Long-term recovery of PCB-contaminated sediments at the Lake Hartwell superfund site: PCB dechlorination. 1. End-member characterization.

Under anaerobic conditions, such as those typically found in buried sediments, the primary metabolic pathway for polychlorinated biphenyls (PCBs) is reductive dechlorination in which chlorine removal and substitution with hydrogen by bacteria result in a reduced organic compound with fewer chlorines. Vertical sediment cores were collected from Lake Hartwell (Pickens County, SC) and analyzed in 5-cm intervals for 107 PCB congeners in a total of more than 280 samples from 18 sediment cores and surface samples. This paper reports on extensive PCB dechlorination measured in Lake Hartwell sediments and the characterization of dechlorination end-member (EM) patterns using chemical forensic methods. PCB congener fingerprinting and a multivariate receptor modeling method, polytopic vector analysis (PVA), were used for identification and characterization of weathered and dechlorinated PCB congener patterns. Dechlorination resulted in a substantial shift in buried sediments from tetra- through decachlorobiphenyl congeners to mono- through trichlorobiphenyl congeners. Mono- through trichlorobiphenyls comprised approximately 80% of the PCBs in buried sediments that underwent maximum dechlorination as compared to approximately 20% in surface sediments. The major concentration decreases were seen in the tetra- through hexachlorobiphenyl homologues, which accounted for over 90% of the dechlorination. Octa- through decachlorobiphenyl congeners also were dechlorinated, but their overall contribution to dechlorination was relatively small due to their low initial concentrations (< 5%). The net accumulation of 2-CB, 2,2'/2,6-DCBs, 2,4'-DCB, 2,2',4-TCB, and 2,2',6-TCB at Lake Hartwell matched characteristic PCB dechlorination products reported in the literature, such as those for Processes M, Q, and C; and the persistence of tetrachlorobiphenyls (TeCBs) that contained 24- and 25-congener groups resembled dechlorination Processes H or H'. Although dechlorination tended to be very extensive in most of the cores, it was not always consistent from core to core or at various depth intervals within a single core. The reason for this variability in dechlorination extent could not be determined from the existing data and did not appear to correlate with such factors as PCB concentration, total organic carbon, or age. The authors used fingerprinting analysis and a PVA multivariate receptor model as exploratory data analysis tools to characterize PCB sources and their alteration patterns. Dominant sources and alteration patterns were determined in this large data set by comparing PVA EM patterns with known source patterns (i.e., Aroclors or Aroclor mixtures) and literature-reported alteration patterns. PVA also afforded an opportunity to characterize the vertical and lateral distributions of the weathered and unweathered PCB source patterns and dechlorination patterns, a task that would have been much more difficult to accomplish through comparison of chromatograms alone.

Long-term recovery of PCB-contaminated surface sediments at the Sangamo-westonl Twelvemile Creek/lake Hartwell Superfund Site.

Natural recovery of contaminated sediments relies on burial of contaminated sediments with increasingly clean sediments over time (i.e., natural capping). Natural capping reduces the risk of resuspension of contaminated surface sediments, and it reduces the potential for contaminant transport into the food chain by limiting bioturbation of contaminated surface or near-surface sediments. This study evaluated the natural recovery of surface sediments contaminated with polychlorinated biphenyls (PCBs) at the Sangamo-Weston/Twelvemile Creek/Lake Hartwell Superfund Site (Lake Hartwell), Pickens County, SC. The primary focus was on sediment recovery resulting from natural capping processes. Total PCB (t-PCB), lead-210 (210Pb), and cesium-137 (137Cs) sediment core profiles were used to establish vertical t-PCB concentration profiles, age date sediments, and determine surface sedimentation and surface sediment recovery rates in 18 cores collected along 10 transects. Four upgradient transects in the headwaters of Lake Hartwell were impacted by historical sediment releases from three upgradient sediment impoundments. These transects were characterized by silt/ clay and sand layering. The highest PCB concentrations were associated with silt/clay layers (1.8-3.5% total organic carbon (TOC)), while sand layers (0.05-0.32% TOC) contained much lower PCB concentrations. The historical sediment releases resulted in substantial burial of PCB-contaminated sediment in the vicinity of these four cores; each core contained less than 1 mg/kg t-PCBs in the surface sand layers. Cores collected from six downgradient Lake Hartwell transects consisted primarily of silt and clay (0.91-5.1% TOC) and were less noticeably impacted by the release of sand from the impoundments. Vertical t-PCB concentration profiles in these cores began with relatively low PCB concentrations at the sediment-water interface and increased in concentration with depth until maximum PCB concentrations were measured at approximately 30-60 cm below the sediment-water interface, ca. 1960-1980. Maximum t-PCB concentrations were followed by progressively decreasing concentrations with depth until the t-PCB concentrations approached the detection limit, where sediments were likely deposited before the onset of PCB use at the Sangamo-Weston plant. The sediments containing the maximum PCB concentrations are associated with the period of maximum PCB release into the watershed. Sedimentation rates averaged 2.1 +/- 1.5 g/(cm2 yr) for 12 of 18 cores collected. The 1994 Record of Decision cleanup requirement is 1.0 mg/kg; two more goals (0.4 and 0.05 mg/kg t-PCBs) also were identified. Average surface sedimentation requirements to meet the three goals were 1.4 +/- 3.7, 11 +/- 4.2, and 33 +/- 11 cm, respectively. Using the age dating results, the average recovery dates to meet these goals were 2000.6 +/- 2.7, 2007.4 +/- 3.5, and 2022.7 +/- 11 yr, respectively. (The 95% prediction limits for these values also are provided.) Despite the reduction in surface sediment PCB concentrations, PCB concentrations measured in largemouth bass and hybrid bass filets continue to exceed the 2.0 mg/kg FDA fish tolerance level.