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Austin K. Baldwin

Publications and source records attributed to Austin K. Baldwin.

At least 19 recordsLinked to original sources

Fate and effects to the benthic community of a copper treatment to eradicate invasive mussels in a large western river, USA

Copper-based chemical treatments are commonly used to eradicate invasive mussels in small ponds and lakes, but their use in large rivers has been limited. In 2023, in response to a detection of invasive quagga mussels, a 10-km reach of the Snake River (Idaho, USA), was treated with an unprecedented 19,300 kg of chelated copper molluscicide to a target concentration of 1,000 µg/L for 10 days. We assessed the transport and fate of the copper and its exposure and effects on the nontarget benthic community downstream. Water samples were collected at seven locations throughout the treatment period, and sediment, periphyton, and benthic macroinvertebrates were collected pre- and posttreatment. Nearly half of the original mass of copper was removed from the water column via sedimentation, sorption to algae, or biological uptake within the 10-km treatment reach and the first 15 km downstream. Even so, dissolved copper concentrations exceeded the acute toxicity threshold at least as far as 28 km downstream for more than 2 weeks. Sediment copper increased by up to 8.3-fold, exceeding the consensus-based sediment quality threshold effect concentration at several sites. Effects on benthic macroinvertebrates varied by taxa. From 0–28 km downstream, invertebrate abundances decreased 52%–94%, with gastropods among the most affected. Of the unique taxa present at these sites pretreatment, 52%–64% were not found posttreatment but were replaced by other taxa, indicating a reorganization of the base of the food web. Additionally, from 0–15 km downstream, the percentage of individuals from tolerant taxa increased two to15-fold. Findings from this study can help watershed managers plan future invasive mussel responses while protecting culturally, economically, and ecologically important nontarget species in large rivers.

Idaho

Spatial patterns and temporal trends in water quality in Idaho’s lower Boise River and its tributaries, 1994–2023

The lower Boise River in southwestern Idaho is a vital cultural, economic, and ecological resource, but some of its beneficial uses are impaired by excess algae, sediment, nutrients, and bacteria. In response, a variety of water quality improvement projects and regulations have been implemented in recent decades. A recent study showed that, from water years 2003 to 2021, concentrations of total phosphorus at the mouth of the Boise River near Parma decreased by 60 percent, indicating the success of the improvement projects and progress towards reaching the regulatory target. However, although the progress of the system as a whole towards reaching the total phosphorus target is well documented, quantifying contributions and trends in total phosphorus loading from individual tributaries and upstream mainstem locations is needed. Similarly, tributary contributions and trends of other constituents of concern are unknown or have not been evaluated in a decade. To evaluate the success of past water-quality improvement efforts and help prioritize future investments, this study characterized spatial and seasonal patterns in concentrations and loads of suspended sediment, total phosphorus, orthophosphate, total nitrogen, nitrate plus nitrite, Escherichia coli bacteria, and periphyton chlorophyll a (chl-a) at three mainstem and seven tributary sites of the lower Boise River during water years 2019–2023. For sites and constituents with adequate data, temporal trends over a 15-year and 30-year period were also evaluated. Recent (in other words, water years 2019–2023) concentrations and loads of suspended sediment and total phosphorus were typically greatest during the irrigation season and often exceeded total maximum daily load targets. However, concentrations and loads of suspended sediment, total phosphorus, and orthophosphate have decreased over the past 15 to 30 years at many sites. In contrast, concentrations of total nitrogen and nitrate plus nitrite showed increasing trends at the Boise River near Parma, likely reflecting the effects of regional changes in agricultural practices in recent decades. Periphyton chl-a concentrations during October–November were highly likely increasing over the 30-year period at Boise River at Eckert, but were uncertain at Middleton and Parma. At Boise River at Middleton, periphyton chl-a concentrations exceeded the total maximum daily load target of 150 milligrams per square meter in 75 percent of samples during water years 2019–2023. Results therefore demonstrate that past watershed improvement efforts have been largely effective at reducing concentrations and loads of suspended sediment, total phosphorus, and orthophosphate in the lower Boise River watershed, but different strategies may be needed to reduce concentrations and loads of total nitrogen, nitrate plus nitrite, Escherichia coli , and periphyton chl-a.

Idaho

Retrospective stepwise prioritization of chemicals detected in Great Lakes tributaries (2008–2018)

Through the U.S. Great Lakes Restoration Initiative, a 10-year, multiagency chemical monitoring effort was undertaken across the Great Lakes. In this effort, 586 chemicals were monitored and 334 were detected in grab/composite water samples. To help inform potential future actions, a stepwise prioritization framework was used to identify compounds for which publicly accessible water quality guidelines or effects information suggested there was potential aquatic ecotoxicity. Because water quality guidelines were only available for some chemicals, this framework used apical toxicity data collated from publicly accessible databases (e.g., the ECOTOXicology Knowledgebase) and alternative data, including literature-derived non-apical effect concentrations, in vitro bioactivities from high-throughput screening, and modeled ecotoxicity. To account for the diverse levels of confidence in these data, chemicals were prioritized within specific action categories, which suggested potential management or experimental activities that may be considered based on the types of data available for each compound. Overall, 11 detected chemicals were identified as high priority in different action categories. This included four chemicals prioritized for environmental management or targeted risk assessment, three chemicals prioritized for effects-based monitoring, one chemical prioritized for apical effects assessment, and three chemicals targeted for non-apical effects evaluation. This framework also identified 164 low-priority chemicals, among which more than 50% were prioritized based on water quality guidelines or apical effect concentrations (thus could be considered low priority for future risk assessment or management activities). Results aim to help regulatory agencies, environmental managers, and other stakeholders focus available resources on carrying out monitoring, experimental, and risk assessments for the chemicals that display the greatest potential to adversely impact Great Lakes ecosystems.

Great Lakes

Leveraging invasive mussel contaminant survey data for stepwise prioritization of chemicals of potential concern in the Great Lakes basin

Historical and ongoing anthropogenic activities coupled with advancements in analytical techniques have led to the detection of large numbers of contaminants in the Laurentian Great Lakes. Consequently, identifying and prioritizing chemicals likely to cause ecological harm represents a challenge for natural resource managers. Previous prioritization efforts have focused on contaminants in sediment, water, and passive samplers, which may not be representative of compounds that bioaccumulate in aquatic organisms. Consequently, this study adopted a stepwise method to prioritize chemicals of potential concern detected in dreissenid mussels from samples collected across the Great Lakes from 2009–2018. The stepwise method considered environmental fate, detection frequency, and exceedance of toxicity quotients based on ecotoxicological effect concentrations. Overall, 153 compounds out of 267 analyzed were detected in dreissenid mussels, 47 of which had water quality effect concentrations, 56 had apical effect concentrations (Tier 1 ECOTOX or apical screening), 17 had nonapical effect concentrations (Tier 2 ECOTOX, Cytotoxic Burst, and ToxCast) and 33 had estimated effect concentrations (quantitative structure-activity relationship, estimated screening, and pharmacological potency). Of the compounds with water quality effect concentrations, nine were designated as high priority, including the herbicide atrazine and five polycyclic aromatic hydrocarbons that were previously identified as potentially hazardous within other matrices. Similar contaminants were identified as high priority in a related study of native unionid mussels in the Great Lakes. A total of 27 compounds were low priority, suggesting that these contaminants do not warrant further action based on this dataset. Overall, these findings will facilitate the development of management strategies to mitigate the effects of contaminants on aquatic organisms within the Great Lakes.

Great Lakes basin

Contrasting magnitude and timing of pulsed aqueous methylmercury bioaccumulation across a reservoir food web

Water column hypoxia is a key process influencing methylmercury (MeHg) production and availability in waterbodies worldwide. During seasonal destratification, large, short-lived pulses of aqueous MeHg may be released into the subsequently mixed water column, but little is known about the fate of these pulses, particularly whether there are concomitant increases in MeHg uptake into aquatic food webs. We examined the magnitude and timing of MeHg uptake across several trophic guilds relative to the reservoir stratification status using biweekly mercury data from water, zooplankton, and fish (Bluegill, Lepomis macrochirus and Smallmouth Bass, Micropterus dolomieu ). Zooplankton MeHg concentrations increased by up to 250% during destratification, concurrent with increases in aqueous MeHg concentrations. Zooplankton and filter-passing MeHg concentrations were positively correlated when the reservoir was mixed ( R 2 = 0.95) and destratifying ( R 2 = 0.57) but not while the reservoir was stratified ( R 2 = 0.21). Mercury concentrations in adult bluegill and juveniles of both fish species increased 20–70% following destratification, with responses lagging 4–8 weeks behind those in water and zooplankton MeHg. Mercury concentrations in piscivorous adult bass varied little over the course of the study. Our findings demonstrate the responsiveness of reservoir food webs to pulses in MeHg availability, suggesting that these pulses could play an important role in biotic MeHg exposure within and downstream of reservoirs.

Idaho, Oregon

Derivation and characterization of environmental hazard concentrations for chemical prioritization: A case study in the Great Lakes tributaries

Ongoing anthropogenic activities and analytical advancements yield continuously expanding lists of environmental contaminants. This represents a challenge to environmental managers, who must prioritize chemicals for management actions (e.g., restriction, regulation, remediation) but are often hindered by resource limitations. To help facilitate prioritization efforts, this study presents several strategies for deriving environmental hazard concentrations using publicly accessible data and open-source computational tools. Using a Great Lakes tributaries aquatic monitoring dataset as a case study, environmental hazard concentrations were obtained or derived for 334 organic chemicals. These concentrations were based on (1) current water quality guidelines; (2) apical screening values; (3) apical and (4) nonapical effect concentrations from the ECOTOXicology Knowledgebase; (5) in vitro effect concentrations from the ToxCast database; (6) cytotoxic burst concentrations collated from the Comptox Dashboard; (7) “estimated screening values” derived from modeled or estimated data and available from various regulatory and nonregulatory agencies; (8) pharmaceutical potency estimates from the MaPPFAST database; and (9) quantitative structure-activity relationship (QSAR)–derived acute toxicity estimates. Environmental fate data included aquatic half-lives and bioconcentration factors collated from the Comptox Dashboard or estimated using QSARs. To identify patterns that could be used for characterization, availability of ecotoxicological concentrations and environmental fate data were evaluated. Furthermore, exceedances of hazard concentrations were evaluated and compared across diverse ecotoxicological data types. Altogether, by providing detailed methodology and practical examples generated with real monitoring data, this study demonstrated that these hazard concentration derivation strategies can be efficiently and effectively used with large, complex datasets and identified critical considerations for future prioritization efforts.

Great Lakes region

Longitudinal and seasonal changes of organic matter sources through a semi-arid river-reservoir system

The quality and quantity of organic matter (OM) in a river system directly affects ecosystem health; thus, managers benefit from an in-depth understanding of the drivers and sources of OM. In the Snake River, a highly altered river-reservoir system in the semi-arid western United States, OM production and loading are key drivers of reservoir anoxia, which leads to several deleterious processes such as mercury methylation. However, sources and quantities of OM to the Snake River, and the effects of impoundment on OM moving through the river-reservoir system, are not well understood. Particulate organic carbon (POC), dissolved organic carbon (DOC), particulate nitrogen (PN), chlorophyll a (chl- a ), and δ 15 N–PN and δ 13 C–POC isotopic ratios were measured bi-weekly for over 2 years at four locations through the Snake River Hells Canyon Reservoir Complex to determine spatial and temporal patterns of OM quantities and sources. POC concentrations increased through the riverine zone upstream of the reservoirs, likely due to in situ primary production and/or inputs from tributaries and agricultural drains; then decreased through the most upstream reservoir likely due to particle settling. Isotopic ratios and other OM source indicators (δ 15 N–PN, δ 13 C–POC, POC:PN, chl- a :POC) show that the dominant source of particulate OM was phytoplankton with seasonal terrestrial/macrophytic inputs. Results highlight the effects of major tributary and agricultural drain inputs, primary production, and impoundment on OM composition and concentration through a large river-reservoir system and may inform water quality management efforts in this and similar systems.

Idaho, Oregon

Riparian methylmercury production increases riverine mercury flux and food web concentrations

The production and uptake of toxic methylmercury (MeHg) impacts aquatic ecosystems globally. Rivers can be dynamic and difficult systems to study for MeHg production and bioaccumulation, hence identifying sources of MeHg to these systems is both challenging and important for resource management within rivers and main-stem reservoirs. Riparian zones, which are known biogeochemical hotspots for MeHg production, are understudied as potential sources of MeHg to rivers. Here, we present a comprehensive quantification of the hydrologic and biogeochemical processes governing MeHg concentrations, loads, and bioaccumulation at 16 locations along 164 km of the agriculturally intensive Snake River (Idaho, Oregon USA) during summer baseflow conditions, with emphasis on riparian production of MeHg. Approximately one-third of the MeHg load of the Snake River could not be attributed to inflowing waters (upgradient, tributaries, or irrigation drains). Across the study reach, increases in MeHg loads in surface waters were significantly correlated with MeHg concentrations in riparian porewaters, suggesting riparian zones were likely an important source of MeHg to the Snake River. Across all locations, MeHg concentrations in surface waters positively correlated with MeHg concentrations in benthic snails and clams, supporting that riparian produced MeHg was assimilated into local aquatic food webs. This study contributes new insights into riparian MeHg production within rivers which can inform mitigation efforts to reduce MeHg bioaccumulation in fish.

Idaho, Oregon

Wildfires influence mercury transport, methylation, and bioaccumulation in headwater streams of the Pacific Northwest

The increasing frequency and severity of wildfires are among the most visible impacts of climate change. However, the effects of wildfires on mercury (Hg) transformations and bioaccumulation in stream ecosystems are poorly understood. We sampled soils, water, sediment, in-stream leaf litter, periphyton, and aquatic invertebrates in 36 burned (one-year post fire) and 21 reference headwater streams across the northwestern U.S. to evaluate the effects of wildfire occurrence and severity on total Hg (THg) and methylmercury (MeHg) transport and bioaccumulation. Suspended particulate THg and MeHg concentrations were 89 and 178% greater in burned watersheds compared to unburned watersheds and increased with burn severity, likely associated with increased soil erosion. Concentrations of filter-passing THg were similar in burned and unburned watersheds, but filter-passing MeHg was 51% greater in burned watersheds, and suspended particles in burned watersheds were enriched in MeHg but not THg, suggesting higher MeHg production in burned watersheds. Among invertebrates, MeHg in grazers, filter-feeders, and collectors was 33, 48, and 251% greater in burned watersheds, respectively, but did not differ in shredders or predators. Thus, increasing wildfire frequency and severity may yield increased MeHg production, mobilization, and bioaccumulation in headwaters and increased transport of particulate THg and MeHg to downstream environments.

Idaho, Oregon, Washington

Potential hazards of polycyclic aromatic hydrocarbons in Great Lakes tributaries using water column and porewater passive samplers and sediment wquilibrium partitioning

The potential for polycyclic aromatic hydrocarbon (PAH)-related effects in benthic organisms is commonly estimated from organic carbon-normalized sediment concentrations based on equilibrium partitioning (EqP). Although this approach is useful for screening purposes, it may overestimate PAH bioavailability by orders of magnitude in some sediments, leading to inflated exposure estimates and potentially unnecessary remediation costs. Recently, passive samplers have been shown to provide an accurate assessment of the freely dissolved concentrations of PAHs, and thus their bioavailability and possible biological effects, in sediment porewater and overlying surface water. We used polyethylene passive sampling devices (PEDs) to measure freely dissolved porewater and water column PAH concentrations at 55 Great Lakes (USA/Canada) tributary locations. The potential for PAH-related biological effects using PED concentrations were estimated with multiple approaches by applying EqP, water quality guidelines, and pathway-based biological activity based on in vitro bioassay results from ToxCast. Results based on the PED-based exposure estimates were compared with EqP-derived exposure estimates for concurrently collected sediment samples. The results indicate a potential overestimation of bioavailable PAH concentrations by up to 960-fold using the EqP-based method compared with measurements using PEDs. Even so, PED-based exposure estimates indicate a high potential for PAH-related biological effects at 14 locations. Our findings provide an updated, weight-of-evidence–based site prioritization to help guide possible future monitoring and mitigation efforts.

Illinois, Indiana, Michigan, Minnesota, New York,

Integrated science for the study of microplastics in the environment—A strategic science vision for the U.S. Geological Survey

Executive Summary Evidence of the widespread occurrence of microplastics throughout our environment and exposure to humans and other organisms over the past decade has led to questions about the possibility of health hazards and mitigation of exposures. This document discusses nanoplastics as well as microplastics (referred to solely as microplastics); the microplastics have a range from 1 micrometer to 5 millimeters (1 μm–5 mm) in length, whereas the nanoplastics are less than 1 μm in length (sidebar ES1). A myriad of environmental exposure pathways with microplastics to humans and wildlife, including ingestion, inhalation, and bodily absorption, are likely to exist. A growing body of evidence has documented bioaccumulation of microplastics in tissues and organs of humans and wildlife, benthic community effects, and potential nutritional and reproductive effects in some wildlife species. Understanding if or when environmental exposures pose a health risk is complicated by the diversity of microplastic sizes, morphologies, polymer types, and chemicals added during manufacturing or sorbed from the environment; ongoing challenges in analytical methods used to detect, quantify, and characterize microplastics and associated chemicals in our ecosystems; and the fact that ecotoxicological studies regarding microplastics are still in their infancy. Therefore, the study of environmental exposures and potential related health hazards of microplastics to the public and wildlife is a One Health (sidebar ES2) research topic that necessitates integrated science approaches. A better understanding of the sources, pathways, fate, and biological effects of microplastics has become a priority of the Federal Government, State governments, Tribes, stakeholders, and the public. Examples of Federal and State microplasticfocused legislation and programs to prioritize microplastic research and reduction include the Federal Microbead-Free Waters Act of 2015, California Senate Bills 1422 and 1263 (2018), the U.S. Environmental Protection Agency (EPA) Trash Free Waters Program, the National Institute of Standards and Technology’s Microplastic and Nanoplastic Metrology project, and Minnesota’s microplastic project. With its unique expertise and capabilities, the U.S. Geological Survey (USGS) is well positioned to help fill some of the most important microplastic science gaps. This strategic science vision document for microplastics identifies current (2023) microplastic science gaps and prioritizes research relevant to the mission, expertise, and capabilities of the USGS. It is intended for USGS scientists and stakeholders to use as a starting point for planning, prioritizing, and designing collaborative environmental microplastic science. Many of the microplastic science gaps and priorities are scalable, from local to national, and thus, can be made commensurate with available funding and evolving analytical and field tools, laboratory capacity, and stakeholder needs. Current (2023) or future research by academia and other Federal or State agencies, and Tribes may be aimed at some of the same microplastic science gaps identified in this document. Therefore, this document can be used as an information resource to maximize strengths and capabilities and minimize redundancy in communication and collaboration.

Circular

Metabolically diverse microorganisms mediate methylmercury formation under nitrate-reducing conditions in a dynamic hydroelectric reservoir

Brownlee Reservoir is a mercury (Hg)-impaired hydroelectric reservoir that exhibits dynamic hydrological and geochemical conditions and is located within the Hells Canyon Complex in Idaho, USA. Methylmercury (MeHg) contamination in fish is a concern in the reservoir. While MeHg production has historically been attributed to sulfate-reducing bacteria and methanogenic archaea, microorganisms carrying the hgcA gene are taxonomically and metabolically diverse and the major biogeochemical cycles driving mercury (Hg) methylation are not well understood. In this study, Hg speciation and redox-active compounds were measured throughout Brownlee Reservoir across the stratified period in four consecutive years (2016–2019) to identify the location where and redox conditions under which MeHg is produced. Metagenomic sequencing was performed on a subset of samples to characterize the microbial community with hgcA and identify possible links between biogeochemical cycles and MeHg production. Biogeochemical profiles suggested in situ water column Hg methylation was the major source of MeHg. These profiles, combined with genome-resolved metagenomics focused on hgcA -carrying microbes, indicated that MeHg production occurs in this system under nitrate- or manganese-reducing conditions, which were previously thought to preclude Hg-methylation. Using this multidisciplinary approach, we identified the cascading effects of interannual variability in hydrology on the redox status, microbial metabolic strategies, abundance and metabolic diversity of Hg methylators, and ultimately MeHg concentrations throughout the reservoir. This work expands the known conditions conducive to producing MeHg and suggests that the Hg-methylation mitigation efforts by nitrate or manganese amendment may be unsuccessful in some locations.

Idaho

Pesticide prioritization by potential biological effects in tributaries of the Laurentian Great Lakes

Watersheds of the Great Lakes Basin (USA/Canada) are highly modified and impacted by human activities including pesticide use. Despite labeling restrictions intended to minimize risks to nontarget organisms, concerns remain that environmental exposures to pesticides may be occurring at levels negatively impacting nontarget organisms. We used a combination of organismal-level toxicity estimates (in vivo aquatic life benchmarks) and data from high-throughput screening (HTS) assays (in vitro benchmarks) to prioritize pesticides and sites of concern in streams at 16 tributaries to the Great Lakes Basin. In vivo or in vitro benchmark values were exceeded at 15 sites, 10 of which had exceedances throughout the year. Pesticides had the greatest potential biological impact at the site with the greatest proportion of agricultural land use in its basin (the Maumee River, Toledo, OH, USA), with 72 parent compounds or transformation products being detected, 47 of which exceeded at least one benchmark value. Our risk-based screening approach identified multiple pesticide parent compounds of concern in tributaries of the Great Lakes; these compounds included: eight herbicides (metolachlor, acetochlor, 2,4-dichlorophenoxyacetic acid, diuron, atrazine, alachlor, triclopyr, and simazine), three fungicides (chlorothalonil, propiconazole, and carbendazim), and four insecticides (diazinon, fipronil, imidacloprid, and clothianidin). We present methods for reducing the volume and complexity of potential biological effects data that result from combining contaminant surveillance with HTS (in vitro) and traditional (in vivo) toxicity estimates. Environ Toxicol Chem 2022;00:1–18. Published 2022. This article is a U.S. Government work and is in the public domain in the USA. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Great Lakes

Mercury sources and budget for the Snake River above a hydroelectric reservoir complex

Understanding sources of mercury (Hg) and methylmercury (MeHg) to a water body is critical for management but is often complicated by poorly characterized Hg inputs and in situ processes, such as inorganic Hg methylation. In this study, we determined inorganic Hg and MeHg concentrations and loads (filter-passing and particulate fractions) for a semi-arid 164-kilometer stretch of the Snake River above the Hells Canyon Complex, a Hg-impaired hydroelectric reservoir complex on the Idaho-Oregon border, and used water quality measurements and Hg stable isotope ratios to create a comprehensive Hg source budget for the river. Results show that whereas most of the streamflow to the study reach comes from the main branch of the Snake River (i.e., the upstream watershed), major tributaries within the study reach contribute a greater proportion of inorganic Hg and MeHg loads. Mercury stable-isotope analyses highlight that Hg within the tributaries is predominantly associated with geologic deposits and snowmelt sources, the latter reflecting wet deposition. Surprisingly, irrigation return drains contribute 40–50 % of particulate inorganic Hg loads despite being ≤4.3 % of the overall water budget. Together, tributaries and irrigation return drains account for 97–100 % of the inorganic Hg and streamflow to the study reach, but ~65 % of the MeHg, indicating in-stream and riparian methylation may be an important and previously unrecognized source of MeHg. Streamflow, total suspended solids, dissolved organic carbon, and agricultural land cover were found to be important controls on the mobilization and transport of different Hg species and fractions. This study represents the first fluvial budget for Hg in the Snake River that accounts for particulate and filter-passing Hg species from both major tributaries and irrigation return drains, and expands our understanding of Hg sources and methylation processes within semi-arid environments. This information is critical to inform management decisions related to elevated Hg burdens in biota.

Idaho, Nevada, Oregon

Biogeochemical and hydrologic synergy control mercury fate in an arid land river-reservoir system

Reservoirs in arid landscapes provide critical water storage and hydroelectric power but influence the transport and biogeochemical cycling of mercury (Hg). Improved management of reservoirs to mitigate the supply and uptake of bioavailable methylmercury (MeHg) in aquatic food webs will benefit from a mechanistic understanding of inorganic divalent Hg (Hg( II )) and MeHg fate within and downstream of reservoirs. Here, we quantified Hg( II ), MeHg, and other pertinent biogeochemical constituents in water (filtered and associated with particles) at high temporal resolution from 2016–2020. This was done (1) at inflow and outflow locations of three successive hydroelectric reservoirs (Snake River, Idaho, Oregon) and (2) vertically and longitudinally within the first reservoir (Brownlee Reservoir). Under spring high flow, upstream inputs of particulate Hg (Hg( II ) and MeHg) and filter-passing Hg( II ) to Brownlee Reservoir were governed by total suspended solids and dissolved organic matter, respectively. Under redox stratified conditions in summer, net MeHg formation in the meta- and hypolimnion of Brownlee reservoir yielded elevated filter-passing and particulate MeHg concentrations, the latter exceeding 500 ng g −1 on particles. Simultaneously, the organic matter content of particulates increased longitudinally in the reservoir (from 9–29%) and temporally with stratified duration. In late summer and fall, destratification mobilized MeHg from the upgradient metalimnion and the downgradient hypolimnion of Brownlee Reservoir, respectively, resulting in downstream export of elevated filter-passing MeHg and organic-rich particles enriched in MeHg (up to 43% MeHg). We document coupled biogeochemical and hydrologic processes that yield in-reservoir MeHg accumulation and MeHg export in water and particles, which impacts MeHg uptake in aquatic food webs within and downstream of reservoirs.

Environmental Science: Processes & Impacts

Prioritizing pesticides of potential concern and identifying potential mixture effects in Great Lakes tributaries using passive samplers

To help meet the objectives of the Great Lakes Restoration Initiative with regard to increasing knowledge about toxic substances, 223 pesticides and pesticide transformation products were monitored in 15 Great Lakes tributaries using polar organic chemical integrative samplers. A screening-level assessment of their potential for biological effects was conducted by computing toxicity quotients (TQs) for chemicals with available US Environmental Protection Agency (USEPA) Aquatic Life Benchmark values. In addition, exposure activity ratios (EAR) were calculated using information from the USEPA ToxCast database. Between 16 and 81 chemicals were detected per site, with 97 unique compounds detected overall, for which 64 could be assessed using TQs or EARs. Ten chemicals exceeded TQ or EAR levels of concern at two or more sites. Chemicals exceeding thresholds included seven herbicides (2,4-dichlorophenoxyacetic acid, diuron, metolachlor, acetochlor, atrazine, simazine, and sulfentrazone), a transformation product (deisopropylatrazine), and two insecticides (fipronil and imidacloprid). Watersheds draining agricultural and urban areas had more detections and higher concentrations of pesticides compared with other land uses. Chemical mixtures analysis for ToxCast assays associated with common modes of action defined by gene targets and adverse outcome pathways (AOP) indicated potential activity on biological pathways related to a range of cellular processes, including xenobiotic metabolism, extracellular signaling, endocrine function, and protection against oxidative stress. Use of gene ontology databases and the AOP knowledgebase within the R-package ToxMixtures highlighted the utility of ToxCast data for identifying and evaluating potential biological effects and adverse outcomes of chemicals and mixtures. Results have provided a list of high-priority chemicals for future monitoring and potential biological effects warranting further evaluation in laboratory and field environments. Environ Toxicol Chem 2023;42:340–366. Published 2022. This article is a U.S. Government work and is in the public domain in the USA. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Great Lakes tributaries

In-reservoir physical processes modulate aqueous and biological methylmercury export from a seasonally anoxic reservoir

Anoxic conditions within reservoirs related to thermal stratification and oxygen depletion lead to methylmercury (MeHg) production, a key process governing the uptake of mercury in aquatic food webs. Once formed within a reservoir, the timing and magnitude of the biological uptake of MeHg and the relative importance of MeHg export in water versus biological compartments remain poorly understood. We examined the relations between the reservoir stratification state, anoxia, and the concentrations and export loads of MeHg in aqueous and biological compartments at the outflow locations of two reservoirs of the Hells Canyon Complex (Snake River, Idaho-Oregon). Results show that (1) MeHg concentrations in filter-passing water, zooplankton, suspended particles, and detritus increased in response to reservoir destratification; (2) zooplankton MeHg strongly correlated with MeHg in filter-passing water during destratification; (3) reservoir anoxia appeared to be a key control on MeHg export; and (4) biological MeHg, primarily in zooplankton, accounted for only 5% of total MeHg export from the reservoirs (the remainder being aqueous compartments). These results improve our understanding of the role of biological incorporation of MeHg and the subsequent downstream release from seasonally stratified reservoirs and demonstrate that in-reservoir physical processes strongly influence MeHg incorporation at the base of the aquatic food web.

Idaho, Oregon

Risk-based prioritization of organic chemicals and locations of ecological concern in sediment from Great Lakes tributaries

With improved analytical techniques, environmental monitoring studies are increasingly able to report the occurrence of tens or hundreds of chemicals per site, making it difficult to identify the most relevant chemicals from a biological standpoint. For this study, organic chemical occurrence was examined, individually and as mixtures, in the context of potential biological effects. Sediment was collected at 71 Great Lakes tributary sites and analyzed for 87 chemicals. Multiple risk-based lines of evidence were used to prioritize chemicals and locations, including comparing sediment concentrations and estimated porewater concentrations to established whole-organism benchmarks (i.e., sediment and water quality criteria and screening values) and to high-throughput toxicity screening data from the U.S. Environmental Protection Agency's ToxCast database, estimating additive effects of chemical mixtures on common ToxCast endpoints, and estimating toxic equivalencies for mixtures of alkylphenols and polycyclic aromatic hydrocarbons (PAHs). This multiple-lines-of-evidence approach enabled the screening of more chemicals, mitigated the uncertainties of individual approaches, and strengthened common conclusions. Collectively, at least one benchmark/screening value was exceeded for 54 of the 87 chemicals, with exceedances observed at all 71 of the monitoring sites. Chemicals with the greatest potential for biological effects, both individually and as mixture components, were bisphenol A, 4-nonylphenol, indole, carbazole, and several polycyclic aromatic hydrocarbons (PAHs). Potential adverse outcomes based on ToxCast gene targets and putative adverse outcome pathways relevant to individual chemicals and chemical mixtures included tumors, skewed sex ratios, reproductive dysfunction, hepatic steatosis, and early mortality, among others. Results provide a screening level prioritization of chemicals with the greatest potential for adverse biological effects and an indication of sites where they are most likely to occur.

Illinois, Indiana, Michigan, Minnesota, New York,