Relatively high concentrations (up to 98.5 ng/g dry wt) of polychlorinated biphenyls (PCBs) have been found in two cores penetrating fluvial sands east of Lake Ontario. One core was taken from the upper Salmon River reservoir on the Tug Hill Plateau and the other from Rice Creek near the lake at Oswego. In both instances, portions of the cores containing PCBs and other organochlorines (OCs) lack excess radiogenic Pb-210 and (SC)-S-137, implying depositional ages predating widespread OC commercial production, use, and release. Within each core there is little vertical variation in PCB composition and highly chlorinated congeners dominate the pattern. In addition, the PCB signature is analytically indistinguishable between cores despite collection over 50 km apart. This argues against local sources, and implies deposition and accumulation by processes operating over a substantial area and time period. Transport and introduction of a residual fraction of colloidal-bound PCBs to the sands via tannin-rich riverine waters is proposed.The PCB congener-specific pattern of air samples collected during the spring and summer of 1999 downwind of the lake at two locations (Rice Creek and Sterling) are similar to the sediments and display anomalous concentrations and chlorination with respect to other air sampling localities in the Great Lakes. A link between the residual fraction of PCBs observed in the sediment and air patterns via volatilization from the terrestrial surface is proposed. Elevated PCB concentrations and chlorination in non-radiogenic fluvial sands and air may reflect regional accumulation and weathering processes operating over many decades and/or enhancement of contaminant deposition and partitioning downwind of the lake related to lake-effect precipitation.
A study was conducted to explore some of the basic processes of polychlorinated biphenyl (PCB) destruction by a new technology termed electrochemical peroxidation process (ECP). ECP represents an enhancement of the classic Fenton reaction (H2O2 + Fe2+) in which iron is electrochemically generated by steel electrodes. Focus was on the extent of adsorption of a mixture of Aroclor 1248 on steel electrodes in comparison to iron filings. Commercially available zero-valent iron filings rapidly adsorbed PCBs from an aqueous solution of Aroclor 1248. Within 4 h, all the PCBs were adsorbed at 1%, 5%, and 10% Fe0 (w/v) concentrations. Little difference in adsorption was found between acidic (2.3) and unamended solutions (pH 5.5), even though significant differences in iron oxidation state and Fe2+ concentrations were measured in solution. PCB adsorption also occurs on steel electrodes regardless of the pH or electric current applied (AC or DC), suggesting the combination of oxidizing (free radical-mediated reactions) and reducing (dechlorination reactions) iron-mediated degradation pathways may be possible. Extraction of the iron powder after 48 h of contact time yielded the progressive recovery of biphenyl with increasing Fe mass(from 0.4% to 3.5%) and changes of the PCB congener-specific pattern as a consequence of dechlorination. A variety of daughter congeners similar to those accumulated during anaerobic microbial dechlorination of Aroclor 1248 in contaminated sediments indicate preferential removal of meta- and para-chlorines.