Chlorophenols Pentachlorophenol

This voluntary risk assessment programme started in 1995 and concerned a list of 25 chemicals dichloromethane, chloroform, tetrachloromethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, vinyl chloride, trichloroethene, tetra-chloroethene, hexachlorobutadiene, monochlorobenzene, 1,4-dichlorobenzene, 1,2-dichlorobenzene, 1,2,4-trichlorobenzene, tetrachlorobenzene, hexachlorobenzene, 2-chlorophenol, 3-chlorophenol, 4-chlorophenol, pentachlorophenol, hexachloro-cyclohexane, dioxins, PCB, DDT, and elemental mercury. 

PCNB. See Pentachloronitrobenzene PCON PCONA. See 4-Chloro-2-nitroaniline PCP. See 4-Chlorophenol Pentachlorophenol PCPI. See 4-Chlorophenyl isocyanate PCPL Solvent, PCP Solvent. See Petroleum... 

Phenolics. Phenol (qv) and the chlotinated phenoHcs formerly comprised the largest class of iadustrial antimicrobials (see Chlorophenols). Table 5 shows the remaining phenoHcs of importance. Use of pentachlorophenol has been severely restricted only one manufacturer suppHes product for the wood preservation market. 

Rhc ne-Poulenc, with a capacity of around 20,000 t/yr, is the world s leading producer of light chlorophenols. Excluding the unknown factors for which no statistics are available (China, Russia), the market for pentachlorophenol can be estimated at - 25, 000 t/yr. The principal producers of pentachlorophenol are given ia Table 4. 

The main applications of mono-, di-, or ttichlorophenols are in agrochemicals and for pentachlorophenol in wood protection. 2-Chlorophenol is used chiefly in the manufacture of an insecticide [41198-08-7] (55,56)... 

PCP presents a different picture from that of the lower chlorophenols and their derivatives. The corresponding dioxin shows much more stability to light than does TCDD, enough to permit its prolonged existence at low concentrations in a photoreactor. As a phenol it can directly yield dioxins, a process favored by its normal mode of application as the sodium salt. Although octachlorodibenzo-p-dioxin has much lower mammalian toxicity than TCDD (6), its formation, properties, and effects demand additional investigation. Technical preparations of PCP are frequently mixtures of tetra- and pentachlorophenols consequently, hepta-and possibly hexachlorodibenzo-p-dioxins might be expected as photolysis products in addition to the octachloro derivative. 

The most convenient and successful synthetic preparation of octa-chlorodibenzo-p-dioxin has been described by Kulka (13). The procedure involves chlorination of pentachlorophenol in refluxing trichlorobenzene to give octachlorodibenzo-p-dioxin in 80% yield. Kulka has explained the reaction as coupling between two pentachlorophenoxy radicals. Large amounts (5—15%) of heptachlorodibenzo-p-dioxin were observed in the unpurified product. Since the pentachlorophenol used in this study contained 0.07% tetrachlorophenol, we feel that tetrachloro-phenol may be produced in situ (Reaction 4). Such a scheme would be analogous to the formation of 2,4-dichlorophenol and 3-chlorophenol produced from 2,4,4 -trichloro-2 -hydroxydiphenyl ether (Reaction 2). The solubility of octachlorodibenzo-p-dioxin was determined in various solvents data are presented in Table II. 

Mutations at the active site of CYPlOl (cytochrome P450j,j jj) from a strain of Pseudomonas putida made possible the monooxygenation of chlorinated benzenes with less than three substituents to chlorophenols, with concomitant NIH shifts for 1,3-dichlorobenzene (Jones et al. 2001). Further mutations made it possible to oxidize even pentachlorobenzene and hexachlorobenzene to pentachlorophenol (Chen et al. 2002). Integration of the genes encoding cytochrome PTSO. into Sphingobium chlorophenolicum enabled this strain to partially transform hexachlorobenzene to pentachlorophenol (Yan et al. 2006). 

Bouchard B, R Beaudet, R Villemur, G MscSween, F Lepine, J-G Bisaillon (1996) Isolation and characterization of Desulfitobacterium frappieri sp. nov., an anaerobic bacterium which reductively dechlorinates pentachlorophenol to 3-chlorophenol. Int J Syst Bacteriol 46 1010-1015. 

The tolerance of the strains to high concentrations of pentachlorophenol—S. chlorophenolica appears to be less sensitive than M. chlorophenolicus (Miethling and Karlson 1996). This may be attribnted to the ability of the cells to adapt their metabolism to avoid synthesis of toxic concentrations of chlorinated hydroquinones, and is consistent with the low levels of these metabolites measnred in the cytoplasm of cells metabolizing pentachlorophenol (McCarthy et al. 1997). Inocnla have also been immobilized on polyurethane that, in addition, ameliorates the toxicity of chlorophenols (Valo et al. 1990). 

Organic carboxylic acids are commonly found in foods, in the adipate process stream, and as pollutants. Fatty acids are the lipophilic portion of glycerides and a major component of the cell membrane. Phenols are widely used in polymers, as wood preservatives, and as disinfectants. Chloro-phenols such as 4-chlorophenol, two isomeric dichlorophenols, 2,4,6-tri-chlorophenol, three isomeric tetrachlorophenols, and pentachlorophenol were separated on a Dowex (The Dow Chemical Co. Midland, MI) 2-X8 anion exchange resin using an acetic acid-methanol gradient.138... 

Jobst H (1998) Chlorophenols and nonylphenols in sewage sludges. Part II did contents of pentachlorophenol and nonylphenols reduce Acta Hydrochim Hydrobiol 26 344-348... 

The toxicity of commercial or technical grades of PCP significantly exceeds that of analytical or purified PCP. Some of this added toxicity is attributed to impurities such as dioxins, dibenzo-furans, chlorophenols, and hexachlorobenzene. Pentachlorophenol is rapidly accumulated and rapidly excreted, and has little tendency to persist in living organisms. It acts by uncoupling oxidative... 

Among all chlorophenols, 2,4,6-trichlorophenol (TCP) and pentachlorophenol (PCP) are listed as priority pollutants by the US Environmental Protection Agency (EPA) (IRIS electronic database) and the EU [256]. In particular, PCP has been classified as a B2 probable carcinogen for humans from animal toxicity studies and human clinical data. 

Figure 8. The bioconcentration ratios of chlorophenols in goldfish at 1 h exposure to their media as a function of the difference between pH and pKa. 4-CP 4-chlorophenol, 2,5-DCP 2,5-dichlorophenol, 3,5-DCP 3,5-dichlorophenol, 2,4,6-TCP 2,4,6-trichlorophenol, PCP pentachlorophenol, 2-CP 2-chlorophenol, 3-CP 3-chlorophenol, 2,4-DCP 2,4-dichlorophenol, 2,3-DCP 2,3-dichlorophenol, 2,4,5-TCP 2,4,5-trichlorophenol, 2,3,4,6-TCP 2,3,4,6-tetrachlorophenol, 2,6-DCP 2,6-dichlorophenol. Reprinted from [185] Water Res., 29, Kishino, T. and Kobayashi, K. Relation between toxicity and accumulation of chlorophenols at various pH, and their absorption mechanism in fish , pp. 431-442. Copyright (1995), with permission from Elsevier...

Lee [42] determined pentachlorophenol and 19 other chlorinated phenols in sediments. Acidified sediment samples were Soxhlet extracted (acetone-hexane), back extracted into potassium bicarbonate, acetylated with acetic anhydride and re-extracted into petroleum ether for gas chromatographic analysis using an electron capture or a mass spectrometric detector. Procedures were validated with spiked sediment samples at 100,10 and lng chlorophenols per g. Recoveries of monochlorophenols and polychlorophenols (including dichlorophenols) were 65-85% and 80-95%, respectively. However, chloromethyl phenols were less than 50% recovered and results for phenol itself were very variable. The estimated lower detection limit was about 0.2ng per g. 

Pentachlorophenol, a large-volume fungicide and wood preservative, contains relatively high levels of hexa-, hepta- and octachlorodibenzodioxins and essentially no tetrachlorodibenzo-p-dioxins [83-85] and polychlorodibenzo-p-dioxin incineration of materials containing chlorophenols readily produces mixtures of polychlorodibenzo-p-dioxins, but 2,3,7,8-tetrachlorodibenzo-p-dioxin is a minor component. On the other hand, the highly toxic 1,2,3,7,8-pentachloro isomer is a major component of polychlorodibenzo-p-dioxins and polychlorodibenzofurans usually produce mixtures of distinctly different relative component abundances [83], On the other hand, the preferential accumulation of certain isomers in animals may prevent source identification from analyses of biological samples. 

Pentachlorophenol (Fig. 19), a wood preservative, is the priority pollutant within the group of chlorophenols that has been most released into the environment. Phenols are also breakdown products from natural organic com-... 

Fig. 20. A typical GC-MS trace of a phenol contaminated soil sample, Bitterfeld, Germany (after [254] with permission). Chlorophenols were extracted using ASE-SPME upper chromatogram, procedure B lower chromatogram, ASE conditions of water, 150°C, 15 min. Peak identifications (1) 2-chlorophenol, (2) 2,4-dichlorophenol, (3) 4-chlorophenol, (4) 4-chloro-3-methylphenol, (5) 2,3,5-trichlorophenol, (6) 2,4,6-trichlorophenol, (7) 2,3,4-trichlo-rophenol, (8) 2,3,4,6-tetrachlorophenol, (9) pentachlorophenol... 

Many chlorophenols are harmful and persistent. It is possible that these may be produced microbiologically in nature in view of the finding that a fungal chloroperoxidase halogenates phenol to yield monochlorophenols and the latter to give dichlorophenols. The sequence continues with producing trichlorophe-nols, tetrachlorophenols, and even pentachlorophenol [208]. 

Soil Under anaerobic conditions, pentachlorophenol may undergo sequential dehalogenation to produce /n-chlorophenol, tetra-, tri-, and dichlorophenols (Kobayashi and Rittman, 1982). In aerobic and anaerobic soils, pentachloroanisole was the major metabolite, with minor quantities of... 

Acetamido-4-amino-6-chloro-s-triazine, see Atrazine Acetanilide, see Aniline, Chlorobenzene, Vinclozolin Acetic acid, see Acenaphthene, Acetaldehyde, Acetic anhydride. Acetone, Acetonitrile, Acrolein, Acrylonitrile, Aldicarb. Amyl acetate, sec-Amyl acetate, Bis(2-ethylhexyl) phthalate. Butyl acetate, sec-Butyl acetate, ferf-Butyl acetate, 2-Chlorophenol, Diazinon. 2,4-Dimethylphenol, 2,4-Dinitrophenol, 2,4-Dinitrotoluene, 1,4-Dioxane, 1,2-Diphenylhydrazine, Esfenvalerate. Ethyl acetate, Flucvthrinate. Formic acid, sec-Hexyl acetate. Isopropyl acetate, Isoamyl acetate. Isobutyl acetate, Methanol. Methyl acetate. 2-Methvl-2-butene. Methyl ferf-butvl ether. Methyl cellosolve acetate. 2-Methvlphenol. Methomvl. 4-Nitrophenol, Pentachlorophenol, Phenol. Propyl acetate. 1,1,1-Trichloroethane, Vinyl acetate. Vinyl chloride Acetoacetic acid, see Mevinphos Acetone, see Acrolein. Acrylonitrile. Atrazine. Butane. 

Chlorophenol, see p-Bromophenol. Chlorobenzene. p-Chloronitrophenol, 2,4-D, 2,4-Dichlorophenol, Pentachlorophenol, Phenol, 2,4,5-T, Triadimefon... 

Carbon tetrachloride. Chloroform, 2-Chlorophenol, Cyclohexanol, Cyclopentene, 1,1-Dichloroethylene, irans-l, 2-Dichloroethylene, IV.yV-Dimethylaniline, lV,lV-Dimethylformamide, 2,4-Dimethylphenol, 2,4-Dinitrotoluene, 1,4-Dioxane, 1,2-Diphenylhydrazine, Ethyl formate. Formaldehyde, Glycine, Methanol, Methylene chloride. Methyl formate, 2-Methvlphenol. Monuron, 4-Nitrophenol, Oxalic acid, Parathion, Pentachlorophenol, Phenol, l idine. Styrene, Trichloroethylene, Vinyl chloride Formylacetic acid, see cis-l,3-Dichloropropylene, irans-1,3-Dichloropropylene IV-Formylcarbamate of 1-naphthol, see Carbaryl Formyl chloride, see Chloroethane, Chloroform, sym-Dichloromethyl ether, ds-1,3-Dichloropropylene, irans-ES-Dichloropropylene, Methyl chloride. Methylene chloride. Trichloroethylene, Vinyl chloride lV-Formyl-4-chloro-o-toluidine, see Chlornhenamidine. 

Halogenated Aromatic Compounds Halogenated Cresols Halogenated Ethers and Epoxides Halogenated Phenolic Compounds Halophenols Chlorophenol Dichlorophenol Halophenols Pentachlorophenol PCP Tetrachlorophenol Trichlorophenol... 

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