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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.

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.

Polychlorinated biphenyls (PCBs) from the commercial mixture Aroclor 1268 were historically released into the Turtle-Brunswick River estuary (southeastern Georgia, USA) from industrial operations. Sum PCBs (ΣPCBs) in blubber samples from Turtle-Brunswick River estuary bottlenose dolphins (Tursiops truncatus) have been reported at concentrations more than 10-fold higher than those observed in dolphins from adjacent regional estuaries. Given that toxicity data specific to Aroclor 1268 and applicable to marine mammals are limited, predicting the toxic effects of Aroclor 1268 in dolphins is uncertain, particularly because of its unique congener profile and associated physiochemical characteristics compared with other PCB mixtures. American mink (Neovison vison) were chosen as a surrogate model for cetaceans to develop marine mammalian PCB toxicity benchmarks. Mink are a suitable surrogate species for cetaceans in toxicity studies because of similarities in diet and taxonomic class, and a characteristic sensitivity to PCBs provides a potential safety factor when using mink toxicology data for cross-species extrapolations. Effects of dietary exposure to Aroclor 1268 on reproduction, growth, and mortality in mink were compared with both a negative control and a positive control (3,3',4,4',5-pentachlorobiphenyl, PCB 126). Aroclor 1268 dietary ΣPCB concentrations ranged from 1.8 µg/g feed wet weight to 29 µg/g feed wet weight. Whelp success was unaffected by Aroclor 1268 exposure at any level. Treatment mean litter size, kit growth, and kit survival were adversely affected relative to the negative control at dietary ΣPCB concentrations of 10.6 µg/g feed wet weight and greater.

Polychlorinated biphenyl (PCB) concentrations reported in preferred prey and blubber of bottlenose dolphins from the Turtle-Brunswick River Estuary (TBRE, Georgia, USA) suggests the potential for adverse effects. However, PCBs in TBRE dolphins are primarily derived from Aroclor 1268, and predicting toxic effects of Aroclor 1268 is uncertain due to the mixture's unique composition and associated physiochemical characteristics. These differences suggest toxicity benchmarks for other PCB mixtures may not be relevant to dolphins exposed to Aroclor 1268. American mink (Neovison vison) were used as a surrogate model for cetaceans to characterize mechanisms of action associated with Aroclor 1268 exposure. Mink share similarities in phylogeny and life history with cetaceans and are characteristically sensitive to PCBs, making them an attractive surrogate species for marine mammals in ecotoxicity studies. Adult female mink and a subsequent F1 generation were exposed to Aroclor 1268 through diet, and effects on enzyme induction, histopathology, thyroid hormone regulation, hematology, organ weights, and body condition index were compared to a negative control and a 3,3',4,4',5-pentachlorobiphenyl (PCB 126) positive control. Aroclor 1268 dietary exposure concentrations ranged from 1.8 to 29 µg/g ww. Anemia, hypothyroidism, and hepatomegaly were observed in mink exposed to Aroclor 1268 beyond various dietary thresholds. Cytochrome P450 induction and squamous epithelial proliferation (SEP) jaw lesions were low in Aroclor 1268 treatments relative to the positive control. Differences in enzyme induction and the development of SEP jaw lesions between Aroclor 1268 treatments and the positive control, coupled with effects observed in Aroclor 1268 treatments not observed in the positive control, indicate that mechanisms additional to the aryl hydrocarbon receptor (AhR)-mediated pathway are associated with Aroclor 1268 exposure. This article is protected by copyright. All rights reserved

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

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 to1.4 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 to6.7 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.

Triclosan, an antimicrobial compound used in personal care products, occurs in the aquatic environment due to residual concentrations in municipal wastewater treatment effluent. We evaluate triclosan-related risks to the aquatic environment, for aquatic and sediment-dwelling organisms and for aquatic-feeding wildlife, based on measured and modeled exposure concentrations. Triclosan concentrations in surface water, sediment, and biota tissue are predicted using a fugacity model parameterized to run probabilistically, to supplement the limited available measurements of triclosan in sediment and tissue. Aquatic toxicity is evaluated based on a species sensitivity distribution, which is extrapolated to sediment and tissues assuming equilibrium partitioning. A probabilistic wildlife exposure model is also used, and estimated doses are compared with wildlife toxicity benchmarks identified from a review of published and proprietary studies. The 95th percentiles of measured and modeled triclosan concentrations in surface water, sediment, and biota tissues are consistently below the 5th percentile of the respective species sensitivity distributions, indicating that, under most scenarios, adverse affects due to triclosan are unlikely. Integr Environ Assess Manag 2010;6:419–440. © 2010 SETAC

The fate and partitioning of the antimicrobial compound, triclosan, in wastewater treatment plants (WWTPs) is evaluated using a probabilistic fugacity model to predict the range of triclosan concentrations in effluent and secondary biosolids. The WWTP model predicts 84% to 92% triclosan removal, which is within the range of measured removal efficiencies (typically 70% to 98%). Triclosan is predominantly removed by sorption and subsequent settling of organic particulates during primary treatment and by aerobic biodegradation during secondary treatment. Median modeled removal efficiency due to sorption is 40% for all treatment phases and 31% in the primary treatment phase. Median modeled removal efficiency due to biodegradation is 48% for all treatment phases and 44% in the secondary treatment phase. Important factors contributing to variation in predicted triclosan concentrations in effluent and biosolids include influent concentrations, solids concentrations in settling tanks, and factors related to solids retention time. Measured triclosan concentrations in biosolids and non-United States (US) effluent are consistent with model predictions. However, median concentrations in US effluent are over-predicted with this model, suggesting that differences in some aspect of treatment practices not incorporated in the model (e.g., disinfection methods) may affect triclosan removal from effluent. Model applications include predicting changes in environmental loadings associated with new triclosan applications and supporting risk analyses for biosolids-amended land and effluent receiving waters. Integr Environ Assess Manag 2010;6:393–404. © 2010 SETAC

Triclosan is an antimicrobial compound found in many consumer products including soaps and personal care products. Most triclosan is disposed of down household drains, whereupon it is conveyed to wastewater treatment plants. Although a high percentage of triclosan biodegrades during wastewater treatment, most of the remainder is adsorbed to sludge, which may ultimately be applied to land as biosolids. We evaluated terrestrial ecological risks related to triclosan in land-applied biosolids for soil microbes, plants, soil invertebrates, mammals, and birds. Exposures are estimated using a probabilistic fugacity-based model. Triclosan concentrations in biosolids and reported biosolids application rates are compiled to support estimation of triclosan concentrations in soil. Concentrations in biota tissue are estimated using an equilibrium partitioning model for plants and worms and a steady-state model for small mammals; the resulting tissue concentrations are used to model mammalian and avian dietary exposures. Toxicity benchmarks are identified from a review of published and proprietary studies. The results indicate that adverse effects related to soil fertility (i.e., disruption of nitrogen cycling) would be expected only under "worst-case" exposures, under certain soil conditions and would likely be transient. The available data indicate that adverse effects on plants, invertebrates, birds, and mammals due to triclosan in land-applied biosolids are unlikely.

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 (

We conducted a quantitative analysis of published results from more than 50 tests of polychlorinated biphenyl (PCB) effects on mink reproduction, which provided a basis for evaluating how well different methods of measuring and assessing PCB concentrations can approximate a toxicologically relevant dose for this endpoint. Several dose metrics were identified for comparison. Dietary dose metrics included the daily intake of total PCBs and the daily intake of 2,3,7,8-tetrachlorodibenzo-p-dioxin toxicity equivalence concentrations (TECs), calculated using World Health Organization toxicity equivalence factors (TEFs). Internal dose metrics included whole-body total PCBs, whole-body TECs calculated using World Health Organization TEFs, and whole-body TECs calculated using alternative TEFs specifically identified for internal dose assessment. Accounting for the bioaccumulative potential (i.e., internal dose) of ingested PCBs proved to be more important than accounting for the concentrations of dioxin-like PCB congeners in explaining the observed variation in reproductive success. This was true regardless of whether internal doses were estimated from dietary data based on homolog concentrations (whole-body total PCBs) or congener concentrations (whole-body TECs). For each of the PCB dose metrics, a range of toxicity reference values is identified based on the species-specific PCB toxicity database compiled for this evaluation.

Total and hexavalent chromium [Cr(VI)] were measured in sediment and sediment porewater in the lower Hackensack River (NJ) to assess the relationship between sediment geochemistry and chromium speciation, which in turn controls the mobility, bioavailability, and toxicity of chromium. Between 2003 and 2005, >100 surface (0 to 15 cm) sediment samples were tested for total chromium and Cr(VI), acid-volatile sulfides (AVS), ferrous iron (Fe(II)), divalent manganese (Mn(II)), ammonia, and organic carbon. Sediment porewater samples were collected by centrifugation or using in situ samplers colocated with the collection of sediments. In whole sediments, total chromium and Cr(VI) concentrations ranged from 5 to 9190 mg/kg dry weight (dw) and from

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.

Polychlorinated biphenyls (PCBs) from the commercial mixture Aroclor 1268 were historically released into the Turtle-Brunswick River estuary (southeastern Georgia, USA) from industrial operations. Sum PCBs (ΣPCBs) in blubber samples from Turtle-Brunswick River estuary bottlenose dolphins (Tursiops truncatus) have been reported at concentrations more than 10-fold higher than those observed in dolphins from adjacent regional estuaries. Given that toxicity data specific to Aroclor 1268 and applicable to marine mammals are limited, predicting the toxic effects of Aroclor 1268 in dolphins is uncertain, particularly because of its unique congener profile and associated physiochemical characteristics compared with other PCB mixtures. American mink (Neovison vison) were chosen as a surrogate model for cetaceans to develop marine mammalian PCB toxicity benchmarks. Mink are a suitable surrogate species for cetaceans in toxicity studies because of similarities in diet and taxonomic class, and a characteristic sensitivity to PCBs provides a potential safety factor when using mink toxicology data for cross-species extrapolations. Effects of dietary exposure to Aroclor 1268 on reproduction, growth, and mortality in mink were compared with both a negative control and a positive control (3,3',4,4',5-pentachlorobiphenyl, PCB 126). Aroclor 1268 dietary ΣPCB concentrations ranged from 1.8 µg/g feed wet weight to 29 µg/g feed wet weight. Whelp success was unaffected by Aroclor 1268 exposure at any level. Treatment mean litter size, kit growth, and kit survival were adversely affected relative to the negative control at dietary ΣPCB concentrations of 10.6 µg/g feed wet weight and greater.

Polychlorinated biphenyl (PCB) concentrations reported in preferred prey and blubber of bottlenose dolphins from the Turtle-Brunswick River estuary (Georgia, USA) suggest the potential for adverse effects. However, PCBs in Turtle-Brunswick River estuary dolphins are primarily derived from Aroclor 1268, and predicting toxic effects of Aroclor 1268 is uncertain because of the mixture's unique composition and associated physiochemical characteristics. These differences suggest that toxicity benchmarks for other PCB mixtures may not be relevant to dolphins exposed to Aroclor 1268. American mink (Neovison vison) were used as a surrogate model for cetaceans to characterize mechanisms of action associated with Aroclor 1268 exposure. Mink share similarities in phylogeny and life history with cetaceans and are characteristically sensitive to PCBs, making them an attractive surrogate species for marine mammals in ecotoxicity studies. Adult female mink and a subsequent F1 generation were exposed to Aroclor 1268 through diet, and effects on enzyme induction, histopathology, thyroid hormone regulation, hematology, organ weights, and body condition index were compared to a negative control and a 3,3',4,4',5-pentachlorobiphenyl (PCB 126)-positive control. Aroclor 1268 dietary exposure concentrations ranged from 1.8 µg/g wet weight to 29 µg/g wet weight. Anemia, hypothyroidism, and hepatomegaly were observed in mink exposed to Aroclor 1268 beyond various dietary thresholds. Cytochrome P450 induction and squamous epithelial proliferation jaw lesions were low in Aroclor 1268 treatments relative to the positive control. Differences in enzyme induction and the development of squamous epithelial proliferation jaw lesions between Aroclor 1268 treatments and the positive control, coupled with effects observed in Aroclor 1268 treatments not observed in the positive control, indicate that mechanisms additional to the aryl hydrocarbon receptor-mediated pathway are associated with Aroclor 1268 exposure.

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.

Three approaches were used in a site-specific sediment toxicity evaluation for hexachlorobutadiene (HCBD), a chemical not previously tested for toxicity in sediment. The results of a sediment dilution study, spiked sediment toxicity tests, and a probabilistic model based on equilibrium partitioning theory were used to estimate ecological effects thresholds for HCBD in sediments of a Gulf Coast estuary. Twenty-nine sediment samples, including 11 undiluted samples and six dilution series, were tested for toxicity under estuarine conditions (10%0 salinity) using Hyalella azteca and Leptocheirus plumulosus. Site sediment was used as diluent, and all samples were assayed for a range of organic and inorganic chemicals. A logistic relationship was observed between HCBD concentrations and organism response, and nonlinear regression explained approximately 90% of the observed variation in amphipod survival as a function of HCBD. Spiked sediment toxicity test results generally agreed with the results of the dilution study, demonstrating the causality of the observed concentration–response relationship. Effects thresholds were estimated as HCBD concentrations corresponding to 80% amphipod survival. The most conservative effects thresholds from the spiked sediment and dilution studies were 0.63 mg/kg normalized to 1% total organic carbon (mg/kg1%OC) for H. azteca and 1.4 mg/kg1%OC for L. plumulosus. Aquatic LC50s for 10 species and a measured acute–chronic ratio from the published literature were used to predict a distribution of sediment effects thresholds for HCBD, with 10th and 90th percentile values of 2.6 and 45 mg/kg1%OC, respectively. The predicted and observed sediment effects thresholds thus agreed relatively well, although the H. azteca and L. plumulosus test results from this study seem to be somewhat more conservative than the majority of published aquatic toxicity test results.

Many evaluations estimating safe levels of hydrophobic organic chemicals in sediments do not account for confounding factors such as physical habitat quality or covariance among chemicals. Controlled experiments demonstrating cause and effect can be conducted with spiked sediment toxicity tests, but application of this methodology has been limited in part by concerns about chemical bioavailability and challenges in achieving target concentrations. Relevant literature was reviewed to assess the utility of standardizing sediment equilibration times; hydrophobicity, complex sediment characteristics, and temperature were identified as potentially equally important factors. Disequilibrium appears likely following limited equilibration time but should yield conservative toxicity test results relative to aged field sediments. Nominal and measured concentrations in over 20 published studies were compared to assess spiked chemical recovery (i.e., measured concentration/nominal concentration). Recovery varied subst...

A probabilistic model was developed to predict effects threshold concentrations for chlorinated benzenes in sediment. Based on published quantitative structure-activity relationships relating the toxicity of chlorinated benzenes to the degree of chlorination, congeners with the same number of chlorine substitutions were considered toxicologically equivalent. Hexachlorobenzene was excluded from the assessment based on a lack of aquatic toxicity at the water solubility limit. The equilibrium partitioning approach was applied in a probabilistic analysis to derive predicted effects thresholds (PETs) for each chlorinated benzene group, with model input distributions defined by published log Kow values and aquatic toxicity data (LC50s and acute to chronic ratios) extracted from the published literature. The probabilistic distributions of PETs generally increased with chlorination, with 20th percentile values ranging from 3.2 mg/kg1%OC for chlorobenzene to 67 mg/kg1%OC for tetrachlorobenzene congeners. The toxicity of total chlorinated benzenes in sediment can be assessed by applying the PETs in a toxic index model, based on the assumption that multiple chlorinated benzene congeners will show approximately additive toxicity, as characteristic of nonpolar narcotic toxicants. The 20th percentile PET values are one to two orders of magnitude higher than published screening-level guidelines, suggesting that the screening-level guidelines will provide overly conservative assessments in most cases. Relevant spiked sediment toxicity data are very limited but seem consistent with the probabilistic model; additional testing could be conducted to confirm the model's predictions.

Hexachlorobenzene (HCB) is a hydrophobic organic chemical that has shown a lack of toxicity in aquatic tests at concentrations up to and exceeding the solubility limit. The equilibrium partitioning approach to deriving sediment quality benchmarks, which assumes that toxicity can be predicted based on contaminant concentrations in interstitial water, predicts that HCB will not produce direct toxicity to benthic invertebrates as a sediment contaminant. However, the potential for toxicity due to direct exposure to sediment-adsorbed HCB has not been thoroughly established. This study evaluated the survival and growth of the estuarine amphipod Leptocheirus plumulosus, the freshwater amphipod Hyalella azteca, and the midge Chironomus tentans (freshwater) following 10-day exposure to sediment spiked with a range of HCB concentrations. H. azteca was tested under both freshwater and estuarine (10 ppt salinity) conditions. No significant toxicity was observed for any test species at the highest test concentration (60 mg/kg normalized to 1% organic carbon). Minimum detectable differences were less than or equal to 20% for three of eight test endpoints. The observed results add to the available weight of evidence indicating a limited potential for HCB-related sediment toxicity to benthic invertebrates.

A recent study conducted by the National Oceanic and Atmospheric Administration (NOAA) reported a highly significant correlation between 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) concentrations and amphipod (Ampelisca abdita) mortality in sediment samples collected from the lower Passaic River and Newark Bay. However, there is a paucity of data regarding the potential effects of 2,3,7,8-TCDD on benthic invertebrates under controlled laboratory exposures. In this study, 10-d whole-sediment bioassays using the marine amphipod A. abdita were conducted on spiked sediment samples representing a range of 2,3,7,8-TCDD concentrations (0–25 μg/kg dry weight). No effects on survival or growth relative to controls were observed at any test concentration. The highest 2,3,7,8-TCDD concentration reported from the NOAA study was 0.62 μg/kg. Therefore, the lack of 2,3,7,8-TCDD toxicity in this study indicates that the mortality observed in the NOAA study was probably due to factors or chemicals other than 2,3,7,8-TCDD. This study demonstrates the utility of spiked sediment bioassays in evaluating cause and effect relationships between sediment contamination and benthic invertebrate mortality.

Fourteen-day, whole-sediment toxicity tests using the amphipod Hyalella azteca and the midge Chironomus tentans were conducted on spiked sediment samples representing a range of hexachlorobenzene (HCB) concentrations. High rates of survival and growth relative to controls were observed in both test species. No observed effects concentrations (NOECs) were equal to the highest HCB concentration tested (42 mg/kg, normalized to 1% total organic carbon). Available literature on the aquatic toxicity of this hydrophobic chemical shows an absence of lethal and sublethal effects from exposure to HCB or below water solubility concentrations, and toxicity from exposure to dissolved HCB in sediment porewater therefore would not be expected. Because whole-sediment toxicity tests integrate exposure to HCB dissolved in porewater and adsorbed to particles, it was considered possible that exposure via sediment ingestion could cause toxicity; however, no such effect was observed in this study.

Monitored natural recovery (MNR) of contaminated sediments is a remedial approach that relies on natural physical, chemical, and biological processes to isolate, destroy, or otherwise reduce the bioavailability or toxicity of contaminants (USEPA, 2005a; NRC, 1997). Like other sediment remedies, MNR typically includes contaminant source control, site investigation, development of a conceptual site model (CSM), and long-term monitoring. Unlike other remedies, MNR does not include a construction phase; however, it is not a “no-action” approach. If monitoring indicates that recovery is not proceeding as predicted, site managers may implement enhanced MNR (EMNR, discussed later in this chapter), combine MNR with other remedies such as capping, removal, or institutional controls, consider alternate remedies, or adjust expectations of MNR recovery (Magar et al., 2009).

Although weakly hydrophobic chemicals such as volatile organic compounds (VOCs) tend not to persist in sediments, they may nevertheless be present in some sediments because of recent or ongoing releases. Standard methods are not available for assessing risks to benthic invertebrates due to VOCs in sediment. More strongly hydrophobic organic chemicals are frequently assessed by using the equilibrium partitioning (EqP) approach, which predicts the bioavailable fraction of chemical (the concentration dissolved in pore water) from the sediment-sorbed fraction, assuming that partitioning is at equilibrium. As typically applied, the EqP approach is ineffective for assessing VOCs in sediment, because the standard EqP equation fails to account for the contribution of dissolved chemical to the total chemical concentration in sediment. For chemicals with low organic carbon-water partition coefficients (KOCs), this results in nonsensical sediment-quality benchmarks that are more conservative (i.e., lower) than benchmarks calculated by assuming 100% bioavailability. A modified EqP equation is presented that accounts for the dissolved fraction of total chemical concentrations in sediment. Results of the standard and modified EqP equations converge with increasing KOC and are essentially identical at log KOC values exceeding approximately 3.5.

A Sediment Quality Triad (SQT) study consisting of chemical characterization in sediment, sediment toxicity and bioaccumulation testing, and benthic community assessments was performed in the Lower Hackensack River, New Jersey. Chemistry data in sediment and porewater were evaluated based on the equilibrium partitioning approach and other published information to investigate the potential for chemical effects on benthic organisms and communities. Relationships were supported by laboratory toxicity and bioaccumulation experiments to characterize chemical effects and bioavailability. Benthic community results were evaluated using a regional, multimetric benthic index of biotic integrity and four heterogeneity indices. Evidence of slight benthic community impairment was observed in five of nine sediment sample stations. Severe lethal toxicity to amphipods (Leptocheirus plumulosus) occurred in four of these five stations. Although elevated total chromium concentrations in sediment (as high as 1900 mg/kg) were the rationale for conducting the investigation, toxicity was strongly associated with concentrations of polycyclic aromatic hydrocarbons (PAHs) rather than total chromium. PAH toxic units (SigmaPAH TU) in sediment and SigmaPAH concentrations in laboratory organisms from the bioaccumulation experiment showed a clear dose-response relationship with toxicity, with 0% survival observed in sediments in which SigmaPAH TU1-2 and SigmaPAH concentrations in Macoma nasuta were2 micromol/g, lipid weight. Metals detected in sediment and porewater, with the possible exception of copper, did not correlate with either toxicity or levels in tissue, likely because acid-volatile sulfide levels exceeded concentrations of simultaneous extracted metals at all sample locations. The study reinforces the value of using multiple lines of evidence approaches such as the SQT and the importance of augmenting chemical and biological analyses with modeling and/or other approaches to evaluate chemical bioavailability and toxicity of sediments.

An understanding of the environmental effects of the use of wildland fire retardant is needed to provide informed decision-making regarding forest management. We compiled data from all post-fire surface water monitoring programs where the fire retardant constituents ammonia, phosphorus, and cyanide were measured, and data were available in the public domain. For streams near four major wildfires, we evaluated whether these chemicals originated primarily from fire or from retardant use. We compared measured concentrations in streams where chemical wildland fire retardant was applied with concentrations in streams draining areas where retardant was not used. Correlations with calcium provided an additional line of evidence, because calcium concentrations in ash are much higher than in retardant. Ammonia, phosphorus, and total cyanide were found in streams in burned areas where retardant was not used, at concentrations similar to those found in areas where retardant was applied. Concentrations of weak acid dissociable cyanide were generally non-detected or very low, whether or not wildland fire retardant was used in the watershed. These results indicate that the application of wildland fire retardant had minimal effects on proximate surface water quality. Cyanide concentrations in post-fire stormwater runoff were not affected by the presence of ferrocyanide in the retardant formulas and were due to pyrogenic sources.

Although weakly hydrophobic chemicals such as volatile organic compounds (VOCs) tend not to persist in sediments, they may nevertheless be present in some sediments because of recent or ongoing releases. Standard methods are not available for assessing risks to benthic invertebrates due to VOCs in sediment. More strongly hydrophobic organic chemicals are frequently assessed by using the equilibrium partitioning (EqP) approach, which predicts the bioavailable fraction of chemical (the concentration dissolved in pore water) from the sediment-sorbed fraction, assuming that partitioning is at equilibrium. As typically applied, the EqP approach is ineffective for assessing VOCs in sediment, because the standard EqP equation fails to account for the contribution of dissolved chemical to the total chemical concentration in sediment. For chemicals with low organic carbon-water partition coefficients (Kocs), this results in nonsensical sediment-quality benchmarks that are more conservative (i.e., lower) than benchmarks calculated by assuming 100% bioavailability. A modified EqP equation is presented that accounts for the dissolved fraction of total chemical concentrations in sediment. Results of the standard and modified EqP equations converge with increasing Koc and are essentially identical at log Koc values exceeding approximately 3.5.

Aquatic toxicity due to the creation and mobilization of chemical constituents by fire has been little studied, despite reports of post-fire fish kills attributed to unspecified pyrogenic toxicants. We examined releases of cyanides from biomass burning and their effect on surface runoff water. In laboratory test burns, available cyanide concentrations in leachate from residual ash were much higher than in leachate from partially burned and unburned fuel and were similar to or higher than the 96-h median lethal concentration (LC50) for rainbow trout (45 microg/l). Free cyanide concentrations in stormwater runoff collected after a wildfire in North Carolina averaged 49 microg/l, again similar to the rainbow trout LC50 and an order of magnitude higher than in samples from an adjacent unburned area. Pyrogenic cyanide inputs, together with other fire-related stressors, may contribute to post-fire fish mortalities, particularly those affecting salmonids.

A site-specific evaluation of mercury toxicity was conducted for sediments of the Calcasieu River estuary (Louisiana, USA). Ten-day whole-sediment toxicity tests assessed survival and growth (dry weight) of the amphipods Hyalella azteca and Leptocheirus plumulosus under estuarine conditions (10 ppt salinity). A total of 32 sediment samples were tested for toxicity, including 14 undiluted site sediment samples and 6 sediment dilution series. All sediment samples were analyzed for total mercury and numerous other chemical parameters, including acid volatile sulfide (AVS) and simultaneously extracted metals (SEM). No toxicity attributable to mercury was observed, indicating that a site-specific threshold for total mercury toxicity to amphipods exceeds 4.1 mg/kg dry weight. Site-specific factors that may limit mercury bioavailability and toxicity include relatively high sulfide levels. Additionally, the chemical extractability of mercury in site sediments is low, as indicated by SEM mercury analyses for three sediment samples containing a range of total mercury concentrations.http://link. springer-ny.com/link/service/journals/00244/bibs/37n4p488.++ +html/HEA

Taylor et al.'s (2003) paper, An Ecological Risk Assessment for Hexachlorobutadiene, provides much useful information on this relatively little-studied compound. However, the authors are incorrect ...

Cause-effect sediment-quality benchmarks for the protection of benthic invertebrates are needed for polychlorinated biphenyls (PCBs) to support predictive risk assessments and retrospective evaluations of the causes of observed sediment toxicity. An in-depth evaluation of PCB aquatic toxicity and organic carbon partitioning was conducted to predict sediment effect concentrations using the equilibrium partitioning (EqP) approach. This evaluation was limited to invertebrate toxicity data, because PCBs may exert toxicity to invertebrates and fish via different toxicological mechanisms. As a result of differences in organic carbon partitioning among PCBs of differing levels of chlorination, the estimated EqP benchmarks increase with increasing degree of chlorination for various commercial and environmental PCB mixtures. Studies of spiked sediment toxicity using PCBs were reviewed, and their results generally were consistent with EqP predictions. Additionally, toxicity and benthic community data were reviewed for eight PCB-contaminated sites; these data also showed agreement with EqP predictions. None of these lines of evidence supports previously proposed, empirical sediment-quality guidelines for PCBs. Reasons for the lack of agreement between cause-effect and association-based benchmarks are discussed, and areas of future research to further refine EqP predictions for PCBs are identified.