Combined steam distillation and electrochemical peroxidation (ECP) treatment of river sediment contaminated by PCBs.

A combined treatment process utilizing steam distillation followed by electrochemical peroxidation (ECP) has been utilized to remove >90% of the polychlorinated biphenyls (PCBs) in St. Lawrence River sediment and destroy 95% of the PCBs recovered in the condensate. 2 l of condensate were collected by boiling 500 grams of sediment containing approximately 4.3 mg PCBs. Most of the PCBs (82.3%) were recovered as a small volume (<1 ml) of yellow oil floating on the condensate and coating glassware surfaces. The aqueous phase PCBs (182 microg/l) were destroyed (95%) by three sequential ECP treatments at 16.8 degrees C and pH 5, utilizing 1 ml of H2O2 (3%) and periodically reversed current (0.75-1.0 A @ 10 volts). Oxidation is primarily mediated by hydroxyl radicals produced by the reaction of hydrogen peroxide with electrochemically generated ferrous iron (Fenton's reagent). This work suggests steam extraction, in combination with advanced oxidation technologies, provides an effective treatment strategy for contaminated solids.

Enhanced airborne polychlorinated biphenyl (PCB) concentrations and chlorination downwind of Lake Ontario.

Air samples were collected simultaneously at three sites downwind of Lake Ontario and at a control site near Lake Erie from March to July of 1999. The Lake Erie site (Stockton, NY) had PCB concentrations similar to rural Integrated Atmospheric Deposition Network (IADN) sampling sites across the Great Lakes, exhibited limited seasonal variation, and approximates regional background. Samples taken along Lake Ontario's southeastern shore (Rice Creek and Sterling, NY) had elevated PCB concentrations averaging approximately 1 ng/m3 and were more chlorinated than air collected at IADN sites and at Stockton. Air samples from Potsdam (approximately 75 km inland) had similar concentrations but were less chlorinated. Clausius-Clapeyron plots revealed a strong correlation between PCB fugacity and temperature near Lake Ontario; however, the extent of chlorination of the air samples rules out volatilization from the lake as a major source. It is hypothesized that volatilization from local surfaces, enriched in higher chlorinated congeners by meteorological or geographic factors, drives both the concentration and composition of airborne PCBs along Lake Ontario's southeastern shore.

Remediation of metal-contaminated aqueous systems by electrochemical peroxidation: an experimental investigation.

An innovative technology, electrochemical peroxidation (ECP), was investigated for remediation of mixed metal-contaminated aqueous systems by application of direct electric current to steel electrodes and of dilute H(2)O(2) solution to promote Fenton's reactions, forming sparingly soluble solid hydrous ferric oxides (HFO). Bench scale experiments evaluated the sorption and distribution of As, Be, Cd, Cr, Cs, Cu, Li, Ni, Pb, Se, V, and Zn among the soluble and solid state HFO formed as part of the ECP process. The effects of pH, hydrogen peroxide concentrations and electric current process times on the efficiency of metal removal were studied. The potential of this technology was demonstrated by effective removal at pH 3.5-4.6 and within 3 min of 0.25 A dc+100 mg H(2)O(2) l(-1), of As, Cr, Pb, Se and V with complete removal of As and Cr, >95.0%. On increasing the pH of the solution to 6.0, the retention of Be and Cu by HFO increased from 0.9-1.9% at pH 3.5 to 76.8-80.7% at pH 6.0 while concentrations of other metals, such as Pb, decreased due to precipitation of Pb hydroxy-complexes. Experiments in the absence of H(2)O(2) revealed that metals were adsorbed by HFO with the same order of affinity, As>Cr>Se>V>Be, as in the presence of H(2)O(2), but, with the exception of Cr, to a lesser extent. H(2)O(2) used in the ECP process was fundamental to increase the adsorption capacity of HFO for As, from 79.2 to 99.2%, due to the oxidation of As(III) to As(V), which has a stronger affinity for HFO. The reduced adsorption may be related to the formation of poorly ordered crystalline akaganeite, which has a lower surface area than ferrihydrite formed when H(2)O(2) was used. The optimal operating conditions were pH<6.0, an H(2)O(2) concentration of 100 mg l(-1) and a current process time not exceeding 3 min.

Iron-mediated reactions of polychlorinated biphenyls in electrochemical peroxidation process (ECP).

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.

Polychlorinated biphenyls in nonaccumulating, century-old sediments: sources, signatures, and mechanism of introduction.

This study documents the occurrence of highly chlorinated PCB congeners in stream sediment deposited over 100 years ago. Penta- to heptachlorinated congeners (> 80%) have been found at concentrations up to 78.8 ng/g (dw) in core samples of a small, rural tributary of Lake Ontario. Lower chlorinated congeners and other organochlorine compounds occur sporadically; 210Pb and 137Cs are lacking. The most plausible mechanism is accumulation of dissolved-phase PCBs in permeable sediments adjacent to the creek channel. The similarity between core and air samples collected in the drainage basin suggests derivation from a residual fraction of atmospherically derived PCB congeners.

Do large-scale remedial and dredging events have the potential to release significant amounts of semivolatile compounds to the atmosphere?

Laboratory studies suggest that substantial amounts of polychlorinated biphenyls are rapidly volatilized from wet contaminated solids during water evaporation. If significant losses also occur during field activities, potential analytical, global, and health implications should be considered in the design and monitoring of remedial actions and the handling of contaminated solids.