Toxicity reference values for methylmercury effects on avian reproduction: Critical review and analysis.

Effects of mercury (Hg) on birds have been studied extensively and with increasing frequency in recent years. The authors conducted a comprehensive review of methylmercury (MeHg) effects on bird reproduction, evaluating laboratory and field studies in which observed effects could be attributed primarily to Hg. The review focuses on exposures via diet and maternal transfer in which observed effects (or lack thereof) were reported relative to Hg concentrations in diet, eggs, or adult blood. Applicable data were identified for 23 species. From this data set, the authors identified ranges of toxicity reference values suitable for risk-assessment applications. Typical ranges of Hg effect thresholds are approximately 0.2 mg/kg to >1.4 mg/kg in diet, 0.05 mg/kg/d to 0.5 mg/kg/d on a dose basis, 0.6 mg/kg to 2.7 mg/kg in eggs, and 2.1 mg/kg to >6.7 mg/kg in parental blood (all concentrations on a wet wt basis). For Hg in avian blood, the review represents the first broad compilation of relevant toxicity data. For dietary exposures, the current data support TRVs that are greater than older, commonly used TRVs. The older diet-based TRVs incorporate conservative assumptions and uncertainty factors that are no longer justified, although they generally were appropriate when originally derived, because of past data limitations. The egg-based TRVs identified from the review are more similar to other previously derived TRVs but have been updated to incorporate new information from recent studies. While important research needs remain, a key recommendation is that species not yet tested for MeHg toxicity should be evaluated using toxicity data from tested species with similar body weights. Environ Toxicol Chem 2017;36:294-319. © 2016 SETAC.

Critical perspectives on mercury toxicity reference values for protection of fish.

Environmental management decisions at mercury-contaminated sediment sites are predicated on the understanding of risks to various receptors, including fish. Toxicity reference values (TRVs) for interpreting risks to fish have been developed to assess mercury concentrations in fish or fish prey. These TRVs were systematically evaluated based on several lines of evidence. First, their conceptual basis and specific derivation were evaluated, including a close review of underlying toxicity studies. Second, case studies were reviewed to investigate whether TRVs are predictive of effects on fish populations in the field. Third, TRVs were compared with available information regarding preindustrial and present-day background concentrations of mercury in fish. The findings show that existing TRVs are highly uncertain, because they were developed using limited data from studies not designed for TRV derivation. Although field studies also entail uncertainty, several case studies indicate no evidence of adverse effects despite mercury exposures that exceed the available TRVs. Some TRVs also fall within the range of background mercury concentrations in predatory or prey fish. Lack of information on the selenium status of mercury-exposed fish is a critical confounding factor, and the form of methylmercury used in toxicity testing may also contribute to differences between TRV-based predictions and field observations of mercury effects on fish. On balance, the available information indicates that several of the TRVs reviewed are lower than necessary to protect fish populations. The 20% effect concentration from a previously published dose-response analysis appears closer to an effect threshold, based on available laboratory data. Additional research is needed to provide a stronger basis to establish dose-response relationships for mercury effects on fish.

Critical review of mercury sediment quality values for the protection of benthic invertebrates.

Sediment quality values (SQV) are commonly used-and misused-to characterize the need for investigation, understand causes of observed effects, and derive management strategies to protect benthic invertebrates from direct toxic effects. The authors compiled more than 40 SQVs for mercury, nearly all of which are "co-occurrence" SQVs derived from databases of paired chemistry and benthic invertebrate effects data obtained from field-collected sediment. Co-occurrence SQVs are not derived in a manner that reflects cause-effect, concentration-response relationships for individual chemicals such as mercury, because multiple potential stressors often co-occur in the data sets used to derive SQVs. The authors assembled alternative data to characterize mercury-specific effect thresholds, including results of 7 laboratory studies with mercury-spiked sediments and 23 studies at mercury-contaminated sites (e.g., chloralkali facilities, mercury mines). The median (± interquartile range) co-occurrence SQVs associated with a lack of effects (0.16 mg/kg [0.13-0.20 mg/kg]) or a potential for effects (0.88 mg/kg [0.50-1.4 mg/kg]) were orders of magnitude lower than no-observed-effect concentrations reported in mercury-spiked toxicity studies (3.3 mg/kg [1.1-9.4 mg/kg]) and mercury site investigations (22 mg/kg [3.8-66 mg/kg]). Additionally, there was a high degree of overlap between co-occurrence SQVs and background mercury levels. Although SQVs are appropriate only for initial screening, they are commonly misused for characterizing or managing risks at mercury-contaminated sites. Spiked sediment and site data provide more appropriate and useful alternative information for characterization and management purposes. Further research is recommended to refine mercury effect thresholds for sediment that address the bioavailability and causal effects of mercury exposure. Environ Toxicol Chem 2015;34:6-21. © 2014 SETAC.

Assessment of mercury bioavailability to benthic macroinvertebrates using diffusive gradients in thin films (DGT).

Mercury-specific diffusive gradient in thin films (DGTs) were used in laboratory microcosms as a biomonitoring tool to assess the lability of mercury (Hg) total and monomethylmercury Hg (MeHg), and to develop a relationship between chemical lability and bioavailability in estuarine sediments. Time-series deployment of DGTs in sediments showed that sediment-bound MeHg is more labile than sediment-bound inorganic Hg. In subsequent experiments, DGTs were deployed simultaneously with three benthic macroinvertebrates (the estuarine amphipod, Leptocheirus plumulosus; the estuarine polychaete, Nereis virens; and the marine clam, Macoma nasuta) in sediments for up to 55 days. All organisms and their co-deployed DGTs exhibited an initial period of rapid Hg uptake followed by slower uptake reaching apparent steady state. Strong correlative relationships were generally observed between paddle-type DGTs and macroinvertebrate tissue data (r(2) between 0.57 and 0.97). Further, %MeHg:Total Hg ratios for M. nasuta and N. virens (38.5 ± 12.2 and 19.2 ± 5.2) were similar to their corresponding ratios for the DGTs (33.1 ± 13.3 and 24.4 ± 11.0), and they were significantly higher than the same ratios for sediment (2.9 ± 0.3) and pore water (8.5 ± 4.9). The %MeHg:Total Hg ratios for L. plumulosus (68.5 ± 6.2) were significantly higher than those for the DGTs. This may be because the tissue and DGT data for this organism were not truly co-located as L. plumulosus burrows close to the sediment surface, and the DGTs sampled the sediment surface. Overall, our results suggest that for benthic macroinvertebrates in estuarine sediments studied here, (a) sediment MeHg is more bioavailable than inorganic Hg, (b) sediment and pore-water concentration measurements are not good predictors for the extent of bioaccumulation of Hg species, and (c) DGTs are an effective biomonitoring tool for the assessment of bioavailability of Hg species.

Advection dominated transport of polycyclic aromatic hydrocarbons in amended sediment caps.

Typical sand caps used for sediment remediation have little sorption capacity to retard the migration of hydrophobic contaminants such as PAHs that can be mobilized by significant groundwater flow. Laboratory column experiments were performed using contaminated sediments and capping materials from a creosote contaminated USEPA Superfund site. Azoic laboratory column experiments demonstrated rapid breakthrough of lower molecular weight PAHs when groundwater seepage was simulated through a column packed with coarse sand capping material. After eight pore volumes of flow, most PAHs measured showed at least 50% of initial source pore water concentrations at the surface of 65 cm capping material. PAH concentration in the cap solids was low and comparable to background levels typically seen in urban depositional sediment, but the pore water concentrations were high. Column experiments with a peat amendment delayed PAH breakthrough. The most dramatic result was observed for caps amended with activated carbon at a dose of 2% by dry weight. PAH concentrations in the pore water of the activated carbon amended caps were 3-4 orders of magnitude lower (0.04 ± 0.02 µg/L for pyrene) than concentrations in the pore water of the source sediments (26.2 ± 5.6 µg/L for pyrene) even after several hundred pore volumes of flow. Enhancing the sorption capacity of caps with activated carbon amendment even at a lower dose of 0.2% demonstrated a significant impact on contaminant retardation suggesting consideration of active capping for field sites prone to groundwater upwelling or where thin caps are desired to minimize change in bathymetry and impacts to aquatic habitats.

Evaluation of sorbent amendments for in situ remediation of metal-contaminated sediments.

The present study evaluated sorbent amendments for in situ remediation of sediments contaminated with two divalent metals. A literature review screening was performed to identify low-cost natural mineral-based metal sorbents and high-performance commercial sorbents that were carried forward into laboratory experiments. Aqueous phase metal sorptivity of the selected sorbents was evaluated because dissolved metals in sediment porewater constitute an important route of exposure to benthic organisms. Based on pH-edge sorption test results, natural sorbents were eliminated due to inferior performance. The potential as in situ sediment amendment was explored by comparing the sorption properties of the engineered amendments in freshwater and saltwater (10 PPT salinity estuarine water) matrices. Self-assembled monolayers on mesoporous supports with thiols (Thiol-SAMMS) and a titanosilicate mineral (ATS) demonstrated the highest sorption capacity for cadmium (Cd) and lead (Pb), respectively. Sequential extraction tests conducted after mixing engineered sorbents with contaminated sediment demonstrated transfer of metal contaminants from a weakly bound state to a more strongly bound state. Biouptake of Cd in a freshwater oligochaete was reduced by 98% after 5-d contact of sediment with 4% Thiol-SAMMS and sorbed Cd was not bioavailable. While treatment with ATS reduced the small easily extractable portion of Pb in the sediment, the change in biouptake of Pb was not significant because most of the native lead was strongly bound. The selected sorbents added to sediments at a dose of 5% were mostly nontoxic to a range of sensitive freshwater and estuarine benthic organisms. Metal sorbent amendments in conjunction with activated carbon have the potential to simultaneously reduce metal and hydrophobic contaminant bioavailability in sediments.

Geochemical stability of chromium in sediments from the lower Hackensack River, New Jersey.

Elevated levels of chromium, partly attributable to historical disposal of chromite ore processing residue, are present in sediment along the eastern shore of the lower Hackensack River near the confluence with Newark Bay. Due to anaerobic conditions in the sediment, the chromium is in the form of Cr(III), which poses no unacceptable risks to human health or to the river ecology. However, as water quality conditions have improved since the 1970s, aerobic conditions have become increasingly prevalent in the overlying water column. If these conditions result in oxidation of Cr(III) to Cr(VI), either under quiescent conditions or during severe weather or anthropogenic scouring events, the potential for adverse ecological effects due to biological exposures to Cr(VI) is possible, though the reaction kinetics associated with oxidation of Cr(III) to Cr(VI) are unfavorable. To investigate the stability of Cr(III) in Hackensack River sediments exposed to oxic conditions, sediment suspension and oxidation experiments and intertidal sediment exposure experiments that exposed the sediments to oxic conditions were conducted. Results revealed no detectable concentrations of Cr(VI), and thus no measurable potential for total chromium oxidation to Cr(VI). Furthermore, total chromium released from sediment to elutriate water in the oxidation and suspension experiments ranged from below detection (<0.01 mg/L) to 0.18 mg/L, below the freshwater National Recommended Water Quality Criteria (NRWQC) of 0.57 mg/L for Cr(III). These results support conclusions of a stable, in situ geochemical environment in sediments in the lower Hackensack River with respect to chromium. Results showed that chemicals other than Cr(VI), including copper, lead, mercury, zinc, and PCBs, were released at levels that may pose a potential for adverse ecological effects.

Importance of implementation and residual risk analyses in sediment remediation.

Management strategies for addressing contaminated sediments can include a wide range of actions, ranging from no action, to the use of engineering controls, to the use of more aggressive, intrusive activities related to removing, containing, or treating sediments because of environmental or navigation considerations. Risk assessment provides a useful foundation for understanding the environmental benefits, residual hazards, and engineering limitations of different remedy alternatives and for identifying or ranking management options. This article, part of a series of panel discussion papers on sediment remediation presented at the Third International Conference on Remediation of Contaminated Sediments held 20-25 January 2005 in New Orleans, Louisiana, USA, reviews 2 types of risk that deserve careful consideration when evaluating remedy alternatives. The evaluation of remedy implementation risks addresses predominantly short-term engineering issues, such as worker and community health and safety, equipment failures, and accident rates. The evaluation of residual risks addresses predominantly longer-term biological and environmental issues, such as ecological recovery, bioaccumulation, and relative changes in exposure and effects to humans, aquatic biota, and wildlife. Understanding the important pathways for contaminant exposure, the human and wildlife populations potentially at risk, and the possible hazards associated with the implementation of different engineering options will contribute to informed decision making with regard to short- and long-term effectiveness, implementability, and potential environmental hazards.

The role of monitored natural recovery in sediment remediation.

The long-term goal of monitored natural recovery (MNR) is to achieve ecological recovery of biological endpoints in order to protect human and ecological health. Insofar as ecological recovery is affected by surface-sediment-contaminant concentrations, the primary recovery processes for MNR are natural sediment burial and contaminant transformation and weathering to less toxic forms. This paper discusses the overall approach for effective implementation of MNR for contaminated sediment sites. Several lines of evidence that may be used to demonstrate natural recovery processes are summarized, including documentation of source control; evidence of contaminant burial; measurement of surface sediment mixing depths and the active sediment benthic layer; measurement of sediment stability; contaminant transformation and weathering; modeling sediment transport, contaminant transport, and ecological recovery; measuring ecological recovery and long-term risk reduction; knowledge of future plans for use and development of the site; and watershed and institutional controls. In general, some form of natural recovery is expected and should be included as part of a remedy at virtually all contaminated sediment sites. Further, MNR investigations and an understanding of natural recovery processes provide cost-effective information and support the evaluation of more aggressive remedies such as capping, dredging, and the use of novel amendments. The risk of dredging or capping may be greater than the risk of leaving sediments in place at sites where capping or dredging offer little long-term environmental gain but pose significant short-term risks for workers, local communities, and the environment.

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 sediments at the Lake Hartwell superfund site: PCB dechlorination. 2. Rates and extent.

This paper reports on extensive polychlorinated biphenyl (PCB) dechlorination measured in Lake Hartwell (Pickens County, SC) sediments. Vertical sediment cores were collected from 18 locations in Lake Hartwell (Pickens County, SC) and analyzed in 5-cm increments for PCB congeners. The preferential loss of meta and para chlorines with sediment depth demonstrated that PCBs in the sediments underwent reductive dechlorination after burial. Notably, ortho chlorines were highly conserved for more than 5 decades; since the first appearance of PCBs, ca. 1950-1955. These dechlorination characteristics resulted in the accumulation of lower chlorinated congeners dominated by ortho chlorine substituents. Dechlorination rates were determined by plotting the numbers of meta plus para chlorines per biphenyl molecule (mol of chlorine/mol of PCB) with sediment age. Regression analyses showed linear correlations between meta plus para chlorine concentrations with time. The average dechlorination rate was 0.094 +/- 0.063 mol of Cl/mol of PCB/yr. The rates measured using the 2001 cores were approximately twice those measured using the 2000 cores, most likely because the 2001 cores were collected only at transects O, L, and I, which had the highest rates measured in 2000. An inverse of the dechlorination rates indicated that 16.4 +/- 11.6 yr was required per meta plus para chlorine removal (ranging from 4.3 to 43.5 yr per chlorine removal). The rates determined from this study were 1-2 orders of magnitude lower than rates reported from laboratory microcosm studies using Hudson River and St. Lawrence River sediments, suggesting that dechlorination rates reported for laboratory experiments are much higher than those occurring in situ.

Assessing and managing contaminated sediments: part I, developing an effective investigation and risk evaluation strategy.

This is the first of a two-part review of the current state-of-the-science pertaining to the assessment and management of contaminated sediments. The goal of this review is to introduce some of the major technical and policy issues stemming from the assessment and management of contaminated sediments, highlight a number of aspects of contaminated sediment assessment and management found to be successful, and, when appropriate, address the barriers that still exist for improving contaminated sediment management. In this paper, Part I, the many key elements of an effective investigation and risk evaluation strategy are reviewed, beginning with the development of a conceptual site model (CSM) and including a discussion of some of the key factors influencing the design of sediment investigations and ecological risk assessment of sediment-bound chemicals on aquatic biota. In Part II of this paper (Apitz et al. 2005), various approaches are reviewed for evaluating sediment risk and monitoring sediment remedy effectiveness. While many of the technical and policy issues described in this review are relevant to dredged material management, the focus of this paper is on sediment assessment for environmental management.

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.

Characterization and FATE of PAH-contaminated sediments at the Wyckoff/Eagle Harbor Superfund Site.

Eagle Harbor, a shallow marine embayment of Bainbridge Island, WA approximately 10 miles west of Seattle, WA), was formerly the site of the Wyckoff wood-treatment facility. The facility used large quantities of creosote in its wood-treating processes from the early 1900s to 1988. Historical creosote seepage into the harbor resulted in substantial accumulation of polycyclic aromatic hydrocarbon (PAH) contamination in the harbor sediments over time. This investigation focused on the distribution and fate of the PAH-contaminated harbor sediments. Analyses of 10 sediment cores using total petroleum hydrocarbon (TPH) fingerprinting, the distribution of 50 PAH analytes, and sediment age dating revealed the contributions of three distinct sources of PAHs to sediment contamination in the harbor during various periods over the past 100 years; namely, creosote, urban runoff, and natural background. Surface sediments (upper 20-30 cm) in the cores closestto the Wyckoff wood-treatment facility and southeast of an existing cap were dominated by urban runoff and weathered creosote; the deeper sediments (> 30 cm) were heavily contaminated with relatively unweathered creosote and some pure-phase creosote. Cores located the furthest from the area of contamination, in the center of the harbor, were dominated by urban runoff, showed no signs of creosote contamination, and had much lower PAH and TPH concentrations than those adjacent to the facility. In the four cores in the center of the Harbor, farthest from the former Wyckoff facility, PAH concentrations increased significantly (p < 0.01) with proximity to the northern shore of the harbor, which is more heavily developed than the southern shore and is where all automobile traffic enters and exits the island through the Bainbridge Island ferry terminal. Deeper portions of these cores were contaminated primarily with natural background PAHs, likely representing preurbanization sediments. Sedimentation rates ranged from 0.54 to 1.10 gm/ cm2 in the four cores located in the middle of the harbor, and for the single nearshore core that could be used to calculate sedimentation rates. Recognition that urban runoff has been a fairly consistent and ongoing source of PAHs to the harbor's sediments for the past 50-70 years may influence future sediment management decisions for this site with respect to long-term monitoring of surface sediments to assess cap performance. The results provided information on the ability of Eagle Harbor sediments to recover under natural conditions, identified the occurrence of creosote-derived PAH weathering in off-cap surface sediments, and distinguished between these distinct PAH sources in the harbor (creosote, urban runoff, and natural background).