Teasing out the Effects of Natural Stressors at Chemically Contaminated Sites.

Aquatic ecosystems are often impacted by a multitude of stressors, many of which are introduced by a combination of anthropogenic activities such as agricultural development, urbanization, damming, and industrial discharge. Determining the primary stressors responsible for ecological impairments at a site can be complex and challenging; however, it is crucial for making informed management decisions. Improper diagnosis of an impaired system can lead to misguided attempts at remediation, which can be both time consuming and costly. We focused on the development, implementation, and evaluation of methodologies that, in combination, allowed us to identify the primary stressors. These included a four-phase, weight-of-evidence (WOE) assessment including in situ Toxicity Identification and Evaluation (iTIE) testing, physicochemical and macrobenthos characterization, reciprocal sediment transplants, and laboratory and in situ toxicity testing. The contaminants of concern (COCs) at the site were elevated levels of ammonia, chloride, pH, and total dissolved solids in groundwater upwellings into a high-quality waterway. Reciprocal transplants of site sediments and nearby reference sediments and traditional benthic sampling showed impaired benthic indices and multiple stations around a contaminated industrial settling basin. Impaired stations had elevated COCs in groundwaters but exhibited a steep vertical concentration gradient, with concentrations decreasing near the sediment-surface water interface. We describe Phase 4 of the study, which focused on teasing out the role of dissolved oxygen sags in benthic macroinvertebrate responses. Extensive submerged and emergent macrophytes, algae, and cyanobacteria co-occurred at the impaired sites and increased throughout the summer. Laboratory testing suggested that ammonia and pH were possibly toxic at the sites, based on groundwater concentrations. The in situ toxicity testing, however, showed toxicity occurring even at stations with low levels of COCs concurrently with large diurnal fluxes in dissolved oxygen (DO). A final phase using a type of iTIE approach utilized limnocorrals with and without aeration and with in situ toxicity measures using Hyalella azteca. The Phase 4 assessment revealed that low DO levels were primarily responsible for impaired benthic communities, and COC upwellings were diluted at the sediment-water interface to nontoxic levels. These findings will allow for improved management decisions for more efficient and effective restoration activities. Environ Toxicol Chem 2024;43:1524-1536. © 2024 SETAC.

Has the Rio Doce "time bomb" been defused? Using a weight-of-evidence approach to determine sediment quality.

The Fundão mine tailings dam rupture of 2015, in the Rio Doce basin, Brazil, resulted in the deposition of tailings downstream of the dam. It has yet to be determined if metals associated with the tailings have contributed toxicity to organisms, burying a time bomb that could be ticking. Currently the data on toxicity to benthic and aquatic organisms have not been assessed sufficiently to allow an informed assessment using an approach based on weight-of-evidence. This study was conducted to ascertain if sediments at "hot spots" that received Fundão tailings reflected elevated concentrations of metals and if these concentrations were sufficient to result in toxicity to freshwater organisms. The lines-of-evidence considered included assessing metals concentrations in relation to sediment quality criteria, establishing biogeochemical characterizations, completing an evaluation of potential metal release upon resuspension to provide information on bioavailability, and identifying acute and chronic toxicity effects using sensitive native species for waters (water flea, Daphnia similis) and sediments (burrowing midge larvae, Chironomus sancticaroli). Only porewater concentrations of iron and manganese exceeded Brazilian surface water criteria, whereas most trace elements exhibited no enrichment or elevated environmental indexes. The concentrations of bioavailable metals were assessed to be low, and metal concentrations did not increase in the overlying water upon resuspension; rather, they decreased through time. Toxicity testing in resuspended waters and bulk sediments resulted in no acute or chronic toxicity to either benthic or aquatic species. The low metal bioavailability and absence of toxicity of the tailings-enriched sediments was attributed to the strong binding and rapid removal of potentially toxic metal ions caused by oxyhydroxides and particles in the presence of iron-rich particulates. The findings of these sediment hot-spot studies indicate the Fundão dam release of tailings more than six years ago is not causing the current release of toxic concentrations of metals into the freshwaters of the Rio Doce. Integr Environ Assess Manag 2024;20:148-158. © 2023 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Evaluation of Capping Materials to Reduce Zinc Flux from Sediments in a Former Mining Pit Lake.

Wilson Mine is a former vanadium mine site located in the Ouachita Mountains near Hot Springs, Arkansas. The site, which drains via two streams to Lake Catherine, has undergone extensive reclamation to significantly reduce groundwater and surface water contact with mine spoils. One of the streams passes through a former mine pit forming East Wilson Pond, and flux from pit lake sediments can result in elevated metal, that is, zinc (Zn), concentrations in overlying water. To mitigate potential risks, an investigation was conducted to evaluate the efficacy of capping materials for partitioning Zn-contaminated sediments from overlying water in East Wilson Pond. A 28-day laboratory study compared the effectiveness of capping materials including combinations of limestone, bentonite clay, and gravel for mitigating Zn flux, including under reasonable worst-case conditions (pH 5.5) encountered in the hypolimnion. Dissolved Zn was monitored over time in overlying water and in sediment porewaters within untreated controls and within the capping layer of treated systems. The use of limestone and/or bentonite clay improved buffering capacity compared to the noncapped control, and pH declined gradually but only modestly in the overlying water and porewater of all treated systems. Concentrations of Zn in overlying water of the noncapped control increased from approximately 30 to 100 µg/L during the study period, while concentrations in the overlying water and porewater of systems containing capping materials remained low (10-30 µg/L). The results demonstrated the effectiveness of the capping materials for neutralizing pH and reducing Zn flux, and a three-layer cap consisting of limestone (top) + bentonite clay (middle) + gravel (bottom) was determined to be most effective. These results were used to inform the selection of materials for the application of a cap to reduce Zn flux from the pit lake sediments. Environ Toxicol Chem 2022;41:193-200. © 2021 SETAC.

A Novel In Situ Toxicity Identification Evaluation (iTIE) System for Determining which Chemicals Drive Impairments at Contaminated Sites.

Human-dominated waterways contain thousands of chemicals. Determining which chemical is the most important stressor is important, yet very challenging. The Toxicity Identification Evaluation (TIE) procedure from the US Environmental Protection Agency uses a series of chemical and physical manipulations to fractionate compounds within a matrix and systematically identify potential toxicants through laboratory bioassay testing. Although this may provide useful information, it lacks ecological realism because it is subject to laboratory-related artifacts and is resource intensive. The in situ Toxicity Identification Evaluation (iTIE) technology was developed to improve this approach and has undergone a number of modifications over the past several years. The novel prototype 3 consists of an array of iTIE ambient water fractionation units. Each unit is connected to a peristaltic pumping system with an organism exposure chamber that receives water from a resin chamber to chemically fractionate test site water. Test organisms included freshwater and marine standard toxicity test species. Postfractionation waters are collected for subsequent chemical analyses. Currently, the resins allow for separation of ammonia, metals, and nonpolar organics; the subsequent toxicity responses are compared between treatments and unfractionated, ambient exposures. The iTIE system was deployed to a depth of 3 m and evaluated in streams and marine harbors. Chemical analyses of water and iTIE chemical sorptive resins confirmed chemical groups causing lethal to sublethal responses. The system proved to be as sensitive or more so than the traditional phase 1 TIE test and required almost half of the resources to complete. This iTIE prototype provides a robust technology that improves stressor-causality linkages and thereby supports strong evidence for ecological risk weight-of-evidence assessments. Environ Toxicol Chem 2020;39:1746-1754. © 2020 SETAC.

Seasonal Toxicity Observed with Amphipods (Eohaustorius estuarius) at Paleta Creek, San Diego Bay, USA.

To assess potential impacts on receiving systems, associated with storm water contaminants, laboratory 10-d amphipod (Eohaustorius estuarius) survival toxicity tests were performed using intact sediment cores collected from Paleta Creek (San Diego Bay, CA, USA) on 5 occasions between 2015 and 2017. The approach included deposition-associated sediment particles collected from sediment traps placed at each of 4 locations during the 2015 to 2016 wet seasons. The bioassays demonstrated wet season toxicity, especially closest to the creek mouth, and greater mortality associated with particles deposited in the wet season compared with dry season samples. Grain size analysis of sediment trap material indicated coarser sediment at the mouth of the creek and finer sediment in the outer depositional areas. Contaminant concentrations of metals (Cd, Cu, Hg, Ni, Pb, and Zn) and organic compounds (polycyclic aromatic hydrocarbons [PAHs], polychlorinated biphenyls [PCBs], and pesticides) were quantified to assess possible causes of toxicity. Contaminant concentrations were determined in the top 5 cm of sediment and porewater (using passive samplers). Whereas metals, PAHs, and PCBs were rarely detected at sufficient concentrations to elicit a response, pyrethroid pesticides were highly correlated with amphipod toxicity. Summing individual pyrethroid constituents using a toxic unit approach suggested that toxicity to E. estuarius could be associated with pyrethroids. This unique test design allowed delineation of spatial and temporal differences in toxicity, suggesting that storm water discharge from Paleta Creek may be the source of seasonal toxicity. Environ Toxicol Chem 2019;39:229-239. © 2019 SETAC.

Laboratory and Field-Based Assessment of the Effects of Sediment Capping Materials on Zinc Flux, Bioavailability, and Toxicity.

A former mining site has been the subject of extensive remediation and restoration, with a significant focus on disconnecting mine spoils from groundwater and managing the quantity and quality of runoff. A remaining task is ensuring concentrations of zinc (Zn) in the stream outflow of a pit lake are reduced below water quality standards. The efficacy of multiple capping materials for decreasing Zn dissolution from sediments was conducted under natural and reasonable worst-case conditions (pH = 5.5). Capping materials included AquaBlok™, limestone, and limestone-bone char. Field exposures were conducted in limnocorrals that isolated overlying water columns above the sediment and capping treatments. Simultaneous in situ and ex situ toxicity tests were conducted using Daphnia magna, Hyalella azteca, and Chironomus dilutus. In situ caged organisms were protected from temperature shock (warm epilimnetic waters) by deploying within a Toxicity Assessment Container System (TACS). Organisms were exposed to surficial sediments, caps, and hypolimnetic overlying waters for 4 d. Ex situ testing was conducted in core tube mesocosms containing sediments and caps at similar temperatures (15-19 °C). Results demonstrated the usefulness of TACS deployment in stratified lake systems. There were no differences in responses between treatments involving sediment capping materials in both in situ and ex situ tests. The lack of differences was likely due to dissolved Zn in surface water being below the hardness-adjusted threshold effects levels (164 µg L-1 ). This field- and laboratory-based weight-of-evidence study provided site-specific data to support the selection of an effective remedy, with reduced uncertainty compared to laboratory and chemistry-only approaches. Environ Toxicol Chem 2019;39:240-249. © 2019 SETAC.

Human Health Benefits from Fish Consumption vs. Risks from Inhalation Exposures Associated with Contaminated Sediment Remediation: Dredging of the Hudson River.

BACKGROUND: Billions of dollars are spent on environmental dredging (ED) to remediate contaminated sediments, with one goal being reduced human health risks. However, ED may increase health risks in unanticipated ways, thus potentially reducing net benefits. OBJECTIVES: To assess the ways that ED may increase health risks in unanticipated ways, thus potentially reducing net benefits, we quantitatively assessed a subset of population health benefits and risks of ED, using the 2009-2015 remediation of the Hudson River Polychlorinated Biphenyls (PCBs) Superfund Site as a case study. Three remediation scenarios were evaluated: No Action (NA), Source Control (SC), and ED. METHODS: We quantified health benefits for each scenario from reduced PCB levels in Hudson River fish, and health risks from ED operations due to increased inhalation exposures to PCBs and fine particulate matter (PM2.5), using disability-adjusted life years (DALYs) as a common metric. Occupational health risks were also considered in a separate sensitivity analysis. Estimates of population-level benefits and risks included Monte Carlo simulation-based uncertainty analysis. RESULTS: Under NA, fish consumption would result in an estimated health burden of 112 DALYs, and ED would lead to a reduction of 15 DALYs in excess of SC. ED operations were estimated to induce a total burden of 33 DALYs, dominated by PM2.5 impacts from rail transport emissions (32 DALYs). Including uncertainty, the net health benefit of ED ranged from -138 to +1,326 avoided DALYs (90% confidence), with a median of -11 avoided DALYs. CONCLUSIONS: For the considered impacts, ED in the Hudson River might not have led to an overall net positive human health impact. The benefits and risks of ED, however, have different degrees of uncertainty and involve different populations. Reducing long-distance transport of dredged sediment is a priority. This comparative approach could be used prospectively to better determine trade-offs involved in different remediation scenarios and to improve remediation design to maximize benefits while minimizing risks. https://doi.org/10.1289/EHP5034.

Hyporheic Interactions Increase Zinc Exposure and Effects on Hyalella azteca in Sediments under Flow-Through Conditions.

Groundwater-surface water interactions in the hyporheic transition zone can influence contaminant exposure to benthic macroinvertebrates. In streams, hyporheic flows are subject to varying redox conditions, which influence biogeochemical cycling and metal speciation. Despite these relationships, little is known about how these interactions influence the ecological risk of contaminants. The present study investigated the effects of hyporheic flows and zinc (Zn)-contaminated sediments on the amphipod Hyalella azteca. Hyporheic flows were manipulated in laboratory streams during 10-d experiments. Zinc toxicity was evaluated in freshly spiked and aged sediments. Hyporheic flows altered sediment and porewater geochemistry, oxidizing the sediments and causing changes to redox-sensitive endpoints. Amphipod survival was lowest in the Zn sediment exposures with hyporheic flows. In freshly spiked sediments, porewater Zn drove mortality, whereas in aged sediments simultaneously extracted metals (SEM) in excess of acid volatile sulfides (AVS) normalized by the fraction of organic carbon (fOC) [(SEM-AVS)/fOC] influenced amphipod responses. The results highlight the important role of hyporheic flows in determining Zn bioavailability to benthic organisms, information that can be important in ecological risk assessments. Environ Toxicol Chem 2019;38:2447-2458. © 2019 SETAC.

Hitting Reset on Sediment Toxicity: Sediment Homogenization Alters the Toxicity of Metal-Amended Sediments.

Laboratory testing of sediments frequently involves manipulation by amendment with contaminants and homogenization, which changes the physicochemical structure of sediments. These changes can influence the bioavailability of divalent metals, and field and mesocosm experiments have shown that laboratory-derived thresholds are often overly conservative. We assessed the mechanisms that lead to divergence between laboratory- and field-derived thresholds; specifically, we assessed the importance of slow equilibration to solid-phase ligands and vertical stratification. To mimic natural physicochemical conditions, we uniquely aged sediment with a flow-through exposure system. These sediments were then homogenized and compared, toxicologically, with freshly metal-amended sediments in a 28-d chronic toxicity bioassay with the amphipod Hyalella azteca. We assessed concentration-response relationships for 3 metals (copper, nickel, and zinc) and 5 geochemically distinct sediments. We observed minimal differences in growth and survival of H. azteca between aged and freshly spiked sediments across all sediments and metals. These trends suggest that a loss of toxicity observed during long-term sediment aging is reversed after sediment homogenization. By comparison with mesocosm experiments, we demonstrate that homogenizing sediment immediately before toxicity assays may produce artificially high toxicity thresholds. We suggest that toxicity assays with sediments that maintain vertical redox gradients are needed to generate field-relevant sediment metal toxicity thresholds. Environ Toxicol Chem 2019;38:1995-2007. © 2019 SETAC.

Weight-of-Evidence Approach for Assessing Removal of Metals from the Water Column for Chronic Environmental Hazard Classification.

The United Nations and the European Union have developed guidelines for the assessment of long-term (chronic) chemical environmental hazards. This approach recognizes that these hazards are often related to spillage of chemicals into freshwater environments. The goal of the present study was to examine the concept of metal ion removal from the water column in the context of hazard assessment and classification. We propose a weight-of-evidence approach that assesses several aspects of metals including the intrinsic properties of metals, the rate at which metals bind to particles in the water column and settle, the transformation of metals to nonavailable and nontoxic forms, and the potential for remobilization of metals from sediment. We developed a test method to quantify metal removal in aqueous systems: the extended transformation/dissolution protocol (T/DP-E). The method is based on that of the Organisation for Economic Co-operation and Development (OECD). The key element of the protocol extension is the addition of substrate particles (as found in nature), allowing the removal processes to occur. The present study focused on extending this test to support the assessment of metal removal from aqueous systems, equivalent to the concept of "degradability" for organic chemicals. Although the technical aspects of our proposed method are different from the OECD method for organics, its use for hazard classification is equivalent. Models were developed providing mechanistic insight into processes occurring during the T/DP-E method. Some metals, such as copper, rapidly decreased (within 96 h) under the 70% threshold criterion, whereas others, such as strontium, did not. A variety of method variables were evaluated and optimized to allow for a reproducible, realistic hazard classification method that mimics reasonable worst-case scenarios. We propose that this method be standardized for OECD hazard classification via round robin (ring) testing to ascertain its intra- and interlaboratory variability. Environ Toxicol Chem 2019;38:1839-1849. © 2019 SETAC.

Metal Toxicity During Short-Term Sediment Resuspension and Redeposition in a Tropical Reservoir.

Billings Complex is the largest water-storage reservoir in São Paulo, Brazil, and has been contaminated since the 1960s. Periodically, Billings sediments are subjected to currents causing resuspension and subsequent release of metals. A short-term (4-h) resuspension was simulated using sediment flux exposure chambers (SeFECs) to better understand the fate, bioavailability, and transport of iron (Fe), manganese (Mn), and zinc (Zn) during these events, as well as possible organism toxicity. Daphnia magna and Hyalella azteca were exposed during the 4-h resuspension, and were monitored after exposure for survival, growth, and reproduction. Resuspension rapidly deoxygenated the overlying water, decreased the pH, and resulted in elevated dissolved Zn above the US Environmental Protection Agency's (2002) criteria for acute toxicity (120 µg L-1 ). However, Zn was scavenged (after 20 h) from solution as new sorption sites formed. Dissolved Mn increased during and after resuspension, with maximum values at 20 h post exposure. An initial release of Fe occurred, likely associated with oxidation of acid-volatile sulfides, but decreased after 1 h of resuspension. The Fe decrease is likely due to precipitation as oxyhydroxides. No acute toxicity was observed during resuspension; however, mortality of D. magna and H. azteca occurred during the postexposure period. Daphnia magna also exhibited chronic toxicity, with decreased neonate production after exposure. This sublethal effect could lead to decreased zooplankton populations over a longer period in the reservoir. Environ Toxicol Chem 2019;38:1476-1485. © 2019 SETAC.

Thermal extremes can intensify chemical toxicity to freshwater organisms and hence exacerbate their impact to the biological community.

Temperature in freshwater ecosystems fluctuates daily, seasonally and yearly. Climate change further induces temperature variations. In this study, we hypothesise that water temperatures, in particular thermal extremes, can significantly influence chemical toxicity to ectothermic organisms. Although temperature-dependent chemical toxicity (TDCT) is a classic research area in ecotoxicology, a unified model for predicting TDCT for freshwater species is yet to be developed. This study aimed to address this challenging issue through a meta-analysis by comparing acute toxicity endpoints (i.e. median lethal or effective concentration data; LC50 or EC50) of 13 chemicals for various freshwater species generated from different temperatures. Our results suggest that in most cases, freshwater species exhibit the highest tolerance towards chemicals at their physical optimal temperature (Topt), and chemical toxicity exacerbates when temperature is higher or lower than Topt (i.e. inverted V-shaped model between temperature and LC50 or EC50). Such observations are further supported by temperature-dependent hazardous concentration 10% (HC10) values derived from species sensitivity distributions constructed using toxicity data generated at different temperatures. A unified mathematical model was also developed to describe the inverted V-shape relationship between temperature and HC10 derivations. Overall, considering the natural variations of freshwater temperatures, the inverted V-shaped TDCT model can be readily applied to derive water quality guidelines and assess ecological risks of chemical contaminants.

Use of multiple lines of evidence to provide a realistic toxic substances control act ecological risk evaluation based on monitoring data: D4 case study.

D4 (octamethylcyclotetrasiloxane) is a high-production-volume cyclic volatile methyl siloxane with a wide range of industrial and consumer applications. This study conducted a robust ecological risk evaluation for D4 using exposure data collected under a nation-wide environmental monitoring program facilitated under the Toxic Substances Control Act (TSCA). This ecological risk evaluation was conducted consistent with the principles outlined in the U.S. Environmental Protection Agency's (EPA's) Guidance to Assist Interested Persons in Developing and Submitting Draft Risk Evaluations under TSCA (U.S. EPA 2017a). The evaluation examined multiple lines of evidence (LoEs) to determine the potential risks from D4 to aquatic receptors in rivers and streams in the United States from municipal wastewater treatment plant (WWTP) discharges and discharges from manufacturing, processing, and/or formulating (MPF) facilities after onsite wastewater treatment. The LoEs consisted of comparing D4 concentrations measured in water and sediment to toxicity thresholds derived from laboratory studies; comparing D4 concentrations measured in biota tissue to critical target lipid body burdens (CTLBBs); comparing fugacity-based chemical activities between toxicity thresholds and measured environmental concentrations; and assessing benthic macroinvertebrate community structure and habitat suitability. The approach taken moves beyond a standard deterministic hazard quotient approach to incorporate more advanced methods for risk prediction, using distributions rather than conservative point estimates of exposure to obtain a realistic view of the probability of harm, consistent with EPA's stated intent to "strive to utilize probabilistic approaches for exposure assessments included in a risk evaluation" (U.S. EPA 2017b). The risk evaluation concluded there is negligible risk to water column and sediment receptors from D4 discharged from MPF facilities after onsite wastewater treatment or from municipal WWTPs that may treat a mix of industrial and consumer wastewater.

In situ microbiota distinguished primary anthropogenic stressor in freshwater sediments.

Conventional assessment and evaluation of sediment quality are based on laboratory-based ecotoxicological and chemical measurements with lack of concern for ecological relevance. Microbiotas in sediment are responsive to pollutants and can be used as alternative ecological indicators of sediment pollutants; however, the linkage between the microbial ecology and ecotoxicological endpoints in response to sediment contamination has been poorly evaluated. Here, in situ microbiotas from the Three Gorges Reservoir (TGR) area of the Yangtze River were characterized by DNA metabarcoding approaches, and then, changes of in situ microbiotas were compared with the ecotoxicological endpoint, aryl hydrocarbon receptor (AhR) mediated activity, and level of polycyclic aromatic hydrocarbons (PAHs) in sediments. PAHs and organic pollutant mixtures mediating AhR activity had different effects on the structures of microbiotas. Specifically, Shannon indices of protistan communities were negatively correlated with the levels of AhR mediated activity and PAHs. The sediment AhR activity was positively correlated with the relative abundance of prokaryotic Acetobacteraceae, but had a negative correlation with protistan Oxytrichidae. Furthermore, a quantitative classification model was built to predict the level of AhR activity based on the relative abundances of Acetobacteraceae and Oxytrichidae. These results suggested that in situ Protista communities could provide a useful tool for monitoring and assessing ecological stressors. The observed responses of microbial community provided supplementary evidence to support that the AhR-active pollutants, such as PAHs, were the primary stressors of the aquatic community in TGR area.

Biogeochemical controls on the speciation and aquatic toxicity of vanadium and other metals in sediments from a river reservoir.

Effects of hydrologic variability on reservoir biogeochemistry are relatively unknown, particularly for less studied metals like vanadium (V). Further, few studies have investigated the fate and effects of sediment-associated V to aquatic organisms in hydrologically variable systems. Our primary objective was to assess effects of hydrologic manipulation on speciation and toxicity of V (range: 635 to 1620mgkg-1) and other metals to Hyalella azteca and Daphnia magna. Sediments were collected from a reservoir located in a former mining area and microcosm experiments were conducted to emulate 7-day drying and inundation periods. Despite high sediment concentrations, V bioavailability remained low with no significant effects to organism survival, growth, or reproduction. The lack of V toxicity was attributed to reduced speciation (III, IV), non-labile complexation, and sorption to Al/Fe/Mn-oxyhydroxides. Zinc (Zn) increased in surface and porewater with inundation, for some sediments exceeding the U.S. EPA threshold for chronic toxicity. While no effects of Zn to organism survival or growth were observed, Zn body concentrations were negatively correlated with H. azteca growth. Results from this study indicate that V bioavailability and environmental risk is dependent on V-speciation, and V is less influenced by hydrologic variability than more labile metals such as Zn.