobiphenyl. This intermediate indicated that the metabolite was formed via a concerted oxidation involving an arene oxide which rearranges spontaneously via an NIH shift. No studies have shown, however, that methanotrophs can degrade more highly chlorinated PCBs, and their utility for bioremediation processes does not seem promising. 

Aroclor 5442 was eight times more estrogenically active in rats than some low chlorinated PCBs, whereas highly chlorinated PCBs and PCTs were inactive [51]. The reproductive effect of PCTs has only been studied in the laboratory. A greater number of abnormal white leghorn chicken embryos was noted after a 20 mg/kg diet of Aroclor 5460 [56]. The hatchability was not effected, even after a 20 mg/kg diet of Aroclor 5442 [57]. 

A chemical destruction method that has been used for the treatment of PCBs in contaminated dielectric liquids or soil is based on the reaction of a polyethylene glycol/potassium hydroxide mixture with PCBs (De Filippis et al. 1997). This method can be used successfully for the destruction of higher chlorinated PCBs with an efficiency of >99%, but was found to be unsuitable for the treatment of di- and trichlorobiphenyls due to low destruction efficiencies (Sabata et al. 1993). Irradiation of PCBs in isooctane and transformer oil by y-radiation resulted in degradation of PCBs to less chlorinated PCBs and PCB-solvent adducts (Arbon et al. 1996). Supercritical fluid technology has shown promise as a method for extraction of PCBs from soils, coupled with supercritical water oxidation of the extracted PCBs (Tavlarides 1993,1998a). Hofelt and Shea (1997) demonstrated the use of semipermeable membrane devices to accumulate PCBs from New Bedford Harbor, Massachusetts water. Another method showing... 

I or chlorinated PCBs and PAHs ]ogK01v=(n+l)blogKo0w where n = number of Cl atoms h log/C°w, (Kow of parent compound)... 

Highly chlorinated PCBs and pesticides (e.g., mirex and DDT) may be dechlorinated anaerobically by functioning as an electron acceptor. DDT is dechlorinated to DDD by many facultative anaerobic microorganisms under anoxic conditions. DDD can be further dechlorinated or degraded aerobically. 

The performance of SCWO for waste treatment has been demonstrated (15,16). In these studies, a broad number of refractory materials such as chlorinated solvents, polychlorinated biphenyls (PCBs), and pesticides were studied as a function of process parameters (17). The success of these early studies led to pilot studies which showed that chlorinated hydrocarbons, including 1,1,1-trichloroethane /7/-T5-6y,(9-chlorotoluene [95-49-8] and hexachlorocyclohexane, could be destroyed to greater than 99.99997, 99.998, and 99.9993%, respectively. In addition, no traces of organic material could be detected in the gaseous phase, which consisted of carbon dioxide and unreacted oxygen. The pilot unit had a capacity of 3 L/min of Hquid effluent and was operated for a maximum of 24 h. 

TSCA also addresses the problem of polychlorinated biphenyls (PCBs) and chlorinated fluorocarbons (CECs). EPA has developed regulations on the cleanup, handling, and disposal of PCBs. The manufacture and use of CECs has been banned for all but essential uses, in accordance with the Montreal Agreement, an international treaty on worldwide use of CECs. 

Reaction vessels for supercritical water oxidation must be highly corrosion resistant because of the aggressive nature of supercritical water and oxidation reaction products at extreme temperatures and pressures. Supercritical oxidation of PCBs and some chlorinated hydrocarbons can be difficult... 

Aerobic, Anaerobic, and Combined Systems. The vast majority of in situ bioremediations ate conducted under aerobic conditions because most organics can be degraded aerobically and more rapidly than under anaerobic conditions. Some synthetic chemicals are highly resistant to aerobic biodegradation, such as highly oxidized, chlorinated hydrocarbons and polynuclear aromatic hydrocarbons (PAHs). Examples of such compounds are tetrachloroethylene, TCE, benzo(a)pyrene [50-32-8] PCBs, and pesticides. 

Environmental problems associated with PCBs are the result of a number of factors. Several open uses of PCBs have resulted in thein direct introduction into the environment, eg, organic diluents careless PCB disposal practices have resulted in significant releases into aquatic and marine ecosystems higher chlorinated PCBs are very stable in thein persistence in different environmental matrices and by a variety of processes (Fig. 1) PCBs are transported throughout the global ecosystem and preferentiaHy bioconcentrate in higher trophic levels of the food chain. 

SW-846, is used to measure emissions of semivolatile principal organic constituents. Method 0010 is designed to determine destruction and removal efficiency (DRE) of POHCs from incineration systems. The method involves a modification of the EPA Method 5 sampling train and may be used to determine particulate emission rates from stationary sources. The method is applied to semivolatile compounds, including polychlorinated biphenyls (PCBs), chlorinated dibenzodioxins and dibenzofurans, polycyclic organic matter, and other semivolatile organic compounds. 

An appreciation of the extent to which invertebrate species may be exposed to such chemicals comes from considering the effects of complex mixtures. In the North Atlantic ecosystem alone, hundreds of pollutant chemicals have been identified. These include metals, synthetic and chlorinated organics and polycyclic aromatic hydrocarbons. Over 300 aromatic hydrocarbons have been detected in some regions of the Chesapeake Bay, and high concentrations of PCBs have been... 

Zebiihr et al. (29) developed an automated system for determining PAHs, PCBs and PCDD/Fs by using an aminopropyl silica column coupled to a porous graphitic carbon column. This method gives five fractions, i.e. aliphatic and monoaromatic hydrocarbons, polycyclic aromatic hydrocarbons, PCBs with two or more ortho-chlorines, mono-ort/io PCBs, and non-ortho PCBs and PCDD/Fs. This method employed five switching valves and was successfully used with extracts of sediments, biological samples and electrostatic filter precipitates. 

As recently as 1970, only about 30 naturally occurring organohalogen compounds were known. It was simply assumed that chloroform, halogenated phenols, chlorinated aromatic compounds called PCBs, and other such substances found in the environment were industrial pollutants. Now, only a third of a century later, the situation js quite different. More than 5000 organohalogen compounds have been found to occur naturally, and tens of thousands more surely exist. From a simple compound like chloromethane to an extremely complex one like vancomycin, a remarkably diverse range of organohalogen compounds exists in plants, bacteria, and animals. Many even have valuable physiological activity. Vancomycin, for instance, is a powerful antibiotic produced by the bacterium Amycolatopsis orientalis and used clinically to treat methicillin-resistant Staphylococcus aureus (MRSA). 

Although higher chlorinated PCBs are degraded more rapidly than lower chlorinated ones in anaerobic sediments, the reverse is true in terrestrial and aquatic food chains (see Section 6.2.2). As explained earlier, hydroxylations tend to be very slow... 

PCB mixtures were once used for a variety of purposes, and came to cause widespread environmental pollution. Over 100 different congeners are present in commercial products such as Aroclor 1248 and Aroclor 1254. PCBs are lipophilic, stable, and of low vapor pressure. Many of the more highly chlorinated PCBs are refractory, showing very strong biomagnification with movement along food chains. 

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... 

---