The polychlorinated biphenyl (PCB) residues in the aquatic sediments from six PCB spill sites showed changes in PCB isomer and homolog (congener) distribution that indicated the occurrence of reductive dechlorination. The PCB dechlorinations exhibited several distinct congener selection patterns that indicated mediation by several different localized populations of anaerobic microorganisms. The higher (more heavily chlorinated) PCB congeners that were preferentially attacked by the observed dechlorination processes included all those that are either pharmacologically active or persistent in higher animals. All the lower (less heavily chlorinated) PCB congeners formed by the dechlorinations were species that are known to be oxidatively biodegradable by the bacteria of aerobic environments.

The polychlorinated biphenyls (PCBs) in sediment and/or fish samples from at least five different locations show changes in gas chromatographic (GC) peak distribution indicative of reductive dechlorination. Several different dechlorination processes, each presumably mediated by a different population of anaerobic bacteria with its own distinctive pattern of PCB congener selectivity, appear to be operating. Six of these processes have been characterized in detail as to the changes occurring in each of the 126 individual PCB congeners or isomer groups detectable by capillary GC or GC‐MS on a DB‐1 column. The patterns of congener reactivity indicate that the observed transformation processes fall into two broad categories: o,m,p‐dechlorinations, which remove chlorine atoms from ortho, meta, and para positions, with congener reactivities primarily determined by reduction potential; and m,p‐dechlorinations, which take chlorines from meta and para positions only, with relative reactivities determined mainly by molecular shape. Both types of dechlorination preferentially remove PCB congeners of toxicological concern, and both produce lower congeners that are biodegradable by environmental aerobes. Thus, dechlorination in anaerobic sediments permits the detoxification and eventual degradation of environmental PCBs.