Chlorophenols, polychlorinated

Such xenobiotics as aliphatic hydrocarbons and derivatives, chlorinated ahphatic compounds (methyl, ethyl, methylene, and ethylene chlorides), aromatic hydrocarbons and derivatives (benzene, toluene, phthalate, ethylbenzene, xylenes, and phenol), polycyclic aromatic hydrocarbons, halogenated aromatic compounds (chlorophenols, polychlorinated biphenyls, dioxins and relatives, DDT and relatives), AZO dyes, compounds with nitrogroups (explosive-contaminated waste and herbicides), and organophosphate wastes can be treated effectively by aerobic microorganisms. 

Chlorophenols may contain a variety of by-products and contaminants such as other chlorophenols, polychlorinated phenoxy-phenols and neutral compounds like polychlorinated benzenes and diphenyl ethers, PCDDs and PCDFs (39). Some of these contaminants may also occur in chlorophenol derivatives like phenoxy acids, other pesticides and hexachlorophene. The possible presence of PCDDs and PCDFs is of special significance because of their extraordinary toxicological properties. 

Laine, M.M., Ahtiainen, J., Wagman, N., Oberg, L.G., and Jprgensen, K.S. 1997. Fate and toxicity of chlorophenols, polychlorinated dibenzo-/ -dioxins, and dibenzofurans during composting of contaminated sawmill sod. Environmental Science and Technology, 31 3244-50. 

To conclude, strong acids and Lewis acids transform polychlorinated gem-dichlorocyclohexadienones in chlorophenols. Polychlorinated gem-dichlorocyclo-hexadienones are true intermediates in the formation of chlorophenols that have one chlorine atom in meta position of the OH. 

Determination of C -C cai bonyl compounds, phthalic acid alkyl esters, mutagen MX and its geometric isomer E-MX, chlorophenols, organochlorine pesticides (OCPs) - a-, P-, J-, 5-HCH, DDE, DDD, DDT, total isomeric-specific content of polychlorinated byphenyls (PCBs) (tri-, tetra-, penta-, hexa-, hepta-, octachloroisomers) in SCAN and SIM mode was canned out. MDE of procedure for OCPs makes up 0.01-0.1 and PCBs - 0.17-0.38 ng/1 at enrichment factor K = (1.50-4.00)T0. ... 

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... 

Schnaak et al. [4] Polychlorinated terphenyls, naphthalenes, chloropesticides, halogenated hydrocarbon solvents, aromatic hydrocarbon solvents (BTEX), chlorobenzenes, poly aromatic hydrocarbons (EPA 610), phenols, chlorophenols, phthalates, petroleum hydrocarbons, LAS and nonylphenol (NP), organotin compounds and 2,4-dichloroaniline 1 pg/kg to 10 mg/kg for chlorine-contained compounds 10 pg/kg to 1 g/kg for solvent and phenols 1 mg/kg to 10 g/kg for EPA610, DEHP, LAS, and mineral oils Sewage sludge... 

Organochlorinated substances Polychlorinated biphenyls Chlorophenols Dioxins... 

Fig. 7 Generic chemical structures of polyhalogenated compounds. X=C1, Br. (I) Polychlorinated biphenyls (PCBs), polybrominated biphenyls (PBBs) (II) chlorophenols (CPs), bromophenols (BPs) (III) polychlorinated diphenyl ethers (PCDE), polybrominated diphenyl ethers (PBDE) (IV) polychlorinated dibenzo-p-dioxin (PCDD), polybrominated dibenzo-p-dioxin (PBDD) (V) polychlorinated dibenzofuran (PCDF), polybrominated dibenzofuran (PBDF) (VI) tetrabromobisphenol A (TBBPA)...

The ARS Technologies, Inc., Ferox process is an in situ remediation technology for the treatment of chlorinated hydrocarbons, leachable heavy metals, and other contaminants. The process involves the subsurface injection and dispersion of reactive zero-valence iron powder into the saturated or unsaturated zones of a contaminated area. ARS Technologies claims that Ferox is applicable for treating the following chemicals trichloroethene (TCE), 1,1,1-trichloroethane (TCA), carbon tetrachloride, 1,1,2,2-tetrachloroethane, lindane, aromatic azo compounds, 1,2,3-trichloropropane, tetrachloroethene (PCE), nitro aromatic compounds, 1,2-dichloroethene (DCE), vinyl chloride, 4-chlorophenol, hexachloroethane, tribromomethane, ethylene dibromide (EDB), polychlorinated biphenyls (PCBs), Freon-113, unexploded ordinances (UXO), and soluble metals (copper, nickel, lead, cadmium, arsenic, and chromium). 

Micro-Flo has been used at many sites throughout Canada to treat wastewater and surface water contaminated with polychlorinated biphenyls (PCBs), chlorophenols, polycyclic aromatic hydrocarbons (PAHs), phenols, dioxins, furans, hydrocarbons, metals, oil, and grease. The technology has also been used to treat water contaminated with paint, paint thinner, and paint solvents. 

These investigations have shown significant associations with several types of cancer, but the most consistent findings have been for soft-tissue sarcoma and non-Hodgkin lymphoma. Although the odds ratios in some case-control studies may have been inflated by recall bias, this cannot explain all of the findings. Nor are they likely to have arisen by chance. It is not possible, however, to exclude a confounding effect of polychlorinated dibenzo-para-dioxins which occur as contaminants in chlorophenols. 

List of abbreviations BOD, biological oxygen demand CA, chloroanisol CCA, copper-chromate-arsenate CP, chlorophenol 2,4-D, dichlorophenoxyacetic acid DCP, dichlorophenol CFSTR, continuous-flow stirred tank reactor FBBR, fluidized-bed biofilm reactor MCP, monochlorophenol NAPL, non-aqueous phase liquid PAH, polycyclic aromatic hydrocarbon PCPP, polychlorinated phenoxyphenol PCDF, polychlorinated dibenzofuran PCDD, polychlorinated dibenzodioxin PCR, polymerase chain reaction PCP, pentachlorophenol PCA, pentachloroanisole TeCP, tetrachlorophenol TeCA, tetrachloroanisole TCC, trichlorocatechol TCP, trichlorophenol TOC, total organic carbon 2,4,5-T, trichlorophenoxyacetic acid UASB, upflow anaerobic sludge blanket reactor VSS, volatile suspended solids. 

Humppi, T., Knuutinen, J. Paasivirta, J. (1984). Analysis of polychlorinated phenoxyphenols in technical chlorophenol formulations and in sawmill environment. Chemosphere, 11, 1235-41. 

Oberg, L. G., Glas, B., Swanson, S. E. Rappe, K. G. (1 >S>0). Peroxidase-catalyzed oxidation of chlorophenols to polychlorinated dibenzo-/>-dioxins and dibenzofurans. Archives of Environmental Contamination and Toxicology, 19, 930-8. 

As discussed in the earlier survey (1), a biogenic source of polychlorinated dibenzo-p-dioxins and dibenzofurans is peroxidase-catalyzed transformation of chlorophenols as first reported by Oberg and Rappe (2041-2044). More recent studies confirm these observations (2045-2048). In addition to lactoperoxidase and horseradish peroxidase, human leukocyte myeloperoxidase catalyzes in vitro formation of dioxins and dibenzofurans from chlorophenols (2046, 2047). Formation rates are in the pmol/mol range (Scheme 3.6) demonstrating that a human biosynthesis of dioxins and furans is not only possible but also likely. These observations are reinforced by the reported in vivo (rats) conversion of the pre-dioxin nona-chloro-2-phenoxyphenol to octachlorodibenzo-p-dioxin (OCDD) (2049), and the production of hepta- and octachlorodibenzo-p-dioxin in the feces of cows fed pentachlorophenol-treated wood (Scheme 3.7) (2050, 2051). 

Oberg LG, Glas B, Swanson SE, Rappe C, Paul KG (1990) Peroxidase-Catalyzed Oxidation of Chlorophenols to Polychlorinated Dibenzo-p-dioxins and Dibenzofurans. Arch Environ Contam Toxicol 19 930... 

Wittsiepe J, Kullmann Y, Schrey P, Selenka F, Wilhelm M (1999) Peroxidase-Catalyzed in Vitro Formation of Polychlorinated Dibenzo-p-dioxins and Dibenzofurans from Chlorophenols. Toxicol Lett 106 191... 

Lopez-Avila et al. [107] showed that microwave-assisted extraction of pesticides and polycyclic aromatic hydrocarbons from soil is a viable alternative to Soxhlet extraction and needs a smaller sample volume and extraction time [108,109]. These techniques have also been compared in the case of chlorophenols. Lopez-Avila et al. compared microwave-assisted extraction with electron capture gas chromatography to ELISA for the determination of polychlorinated biphenyls in soils. Both techniques are applicable to field screening and monitoring applications. Microwave-assisted extraction [111, 112] and solid-phase microextraction [113] have been applied to the extraction of pesticides from soil. It was observed by these and other workers [114] that the selectivity of microwave-assisted extraction is highly dependent on the soil composition. 

Halogenated hydrocarbons Dichloromethane, trichloroethene, tetrachloroethene, tetrachloromethane, trichloromethane, 2-chlorophenol, 3-bromoheptane, pentabromotoluene, hexabromobenzene, polychlorinated biphenyls (PCB)... 

Kaiser, K.L.E., Dixon, D.G., Hodson, PV. (1984) QSAR studies on chlorophenols, chlorobenzenes and para-substituted phenols. In QSAR in Environmental Toxicology. Kaiser, K. L. E., Ed., pp. 189-206, D. Reidel Publishing Co., Dordrecht, The Netherlands. Kamlet, M.J., Doherty, R.M., Carr, P.W., Mackay, D., Abraham, M.H., Taft, R.W. (1988) Linear solvation energy relationship. 44. Parameter estimation rules that allow accurate prediction of octanol/water partition coefficients and other solubility and toxicity properties of polychlorinated biphenyls and polycyclic aromatic hydrocarbons. Environ. Sci. Technol. 22, 503-509. Kanazawa, J. (1981) Measurement of the bioconcentration factors of pesticides by fresh-water fish and their correlation with physicochemical properties of acute toxicities. Pest. Sci. 12, 417-424. 

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