Chlorophenols, toxicities

Makinen, P. M., Theno, T. J., Ferguson, J. F., Ongerth, J. E., and Puhakka, J. A., Chlorophenol Toxicity Removal and Monitoring in Aerobic Treatment Recovery from Process Upsets, Environ. Sci. Technol. 27 1434 (1993)... 

Makinen PM, Theno TJ, Ferguson JF, Ongerth JE, Puhakka JA (1993) Chlorophenol toxicity removal and monitoring in aerobic treatment recovery from process upsets. Env Sci Technol 27 1434-1439... 

Chlorophenyl trifluoromethanesulfonate Methanesulfonic acid, trifluoro-,j-chlorophenyl ester (8) Methanesulfonic acid, trifluoro-, 4-chlorophenyl ester (9) (29540-84-9) 4-Chlorophenol TOXIC Phenol, p-chloro- (8) Phenol, 4-chloro- (9) (106-48-9) Pyridine (8, 9) (110-86-1)... 

Wastewater. Phenol is a toxic poUutant to the waterways and has an acute toxicity (- 5 m g/L) to fish. Chlorination of water gives chlorophenols, which impart objectionable odor and taste at 0.01 mg/L. Biochemical degradation is most frequently used to treat wastewater containing phenol. Primary activated sludge, along with secondary biological treatment, reduces phenol content to below 0.1 mg/L (69). 

Effects in Animals. The LD ia rats for all light chlorophenols, irrespective of the administration route, ties between 130 and 4000 mg/kg body weight. The toxicity of these compounds ia order of increasing strength is tetrachlorophenols > monochloropheno1 s > dichlorophenols > trichlorophenols when the chlorophenol is administered either orally or by subcutaneous iajection. 

Because of lower toxicity and high antimicrobial activity, the phenols having the greatest use in disinfections are o-phenylphenol (Dowicide 1) [90-43-7J, C 2H qO i9-benzyl-/)-chlorophenol (Santophen 1) [120-32-1J, C H CIO and -Z fZ-amylphenol [80-46-6] They possess similar general... 

Many very hazardous solvents, such as benzene and carbon tetrachloride, were widely used until the 1970s. The situation was very similar for the use of pesticides. Among the toxic pesticides that were still in wide use 20 years ago were chlorophenols, DDT, lindane, and arsenic salts, all of which are classified as human carcinogens as well as being acutely toxic. Fortunately, use of these kinds of very toxic chemicals is now limited in the industrialized world. However, because the number of chemicals used in various industries continues to increase, the risks of long-term health hazards due to long-term exposure to low concentrations of chemicals continues to be a problem in the workplace. 

Both PCDDs and PCDEs are refractory lipophilic pollutants formed by the interaction of chlorophenols. They enter the environment as a consequence of their presence as impurities in pesticides, following certain industrial accidents, in effluents from pulp mills, and because of the incomplete combustion of PCB residues in furnaces. Although present at very low levels in the environment, some of them (e.g., 2,3,7,8-TCDD) are highly toxic and undergo biomagnification in food chains. 

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. 

Industrial workers involved in chlorinated aromatic production including chlorophenol suffered dioxin-induced chloracne 2,3). Chloracne and other serious health disturbances have been attributed to polychloro-dibenzo-p-dioxins in workers involved in manufacturing 2,4,5-T 4, 5). Dioxins are toxic to chick embryos, guinea pigs, rabbits, and monkeys 6, 7, 8, 9, 10). 

Whereas photolysis of 2- and 4-chlorophenols in aqueous solution produced catechol and hydroquinone, in ice the more toxic dimeric chlorinated dihydroxybiphenyls were formed (Blaha et al. 2004). 

Blaha L, J Klanova, P Klan, J Janosek, M Skarek, R Ruzicka (2004) Toxicity increases in ice containing mono-chlorophenols upon photolysis environmental consequences. Environ Sci Technol 38 2873-2878. 

Haggblom MM, RJ Valo (1995) Bioremedation of chlorophenol wastes. In Microbial Transformation and Degradation of Toxic Organic Chemicals (Eds LY Young and CE Cerniglia), pp. 389-434. Wiley-Liss, New York, USA. 

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). 

Shigeoka, T., Sato, Y., Takeda, Y. (1988) Acute toxicity of chlorophenols to green algae, Selenastrum capricomutum and Chlorella vulgaris, and quantitative structure-activity relationships. Environ. Toxicol. Chem. 7, 847-854. 

PCDDs are present as trace impurities in some commercial herbicides and chlorophenols. They can be formed as a result of photochemical and thermal reactions in fly ash and other incineration products. Their presence in manufactured chemicals and industrial wastes is neither intentional nor desired. The chemical and environmental stability of PCDDs, coupled with their potential to accumulate in fat, has resulted in their detection throughout the global ecosystem. The number of chlorine atoms in PCDDs can vary between one and eight to produce up to 75 positional isomers. Some of these isomers are extremely toxic, while others are believed to be relatively innocuous. 

Data on the bioavailability of PCDDs are limited. It is known that PCDDs incorporated into wood as a result of chlorophenol (preservative) treatment are bioavailable. Swine and poultry using chlorophenol-treated wooden pens or litter have been found to be contaminated with PCDDs (NRCC 1981). Toxicities of individual PCDD isomers can vary by a factor of 1000 to 10,000 for isomers as closely related as 2,3,7,8-TCDD and 1,2,3,8-TCDD, or 1,2,3,7,8-penta-CDD and 1,2,4,7,8-penta-CDD (Rappe 1984). Isomers with the highest biological activity and acute toxicity have four to six chlorine atoms, and all lateral (i.e., 2,3,7, and 8) positions substituted with chlorine. On this basis, the most toxic PCDD isomers are 2,3,7,8-TCDD, 1,2,3,7,8-penta-CDD, 1,2,3,6,7,8-hexa-CDD, 1,2,3,7,8,9-hexa-CDD, and 1,2,3,4,7,8-hexa-CDD (Rappe 1984). Ishizuka et al. (1998) have assigned toxic equivalencies for various PCDDs, with 2,3,7,8-TCDD given a value of 1 (highest biological activity), followed by a value of 0.5 for 1,2,3,7,8-penta-CDD a value of 0.1 for three PCDD isomers (1,2,3,4,7,8-hexa-CDD, 1,2,3,4,7,8-hexa-CDD, 1,2,3,7,8,9-hexa-CDD), a value of 0.01 for 1,2,3,4,6,7,8-hepta-CDD and a value of 0.001 for 1,2,3,4,6,7,8,9-octa-CDD. 

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... 

Commercial PCP preparations often contain variable amounts of chlorophenols, hexachloroben-zene, phenoxyphenols, dioxins, dibenzofurans, chlorinated diphenyl ethers, dihydroxybiphenyls, anisoles, catechols, and other chlorinated dibenzodioxin and dibenzofuran isomers. These contaminants contribute to the toxicity of PCP — sometimes significantly — although the full extent of their interactions with PCP and with each other in PCP formulations are unknown. Unless these contaminants are removed or sharply reduced in existing technical- and commercial-grade PCP formulations, efforts to establish sound PCP criteria for protection of natural resources may be hindered. 

Van Gestel, C.A.M. and W.C. Ma. 1988. Toxicity and bioaccumulation of chlorophenols in earthworms, in relation to bioavailability in soil. Ecotoxicol. Environ. Safety 15 289-297. 

The destruction of 2-chlorophenol (CP, M = 128.5 g mol-1), a toxic organochlorine compound, by radiative treatment was investigated by Evans et al. (1995). The following data were measured as a fimction of time in a 50 cm3 closed cell ... 

---