Dechlorination transform

Transformation of DDT to DDD by reductive dechlorination has been demonstrated in a number of aquatic plants, although the reaction appears to be abiotic mediated by some component of the plants (Garrison et al. 2000). 

The anaerobic degradation of halogenated alkanoic acids has, however, been much less exhaustively examined. Geobacter (Trichlorobacter) thiogenes was able to transform trichloroacetate to dichloroacetate by coupling the oxidation of acetate to CO2 with the reduction of sulfur to sulfide that carries out the dechlorination (De Wever et al. 2000). 

Considerable effort has been devoted to the anaerobic transformation of polychlorinated Cj alkanes and C2 alkenes in view of their extensive use as industrial solvents and their identification as widely distributed groundwater contaminants. Early experiments, which showed that tetrachloroethene was transformed into chloroethene (Vogel and McCarty 1985) (Figure 7.67), aroused concern though it has now been shown that complete dechlorination can be accomplished by some organisms. 

Under methanogenic conditions, a strain of Methanosarcina sp. transformed tetrachloroethene to trichloroethene (Fathepnre and Boyd 1988). In the presence of suitable electron donors snch as methanol, complete rednction of tetrachloroethene to ethene may be achieved in spite of the fact that the dechlorination of vinyl chloride appeared to be the rate-limiting step (Freedman and Gossett 1989). 

Reductive dechlorination in combination with the elimination of chloride has been demonstrated in a strain of Clostridium rectum (Ohisa et al. 1982) y-hexachlorocyclohexene formed 1,2,4-trichlorobenzene and y-l,3,4,5,6-pentachlorocyclohexene formed 1,4-dichlorobenzene (Figure 7.69). It was suggested that this reductive dechlorination is coupled to the synthesis of ATP, and this possibility has been clearly demonstrated during the dehalogenation of 3-chlorobenzoate coupled to the oxidation of formate in Desulfomonile tiedjei (Mohn and Tiedje 1991). Combined reduction and elimination has also been demonstrated in methanogenic cultures that transform 1,2-dibromoethane to ethene and 1,2-dibromoethene to ethyne (Belay and Daniels 1987). 

Toxaphene is a complex mixture of compounds prepared by chlorinating camphene, and contains several hundred polychlorinated bornanes. After incubation with Sulfurospirillum (Dehalospirillum) multivorans only the hexa- (B6-923) and the heptachlorinated (B7-1001) remained. The nonachlorinated congener B9-1679 could be transformed by preferential dechlorination of the em-dichloro groups with formation of the heptachlorinated B7-1001 (Ruppe et al. 2003). Further examination showed that this congener could be dechlorinated to penta- and hexachlorinated bornanes (Ruppe et al. 2004). 

In anaerobic microcosms, l,l,2-trichloro-l,2,2-trifiuoroethane (CFC-113) was transformed by successive reductive dechlorination to l,2-dichloro-l,2,2-trifiuoroethane (HCFC-123a), and under methanogenic conditions to l-chloro-l,2,2-trifiuoroethane (HCFC-133) and l-chloro-l,l,2-triflnoroethane (HCFC-133b) without evidence for the reductive replacement of fluorine (Fignre 7.70b) (Lesage et al. 1992). 

Bedard DL, JE Quensen III (1995) Microbial reductive dechlorination of polychlorinated biphenyls. In Microbial transformation and Degradation of Toxic Organic Chemicals (Eds LY Yonng, CE Cemiglia), pp. 127-216. Wiley-Liss, New York. 

Chlorinated anilines are produced by the reduction of PCNB that is used as a fungicide against a variety of commercial crops. The transformation of PCNB has been examined with a methanogenic enrichment culture from contaminated sediment, although this contained neither PCNB nor its reduction product pentachloroaniline (PCNA). The culture not only reduced the initial PCNB, but also carried out sequential dechlorination to tetra-, tri-, dichloroanilines, and ultimately to 3- and 4-chloroaniline (Tas and Pavlostathis 2005). 

The higher content of DDT metabolites (DDE + DDD) compared with DDT itself (i.e., (DDE + DDD)/DDT > 1) in surface waters indicates a high degree of microbial transformation of the initial compound in the soil. The DDE and DDD are formed by DDT dehydrochlorination and dechlorination, respectively. On the whole it means that loss or leaching of toxic compounds take place from RPA formed some decades ago. 

Always based on the use of IR spectrophotometry, a novel attenuated total reflection-Fourier-transform infrared (ATR-FTIR) sensor [42] was proposed for the on-line monitoring of a dechlorination process. Organohalogenated compounds such as trichloroethylene (TCE), tetrachloroethylene (PCE) and carbon tetrachloride (CT) were detected with a limit of a few milligrams per litre, after extraction on the ATR internal-reflection element coated with a hydro-phobic polymer. As for all IR techniques, partial least squares (PLS) calibration models are needed. As previously, this system is promising for bioprocess control and optimization. 

Mirex is a very persistent compound in the environment and is highly resistant to both chemical and biological degradation. The primary process for the degradation of mirex is photolysis in water or on soil surfaces photomirex is the major transformation product of photolysis. In soil or sediments, anaerobic biodegradation is also a major removal mechanism whereby mirex is slowly dechlorinated to the 10-monohydro derivative. Aerobic biodegradation on soil is a very slow and minor degradation process. Twelve years after the application of mirex to soil, 50% of the mirex and mirex-related compounds remained on the soil. Between 65--73% of the residues recovered were mirex and 3-6% were chlordecone, a transformation product (Carlson et al. 1976). 

Little information about TeCA transformation in groundwater is available however, reductive dechlorination, dehydrochlorination, and dichloroelimina-tion are three possible reactions for TeCA transformations. The following is a brief summary of biotransformation research conducted for TeCA ... 

Reductive dechlorination or reductive hydrogenolysis is a common transformation of 1- and 2-carbon chlorinated aliphatics under methanogenic conditions [373,374]. 1,1,1-Trichloroethane (l,l,l-TCA),for example,is converted to 1,1-dichloroethane (1,1-DCA) [375], and Perchloroethylene (PCE) is successively converted to TCE, cDCE, VC, and ethane [274]. Each reductive dechlorination is a two-electron transfer reaction. 

Bouwer and McCarty [374] suggested 1,1,2-TCA is an intermediate of TeCA transformation in continuous-flow column experiments and TCE as an intermediate in a batch experiment under methanogenic conditions. Those transformations are reductive dechlorination and dehydro chlorination, respectively. 

Schanke and Wackett [379] reported TeCA degradation by transition-metal coenzymes. cDCE (53%), tDCE (29%), VC (14%), ethylene (1%), and traces of 1,1,2-TCA were the products from this abiotic transformation with vitamin B12 and titanium(III) citrate. Both dechlorination and dichloroelimination had occurred the major route of degradation was reductive dihaloelimina-tion. 

TCE is the other major contaminant at the site and is a common groundwater contaminant in aquifers throughout the United States [425]. Since TCE is a suspected carcinogen, the fate and transport of TCE in the environment and its microbial degradation have been extensively studied [25,63, 95,268,426,427]. Reductive dechlorination under anaerobic conditions and aerobic co-metabolic processes are the predominant pathways for TCE transformation. In aerobic co-metabolic processes, oxidation of TCE is catalyzed by the enzymes induced and expressed for the initial oxidation of the growth substrates [25, 63, 268, 426]. Several growth substrates such as methane, propane, butane, phenol, and toluene have been shown to induce oxygenase enzymes which co-metabolize TCE [428]. 

Despite the environmental stability of these compounds, a number of reports have indicated that under reducing conditions prevailing in sediments dioxins may undergo transformation reactions, including dechlorination. The potential importance of reductive dechlorination, and perhaps one of the reasons for the emphasis on this transformation process, is illustrated by recent evidence that... 

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