Variation in natural attenuation rates of polychlorinated biphenyls (PCBs) in fish from streams and reservoirs in East Tennessee observed over a 35-year period.

Environmental contamination due to human activities is a major concern, particularly for persistent chemicals. Within catchments, persistent chemicals linked to negative health outcomes such as polychlorinated biphenyls (PCBs) have great potential to be transported, through adsorption or biological uptake, with downstream locations acting as sinks for accumulation. Here we present long-term trends in PCB bioaccumulation in fish found in lower-order tributaries on the Oak Ridge Reservation, an impacted US Department of Energy property in East Tennessee, USA, and a large reservoir system adjacent to it composed of parts of the Clinch and Tennessee Rivers. Given that the reservoir system has experienced no direct PCB mitigation activities, this record offers an opportunity to explore potential natural attenuation of PCBs within a large lotic ecosystem. Attenuation rates ranged from 0% to 8% yr-1 in minnows and sunfish at stream sites and 5.4-11.3% yr-1 in catfish at reservoir sites. These rates are comparable to findings from similar studies in other regions, suggesting a consistency in responses since the banning of PCB production in 1979. Further, results suggest that PCB sources from discharge outfalls are important locally but are not primarily responsible for sustaining PCB contamination in downstream reservoirs.

Stannous chloride as a tool for mercury stripping in contaminated streams: Experimental assessment of toxicity in an invertebrate model species.

The chronic toxicity of an innovative Hg water treatment system using tin (Sn) (II) chloride (SnCl2) followed by air stripping was assessed through measurements of survival, growth, and reproduction rate in the freshwater cladoceran Ceriodaphnia dubia, a model species for toxicity testing. We first calculated the concentrations of Hg causing 25% reduction in survival and reproduction (Lethal or Inhibition Concentrations, or LC25 and IC25, for survival and reproduction, respectively) through exposure to aqueous Hg at concentrations ranging from 0 to 25,000 ng L-1. Then, we treated media (DMW and natural stream water) contaminated with Hg at LC25 and IC25 concentrations with SnCl2 at a Sn:Hg stoichiometric ratio of 8:1 and air stripping and exposed C. dubia to this Sn-amended media. Our results showed that Hg significantly affected survival, reproduction rates and impaired growth. SnCl2-treatment removed 100% of the Hg from the media at all concentrations tested with no deleterious effects on survival, growth and reproduction. Our results confirmed the efficacy of SnCl2 in removing aqueous Hg from stream water and showed that the added Sn did not impact C. dubia at the concentrations tested, supporting the suitability of SnCl2-based treatments in appropriate Hg-contaminated environments.

Integrated watershed process model for evaluating mercury sources, transport, and future remediation scenarios in an industrially contaminated site.

We used the Soil Water Assessment Tool (SWAT) as a framework to develop an empirical Hg flux model for Upper East Fork Poplar Creek (UEFPC), a Hg-contaminated watershed in Oak Ridge, Tennessee. By integrating long-term Hg monitoring data with simulated flow and suspended solid loads in a site-specific empirical Hg transport model, we (1) quantified the spatial, temporal, and flow regime controls on daily Hg flux (adjusted R2 = 0.82) and (2) made predictions about Hg flux under future climate, land use, and management scenarios. We found that 62.79% of the average daily Hg flux in the watershed is currently driven by base flow, whereas variability in Hg flux is driven by storm and extreme flow. We estimate an average annual Hg flux of 28.82 g day-1 leaving the watershed under baseline precipitation, with an estimated 43.73% reduction in daily Hg flux under drought conditions and a 296% increase in daily Hg flux in extreme precipitation scenarios. We estimated that a new mercury treatment facility would result in a 24.7% reduction in Hg flux under baseline conditions and a 33.4% reduction under extreme precipitation scenarios. The study demonstrated the merit of this approach, which can be replicated for sites where information on flow, suspended solids, and Hg concentrations is available.

Comparing Trace Element Bioaccumulation and Depuration in Snails and Mayfly Nymphs at a Coal Ash-Contaminated Site.

We examined the bioaccumulation of essential (Cu, Fe, Se, and Zn) and nonessential (As and Hg) trace elements in 2 aquatic invertebrate species (adult snails and mayfly nymphs) with different feeding habits at the site of a coal ash spill. Differences in food web pathway, exposure concentrations, and biological processing affected bioaccumulation patterns in these species. Mayflies had higher body burdens, but snails had higher retention of most elements studied. Environ Toxicol Chem 2020;39:2437-2449. © 2020 SETAC.

The Effect of Dietary Exposure to Coal Ash Contaminants within Food Ration on Growth and Reproduction in Daphnia magna.

Coal ash contains numerous contaminants and is the focus of regulatory actions and risk assessments due to environmental spills. We exposed Daphnia magna to a gradient of coal ash contamination under high and low food rations to assess the sublethal effects of dietary exposures. Whereas exposure to contaminants resulted in significant reductions in growth and reproduction in daphnids, low, environmentally relevant food rations had a much greater effect on these endpoints. Environ Toxicol Chem 2020;39:1998-2007. © 2020 SETAC.

Integration of ecosystem science into radioecology: A consensus perspective.

In the Fall of 2016 a workshop was held which brought together over 50 scientists from the ecological and radiological fields to discuss feasibility and challenges of reintegrating ecosystem science into radioecology. There is a growing desire to incorporate attributes of ecosystem science into radiological risk assessment and radioecological research more generally, fueled by recent advances in quantification of emergent ecosystem attributes and the desire to accurately reflect impacts of radiological stressors upon ecosystem function. This paper is a synthesis of the discussions and consensus of the workshop participant's responses to three primary questions, which were: 1) How can ecosystem science support radiological risk assessment? 2) What ecosystem level endpoints potentially could be used for radiological risk assessment? and 3) What inference strategies and associated methods would be most appropriate to assess the effects of radionuclides on ecosystem structure and function? The consensus of the participants was that ecosystem science can and should support radiological risk assessment through the incorporation of quantitative metrics that reflect ecosystem functions which are sensitive to radiological contaminants. The participants also agreed that many such endpoints exit or are thought to exit and while many are used in ecological risk assessment currently, additional data need to be collected that link the causal mechanisms of radiological exposure to these endpoints. Finally, the participants agreed that radiological risk assessments must be designed and informed by rigorous statistical frameworks capable of revealing the causal inference tying radiological exposure to the endpoints selected for measurement.

Methylmercury sorption onto engineered materials.

Four commercially available sorbents (BioChar (BC), ThiolSAMMS® (TS), SediMite (SM), and Organoclay™ PM-199 (OC-199)) were tested for their ability to sorb methylmercury (MeHg) and MeHg complexed with dissolved organic matter (DOM). Testing sorption behavior with DOM is more representative of the environmental conditions and mercury speciation expected during in-situ remediation efforts. Isotherms were fit using a robust, iterative re-weighting scheme. This fitting approach improves upon the traditionally used indirect sorption method by removing the dependence between aqueous and solid phase concentrations in isotherm fitting. Developed isotherms show that without DOM, BC, TS, and SM adsorbed similar amounts of MeHg while OC-199 sorbed substantially less MeHg. Below an equilibrium concentration of 5.6 ng L-1 BC was the best performing sorbent, between 5.6 and 20.9 ng L-1 SM sorbed the most MeHg, and above an equilibrium concentration of 20.9 ng L-1 TS outperformed the other sorbents. BC and OC-199 showed indication of MeHg sorption saturation over the tested concentration range of 3.5-680 ng L-1. With DOM, SM outperformed the other sorbents at equilibrium concentrations less than 0.98 ng L-1 and TS was the superior MeHg:DOM sorbent at higher concentrations. MeHg:DOM sorption was controlled by DOM-sorbent interactions. DOM decreased MeHg sorption onto BC and SM whereas TS exhibited similar sorption with and without DOM. OC-199 had slightly higher MeHg uptake with DOM. East Fork Poplar Creek (EFPC), an industrially Hg contaminated site, was used as a case study example to build a relationship between aqueous and fish MeHg concentrations and subsequently compare the cost of sorbent materials required to meet regulatory objectives. For this case study, SM provided the most cost-effective sorbent option for in-situ remediation efforts to reduce aqueous MeHg concentrations.

Incorporating Suborganismal Processes into Dynamic Energy Budget Models for Ecological Risk Assessment.

A working group at the National Institute for Mathematical and Biological Synthesis (NIMBioS) explored the feasibility of integrating 2 complementary approaches relevant to ecological risk assessment. Adverse outcome pathway (AOP) models provide "bottom-up" mechanisms to predict specific toxicological effects that could affect an individual's ability to grow, reproduce, and/or survive from a molecular initiating event. Dynamic energy budget (DEB) models offer a "top-down" approach that reverse engineers stressor effects on growth, reproduction, and/or survival into modular characterizations related to the acquisition and processing of energy resources. Thus, AOP models quantify linkages between measurable molecular, cellular, or organ-level events, but they do not offer an explicit route to integratively characterize stressor effects at higher levels of organization. While DEB models provide the inherent basis to link effects on individuals to those at the population and ecosystem levels, their use of abstract variables obscures mechanistic connections to suborganismal biology. To take advantage of both approaches, we developed a conceptual model to link DEB and AOP models by interpreting AOP key events as measures of damage-inducing processes affecting DEB variables and rates. We report on the type and structure of data that are generated for AOP models that may also be useful for DEB models. We also report on case studies under development that merge information collected for AOPs with DEB models and highlight some of the challenges. Finally, we discuss how the linkage of these 2 approaches can improve ecological risk assessment, with possibilities for progress in predicting population responses to toxicant exposures within realistic environments. Integr Environ Assess Manag 2018;14:615-624. © 2018 SETAC.

Heterogeneity in Nitrogen Sources Enhances Productivity and Nutrient Use Efficiency in Algal Polycultures.

Algae hold much promise as a potential feedstock for biofuels and other products, but scaling up biomass production remains challenging. We hypothesized that multispecies assemblages, or polycultures, could improve crop yield when grown in media with mixed nitrogen sources, as found in wastewater. We grew mono- and poly- cultures of algae in four distinct growth media that differed in the form (i.e., nitrate, ammonium, urea, plus a mixture of all three) but not the concentration of nitrogen. We found that mean biomass productivity was positively correlated with algal species richness, and that this relationship was strongest in mixed nitrogen media (on average 88% greater biomass production in 5-species polycultures than in monocultures in mixed nitrogen treatment). We also found that the relationship between nutrient use efficiency and species richness was positive across nitrogen treatments, but greatest in mixed nitrogen media. While polycultures outperformed the most productive monoculture only 0-14% of the time in this experiment, they outperformed the average monoculture 26-52% of the time. Our results suggest that algal polycultures have the potential to be highly productive, and can be effective in recycling nutrients and treating wastewater, offering a sustainable and cost-effective solution for biofuel production.

Identifying non-reference sites to guide stream restoration and long-term monitoring.

The reference condition paradigm has served as the standard for assessing the outcomes of restoration projects, particularly their success in meeting project objectives. One limitation of relying solely on the reference condition in designing and monitoring restoration projects is that reference conditions do not necessarily elucidate impairments to effective restoration, especially diagnosing the causal mechanisms behind unsuccessful outcomes. We provide a spatial framework to select both reference and non-reference streams to guide restoration planning and long-term monitoring through reliance on anthropogenically altered ecosystems to understand processes that govern ecosystem biophysical properties and ecosystem responses to restoration practices. We then applied the spatial framework to East Fork Poplar Creek (EFPC), Tennessee (USA), a system receiving 30years of remediation and pollution abatement actions from industrialization, pollution, and urbanization. Out of >13,000 stream reaches, we identified anywhere from 4 to 48 reaches, depending on the scenario, that could be used in restoration planning and monitoring for specific sites. Preliminary comparison of fish species composition at these sites compared to EFPC sites were used to identify potential mechanisms limiting the ecological recovery following remediation. We suggest that understanding the relative role of anthropogenic pressures in governing ecosystem responses is required to successful, process-driven restoration.

Relating fish health and reproductive metrics to contaminant bioaccumulation at the Tennessee Valley Authority Kingston coal ash spill site.

A 4.1 million m(3) coal ash release into the Emory and Clinch rivers in December 2008 at the Tennessee Valley Authority's Kingston Fossil Plant in east Tennessee, USA, prompted a long-term, large-scale biological monitoring effort to determine if there are chronic effects of this spill on resident biota. Because of the magnitude of the ash spill and the potential for exposure to coal ash-associated contaminants [e.g., selenium (Se), arsenic (As), and mercury (Hg)] which are bioaccumulative and may present human and ecological risks, an integrative, bioindicator approach was used. Three species of fish were monitored-bluegill (Lepomis macrochirus), redear sunfish (L. microlophus), and largemouth bass (Micropterus salmoides)-at ash-affected and reference sites annually for 5 years following the spill. On the same individual fish, contaminant burdens were measured in various tissues, blood chemistry parameters as metrics of fish health, and various condition and reproduction indices. A multivariate statistical approach was then used to evaluate relationships between contaminant bioaccumulation and fish metrics to assess the chronic, sub-lethal effects of exposure to the complex mixture of coal ash-associated contaminants at and around the ash spill site. This study suggests that while fish tissue concentrations of some ash-associated contaminants are elevated at the spill site, there was no consistent evidence of compromised fish health linked with the spill. Further, although relationships between elevated fillet burdens of ash-associated contaminants and some fish metrics were found, these relationships were not indicative of exposure to coal ash or spill sites. The present study adds to the weight of evidence from prior studies suggesting that fish populations have not incurred significant biological effects from spilled ash at this site: findings that are relevant to the current national discussions on the safe disposal of coal ash waste.

The effects of a stannous chloride-based water treatment system in a mercury contaminated stream.

We assessed the impacts of an innovative Hg water treatment system on a small, industrially-contaminated stream in the southeastern United States. The treatment system, installed in 2007, removes Hg from wastewater using tin (Sn) (II) chloride followed by air stripping. Mercury concentrations in the receiving stream, Tims Branch, decreased from >100 to ∼10 ng/L in the four years following treatment, and Hg body burdens in redfin pickerel (Esox americanus) decreased by 70% at the most contaminated site. Tin concentrations in water and fish increased significantly in the tributary leading to Tims Branch, but concentrations remain below levels of concern for human health or ecological risks. While other studies have shown that Sn may be environmentally methylated and methyltin can transfer its methyl group to Hg, results from our field studies and sediment incubation experiments suggest that the added Sn to the Tims Branch watershed is not contributing to methylmercury (MeHg) production or bioaccumulation in this system. The stannous chloride treatment system installed at Tims Branch was effective at removing Hg inputs and reducing Hg bioaccumulation in the stream, but future studies are needed to assess longer term impacts of Sn on the environment.

Selenium bioaccumulation in fish exposed to coal ash at the Tennessee Valley Authority Kingston spill site.

In December 2008, 4.1 million cubic meters of coal ash were released into the Emory and Clinch Rivers by the Tennessee Valley Authority Kingston Fossil Plant. Coal ash contains several contaminants, including the bioaccumulative metalloid selenium (Se). Because Se is predominantly accumulated in aquatic organisms through dietary rather than aqueous exposure, tissue-based toxicity thresholds for Se are currently being considered. The proposed threshold concentrations range between 4 µg/g and 9 µg/g Se (dry wt.) in whole body fish, with a proposed fillet threshold of 11.8 µg/g. In the present study, the authors examined the spatial and temporal trends in Se bioaccumulation and examined the relationship between the Se content in fillets and in whole bodies of fish collected around the Kingston spill site to determine whether Se bioaccumulation was a significant concern at the ash spill site. Whereas Se concentrations in fish (whole bodies and fillets) were elevated at sampling locations affected by the Kingston ash spill relative to reference locations, concentrations do not appear to be above risk thresholds and have not been increasing over the 5-yr period since the spill. These findings are not only relevant to guiding the human health and ecological risk assessments at the Kingston ash spill site, but because of current national discussions on appropriate guidelines for Se in fish as well for the disposal of coal combustion wastes, the results are also relevant to the general understanding of Se bioaccumulation in contaminated water bodies.

The use of tetragnathid spiders as bioindicators of metal exposure at a coal ash spill site.

On 22 December 2008, a dike containing coal fly ash from the Tennessee Valley Authority Kingston Fossil Fuel Plant (TN, USA) failed, resulting in the largest coal ash spill in US history. The present study was designed to determine sediment metal concentrations at multiple site locations and to determine whether site-specific bioaccumulation of metals existed in tetragnathid spiders. Selenium and nickel were the only 2 metals to exceed the US Environmental Protection Agency sediment screening levels. Selenium concentrations in spiders were significantly higher at ash-affected sites than in those from reference sites. The ratio of methylmercury to total mercury in spiders was found to be similar to that in other organisms (65-75%), which highlights the potential use of tetragnathid spiders as an indicator species for tracing contaminant transfer between the aquatic and terrestrial ecosystems.

Sources of mercury in a contaminated stream--implications for the timescale of recovery.

Mercury contamination in East Fork Poplar Creek in Tennessee arises from dissolved mercury exiting a headwater industrial complex and residual mercury in the streambed and soil throughout the watershed downstream. The headwater inputs generate chronic base flow concentrations of total mercury of about 1,000 ng/L, but most of the annual export of mercury from the system appears to originate farther downstream. Effective targeting of remedial efforts requires determining how long downstream sources might continue to contaminate the system following elimination of the headwater mercury inputs. The authors calculations suggest that (1) contaminated soils and sediments account for >80% of the annual mercury export from the entire watershed, with most export occurring during wet weather events; (2) bank erosion and resuspension of streambed particulates are the major mercury sources maintaining high annual mercury export rates; and (3) the inventory of particle-associated mercury in the streambed was not large enough to sustain the estimated export rates for more than a few years. The authors findings imply that to prevent waterborne mercury contamination in this system from continuing for decades, remedial actions will have to control the headwater mercury source that sustains day-to-day base flow mercury concentrations and the riparian stream-bank sources that generate most of the mercury export from the system.

Decreasing aqueous mercury concentrations to meet the water quality criterion in fish: examining the water-fish relationship in two point-source contaminated streams.

East Fork Poplar Creek (EF) and White Oak Creek (WC) are two mercury-contaminated streams located on the United States (U.S.) Department of Energy Oak Ridge Reservation in East Tennessee. East Fork Poplar Creek is the larger and more contaminated of the two, with average aqueous mercury (Hg) concentrations exceeding those in reference streams by several hundred-fold. Remedial actions over the past 20 years have decreased aqueous Hg concentrations in EF by 85% (from >1600 ng/L to <400 ng/L). Fish fillet concentrations, however, have not responded to this decrease in aqueous Hg and remain above the U.S. Environmental Protection Agency National Recommended Water Quality Criteria (NRWQC) of 0.3 mg/kg. The lack of correlation between aqueous and fish tissue Hg concentrations in this creek has led to questions regarding the usefulness of target aqueous Hg concentrations and strategies for future remediation efforts. White Oak Creek has a similar contamination history but aqueous Hg concentrations in WC are an order of magnitude lower than in EF. Despite the lower aqueous Hg concentrations (<100 ng/L), fish fillet concentrations in WC have also been above the NRWQC, making the aqueous Hg remediation goal of 200 ng/L in EF seem unlikely to result in an effective decrease in fillet Hg concentrations. Recent monitoring efforts in WC, however, suggest an aqueous total Hg threshold above which Hg bioaccumulation in fish may not respond. This new information could be useful in guiding remedial actions in EF and in other point-source contaminated streams.

Monitoring fish contaminant responses to abatement actions: factors that affect recovery.

Monitoring of contaminant accumulation in fish has been conducted in East Fork Poplar Creek (EFPC) in Oak Ridge, Tennessee since 1985. Bioaccumulation trends are examined over a twenty year period coinciding with major pollution abatement actions by a Department of Energy facility at the stream's headwaters. Although EFPC is enriched in many contaminants relative to other local streams, only polychlorinated biphenyls (PCBs) and mercury (Hg) were found to accumulate in the edible portions of fish to levels of human health concern. Mercury concentrations in redbreast sunfish were found to vary with season of collection, sex and size of individual fish. Over the course of the monitoring, waterborne Hg concentrations were reduced >80%; however, this did not translate into a comparable decrease in Hg bioaccumulation at most sites. Mercury bioaccumulation in fish did respond to decreased inputs in the industrialized headwater reach, but paradoxically increased in the lowermost reach of EFPC. As a result, the downstream pattern of Hg concentration in fish changed from one resembling dilution of a headwater point source in the 1980s to a uniform distribution in the 2000s. The reason for this remains unknown, but is hypothesized to involve changes in the chemical form and reactivity of waterborne Hg associated with the removal of residual chlorine and the addition of suspended particulates to the streamflow. PCB concentrations in fish varied greatly from year-to-year, but always exhibited a pronounced downstream decrease, and appeared to respond to management practices that limited episodic inputs from legacy sources within the facility.

A probabilistic assessment of the chemical and radiological risks of chronic exposure to uranium in freshwater ecosystems.

Uranium (U) presents a unique challenge for ecological risk assessments (ERA) because it induces both chemical and radiological toxicity, and the relative importance of these two toxicities differs among the various U source terms (i.e., natural, enriched, depleted). We present a method for the conversion between chemical concentrations microg L(-1)) and radiological dose rates (microGy h(-1)) for a defined set of reference organisms, and apply this conversion method to previously derived chemical and radiological benchmarks to determine the extent to which these benchmarks ensure radiological and chemical protection, respectively, for U in freshwater ecosystems. Results show that the percentage of species radiologically protected by the chemical benchmark decreases with increasing degrees of U enrichment and with increasing periods of radioactive decay. In contrast, the freshwater ecosystem is almost never chemically protected by the radiological benchmark, regardless of the source term or decay period considered, confirming that the risks to the environment from uranium's chemical toxicity generally outweigh those of its radiological toxicity. These results are relevant to developing water quality criteria that protect freshwater ecosystems from the various risks associated with the nuclear applications of U exploitation, and highlight the need for (1) further research on the speciation, bioavailability, and toxicity of U-series radionuclides under different environmental conditions, and (2) the adoption of both chemical and radiological benchmarks for coherent ERAs to be conducted in U-contaminated freshwater ecosystems.

Dominance of dietary intake of metals in marine elasmobranch and teleost fish.

Metal accumulation in marine fish is a global public health concern, because the consumption of seafood provides the largest dose of many toxic metals to humans. While water quality criteria often rely on aqueous exposures of metals to fish in developing safety guidelines, it is increasingly recognized that marine fish obtain an important fraction of their metal body burden from their diet. Using experimental data, we modeled the accumulation of six metals (Am, Cd, Cs, Co, Mn, Zn) from diet and from the aqueous phase in two marine fish species, the teleost Psetta maxima and elasmobranch Scyliorhinus canicula. We estimated steady-state metal concentrations and calculated the relative contributions of dietary and aqueous intake in both species. For both species >60% and often >90% of Mn, Cd, and Zn derives from dietary intake in these species, even at the lowest ingestion rates reported for these fish. At low ingestion rates, Am was obtained predominantly from the aqueous phase and Cs varied considerably depending on prey selection. Inter-specific differences were noted, especially in Co uptake. Model predictions of steady-state tissue metal concentrations are within the range of field measurements for these species. Our findings underscore the importance of including dietary exposure in understanding metal accumulation in marine fish.