Sources of 2,3,7,8-Tetrachlorodibenzo-p-dioxin and Other Dioxins in Lower Passaic River, New Jersey, Sediments.

Elevated levels of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and other contaminants have been reported in lower Passaic River, New Jersey, USA, sediments since the 1980s. Nearly 8000 surficial and buried sediment samples have been collected along the 17 miles (27.4 km) of river and analyzed for various contaminants, including the seventeen 2,3,7,8-substituted PCDD/F congeners. Principal component analysis and hierarchical cluster analysis reveal spatial heterogeneity in the distribution of dioxin congeners, with respect to both sediment depth and river mile. Polytopic vector analysis resolved 11 unique 2,3,7,8-substituted dioxin congener profiles in the river sediment. The profiles were consistent with multiple dioxin source types, including manufacture of certain dyes and pigments, chlorinated industrial chemicals, hexachlorophene, polychlorinated biphenyls, waste disposal and incineration, the production and use of 2,4,5-trichorophenol (2,4,5-TCP), and other industrial processes. The distribution of dioxin profiles in surface and buried river sediments is indicative of multiple inputs of 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) and other dioxins at different locations along the lower Passaic River. These findings are inconsistent with historical claims that a former herbicide manufacturing plant in the lower reach of the river is the only significant 2,3,7,8-TCDD source and consistent with evidence of several different inputs associated with the production, use, and/or disposal of 2,4,5-TCP at several locations along the lower Passaic River. Environ Toxicol Chem 2021;40:1499-1519. © 2020 SETAC.

Selenium and mercury in freshwater fish muscle tissue and otoliths: a comparative analysis.

Evaluating potential ecological and human health risks of exposure to bioaccumulative trace elements is typically implemented using analysis of tissue samples. Increasingly, the microchemistry of fish calcified structures is used to elucidate the lifetime exposure to trace elements. In the present study, we measured total mercury (THg), methylmercury (MeHg), and selenium (Se) in muscle tissue and otolith samples from 12 species of fish collected at reference sites and locations influenced by power plant wastewater. Muscle tissue concentrations of Se were sensitive to recent wastewater exposure magnitude, stream type, trophic level, and species (p < 0.001). For Hg, concentrations in muscle tissue and otoliths were affected only by trophic level and species. Levels of THg and Se in muscle tissue and otolith samples were positively correlated for those species with a robust sample size. Some individual fish from 3 species (channel catfish, hybrid striped bass, and freshwater drum) showed significantly increasing or decreasing lifetime concentrations of either THg or Se in otolith samples. Multiple regression analysis indicated that for bluegill muscle tissue Se concentrations could be best explained utilizing water concentrations of selenium, sulfate, and molybdenum (r2 = 0.87; p < 0.001). Because of the increased cost and specialized sample processing requirements of analyzing trace elements in otolith structures, it may be prudent to limit these analyses to those species where insights into temporal trends are sought or where evidence indicates that fish move into or out of contaminated water bodies. Environ Toxicol Chem 2019;38:1467-1475. © 2019 SETAC.

Visible-Light-Induced, Catalyst-Free Radical Arylations of Arenes and Heteroarenes with Aryldiazonium Salts.

In the absence of a photocatalyst and other additives, the radical arylation of diverse arenes and heteroarenes has been achieved with aryldiazonium salts under visible-light irradiation from a blue light-emitting diode (LED). Although the course of some reactions can be rationalized by the formation of strongly light-absorbing charge-transfer (CT) complexes between the diazonium ion and the aromatic substrate, several further examples indicated that the simple presence of an aromatic substrate, showing only weak interactions to the diazonium ion, is fully sufficient to enable product formation.

Evaluation of triclosan in Minnesota lakes and rivers: Part II - human health risk assessment.

Triclosan, an antimicrobial compound found in consumer products, has been detected in low concentrations in Minnesota municipal wastewater treatment plant (WWTP) effluent. This assessment evaluates potential health risks for exposure of adults and children to triclosan in Minnesota surface water, sediments, and fish. Potential exposures via fish consumption are considered for recreational or subsistence-level consumers. This assessment uses two chronic oral toxicity benchmarks, which bracket other available toxicity values. The first benchmark is a lower bound on a benchmark dose associated with a 10% risk (BMDL10) of 47mg per kilogram per day (mg/kg-day) for kidney effects in hamsters. This value was identified as the most sensitive endpoint and species in a review by Rodricks et al. (2010) and is used herein to derive an estimated reference dose (RfD(Rodricks)) of 0.47mg/kg-day. The second benchmark is a reference dose (RfD) of 0.047mg/kg-day derived from a no observed adverse effect level (NOAEL) of 10mg/kg-day for hepatic and hematopoietic effects in mice (Minnesota Department of Health [MDH] 2014). Based on conservative assumptions regarding human exposures to triclosan, calculated risk estimates are far below levels of concern. These estimates are likely to overestimate risks for potential receptors, particularly because sample locations were generally biased towards known discharges (i.e., WWTP effluent).

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.

An updated evaluation of the carcinogenic potential of 1,4-dioxane.

This paper presents a critical review of the information pertaining to the potential carcinogenicity of 1,4-dioxane. The primary target organs for cancer via the oral route are the liver and the nasal cavity, however, the relevance of nasal cavity tumors to human exposures has been questioned. Liver tumors were accompanied by degenerative changes and appear only to occur at high doses where clearance mechanisms are saturated and liver toxicity is significant. Genetic toxicity data suggests that 1,4-dioxane is a very weak genotoxin. An increase in hepatocyte cell proliferation was reported and 1,4-dioxane was shown to act as a tumor promoter in rat liver and mouse skin carcinogenicity assays. Two reports are available from the literature regarding physiologically based pharmacokinetic (PBPK) modeling approaches to assess the risk of liver cancer for 1,4-dioxane. A comparison of cancer risk estimates from linear and nonlinear models in the presence or absence of PBPK modeling suggests that USEPAs current cancer slope factor significantly overestimates the potential cancer risk from 1,4-dioxane. This critical review of the scientific literature indicates that a formal reevaluation of the carcinogenic potency of 1,4-dioxane is warranted.

Inhibition of digestive enzyme activities by copper in the guts of various marine benthic invertebrates.

Digestive systems of deposit and suspension feeders can be exposed to high concentrations of copper (Cu) by ingestion of contaminated sediments. We assessed a potential impact of this Cu exposure on digestive enzyme activities in a wide range of benthic organisms by monitoring enzyme activities in their gut fluids during in vitro titrations with dissolved Cu, which mimics Cu solubilization from sediments. Increasing Cu inhibited digestive protease activities at threshold values, which varied widely among organisms, from 8 microM for an echinoderm to 0.4 M for an echiuran. More Cu was required to inhibit proteases in guts containing higher amino acid concentrations because strong Cu-binding sites on amino acids prevent Cu interaction with the enzymatically active sites. Threshold Cu concentrations were similar for proteases, esterases, lipases, and alpha- and beta-glucosidases, suggesting the same inhibition mechanism. Copper was less effective at inhibiting enzymes at lower pH, suggesting that protons can compete with Cu ion for binding to enzymatically active sites or that enzyme conformation is less vulnerable to Cu inhibition at lower pH. These results lead to the counterintuitive conclusion that deposit feeders with low enzyme activity, low amino acid concentration, and high pH values are most vulnerable to harm from sedimentary Cu by this mechanism, although they solubilize less sedimentary Cu than their counterparts with high enzyme activity, high amino acid concentrations, and low gut pH. In general, digestive systems of echinoderms may therefore be more susceptible to Cu contamination than those of polychaetes, with various other phyla showing intermediate susceptibilities. If threshold Cu values are converted to solid-phase sedimentary Cu concentrations, the thresholds are at least consistent with Cu loadings that have been observed to lead to biological impacts in the field.