Chlorinated phenols and anilines are transformed and detoxified in soil through oxidative coupling reactions mediated by enzymes or metal oxides. The reactions may be influenced by humic constituents, such as syringaldehyde or catechol, that originate from lignin decomposition and are also subject to oxidative coupling. In this study, the effect of humic constituents on xenobiotic transformation was evaluated in vitro based on the determination of unreacted chlorophenols and chloroanilines. In experiments with peroxidase, laccase, and birnessite (δ-MnO2), the transformation of most chlorophenols was considerably enhanced by the addition of syringaldehyde. Less enhancement was observed using 4-hydroxybenzoic acid, and the addition of catechol resulted in a reduction of most transformations. The opposite was observed in experiments with tyrosinase, in which case catechol caused considerable enhancement of chlorophenol transformation. The varying effect of catechol can be explained by different transformation mechanisms involving either o-quinone coupling (with tyrosinase) or free radical coupling (with peroxidase, laccase, or birnessite). Regardless of the agent used to mediate the reactions, chloroanilines seemed to undergo nucleophilic addition to quinone oligomers, which resulted from coupling of the humic constituents. Catechol, which readily forms quinones and quinone oligomers, was most efficient in enhancing these reactions.

Trophic transfer of polychlorinated biphenyl (PCB) congeners in zebra mussels (Dreissena polymorpha), round gobies (Neogobius melanstomus), and smallmouth bass (Micropterus dolomieu) were assessed in four sites along the south shore of the west and central basin of Lake Erie (all sites were in OH, USA). Total PCB levels in smallmouth bass (1,091-1,520 ng/g wet weight) and round gobies (118-256 ng/g wet weight) were similar among sites despite a west-to-east decrease in total PCB concentrations in zebra mussels (29-97 ng/g wet weight). At all sites, PCB body burden increased three- to fivefold at each successive trophic level, suggesting biomagnification in this nonnative food chain. Whereas fish species were dominated by the hexachlorine homologue, zebra mussels were dominated by penta- and hexachlorine homologues; the average degree of chlorination of PCBs was 56.1% for zebra mussels, 60.4% for round goby, and 59.9% for smallmouth bass bodies. Predictive structure-activity relationships based on chemical characteristics, such as the octanol-water partition coefficient (log K(ow)), had little predictive power on bioaccumulation and biotransformation of PCB congeners because of nonlinearity, threshold relationships, and species-specific differences. Calculated trophic transfer for the smallmouth bass-round goby linkage was higher than for the round goby-zebra mussel linkage. Only when PCB congeners were grouped by chemical structure first (vicinal [adjacent] H-atom position in the phenyl ring) were linear relationships achieved. It appeared that the chemical group to which each congener belonged influenced biotransformation more than species-specific (round gobies vs smallmouth bass) differences. Biotic changes at midtrophic levels, such as exotic species invasions, may have an increasingly important role in determining pollutant cycling and hence pollutant residues in top predators.

Enzyme treatment is currently considered for remediation of terrestrial systems polluted with organic compounds. In this study, two soils from Pennsylvania with 2.8 or 7.4% organic matter contents (Soils 1 and 2, respectively) were amended with 14C-labeled 2,4-dichlorophenol (2,4-DCP) and incubated with a laccase from Trametes villosa (free or immobilized on montmorillonite). 2,4-DCP was either transformed to methanol-soluble polymeric products (11-32%) or covalently bound to soil organic matter (53-85%); unaltered 2,4-DCP could be recovered from soil by methanol extraction (0-38%) at the completion of a 14-d incubation period. In Soil 1, both free and immobilized laccase removed 100% of 2,4-DCP without regard for moisture conditions. In Soil 2, immobilized laccase removed more 2,4-DCP (about 95%, regardless of moisture conditions) than free enzyme (55, 75, and 90% at 30, 55, and 100% of maximum water-holding capacity, respectively). Binding of 2,4-DCP in the humin fraction was nearly the same for free and immobilized laccase. More 2,4-DCP, however, was bound to humic and fulvic acids in the presence of immobilized laccase than in the presence of free laccase. In general, immobilized laccase performed better than free laccase. However, for practical applications, the higher activity of immobilized laccase is offset by a 23% loss in enzyme activity during immobilization, which approximates the 30% increase in free laccase needed to achieve the same level of remediation. Furthermore, immobilized laccase is more costly than free T. villosa laccase.

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