Environmental context Microplastics are widespread aquatic contaminants that can alter the environmental behavior of co-occurring pollutants. This study shows that polystyrene microplastics substantially modify silver nanoparticle bioaccumulation in Daphnia magna, increasing waterborne uptake, accelerating elimination and ultimately elevating predicted steady-state silver burdens. These findings can improve understanding of microplastic–nanoparticle interactions and can support future assessments of contaminant fate and ecological risk in aquatic systems.

Uranium (U) mining increases environmental exposures. Understanding how U is taken up by organisms can aid in evaluating the potential for bioaccumulation and toxicity. Although the importance of aqueous geochemical speciation is well recognized for U bioavailability after dissolved exposures, far less is known about the processes controlling U bioavailability after dietary exposures. This study characterizes the biogeochemical drivers of dietary U uptake in the freshwater snail Lymnaea stagnalis in laboratory experiments. Solids tested included benthic diatoms pre-exposed to dissolved U(VI), soils from contaminated U mine sites, and colloidal hydrous ferric oxide (HFO) synthesized in the presence of dissolved U(VI) or with U complexed by natural organic matter (NOM). Results showed that U was bioavailable from all solids. Uranium assimilation efficiency (AE), a proxy for dietary U bioavailability, varied among solids. AE was lowest for the U-contaminated soils (25 ± 17%) and highest for the U-laden diatoms (71 ± 13%). AE varied slightly among HFO preparations, suggesting modest influences of NOM and iron on U bioavailability. Increases in dietary U exposures reduced feeding rates, and the extent of feeding inhibition appeared inversely related to U bioavailability. The high U assimilation and range of bioavailability have implications for toxicity risks inferred without considering dietary uptake.

Historic copper mining left a legacy of metal-rich tailings resulting in ecological impacts along and within Torch Lake, an area of concern in the Keweenaw Peninsula, Michigan, USA. Given the toxicity of copper to invertebrates, this study assessed the influence of this legacy on present day nearshore aquatic and terrestrial ecosystems. We measured the metal (Co, Cu, Ni, Zn, Cd) and metalloid (As) concentrations in sediment, pore water, surface water, larval and adult insects, and two riparian spider taxa collected from Torch Lake and a nearby reference lake. Overall, elevated metal and metalloid concentrations, particularly Cu, were measured in all sediment samples and some surface and pore water samples collected from Torch Lake. For instance, Cu concentrations in the Torch Lake sediment were similar to 200% higher than the reference lake and all measured concentrations exceeded predicted effects concentrations by at least ninefold. Within larval insect tissues, we observed 160% higher Cu concentrations than measured in the reference lake, and Cu was the only measured element above predicted effects concentrations in Torch Lake. Adult insects collected at both lakes had similar metal concentrations irrespective of exposure levels. Yet we found 100% higher copper concentrations in Torch Lake riparian spiders, demonstrating elevated exposure risk to insectivores across the aquatic-terrestrial boundary. Our results highlight that other metals in the mixture may not be as concerning to adjacent riparian ecosystems, but copper remains a contaminant of concern in Torch Lake 60 years after mining ceased.

Critical minerals (or critical elements) are minerals or elements that are essential to global security and development and have supply chains vulnerable to disruption. In general, knowledge of the environmental behavior and health effects of critical elements is needed to support the development of safe and environmentally responsible supplies. This knowledge includes identifying potential consequences of increased critical element production and use, alternative critical element sources such as mine wastes, and adverse effects of critical elements on ecosystem condition and organismal health. Here we identify significant data gaps in the understanding of critical elements in surficial and aquatic environments, and the need, given the large number of commodities (50) identified on the 2022 critical minerals list for the United States, for an approach to prioritize them for study of their environmental fate and effects. We propose a multidisciplinary approach for this prioritization, considering measures of occurrence, geochemistry, bioavailability, and toxicity. We describe relatively easy-to-obtain metrics for each of these topic areas and demonstrate the utility of this integrated prioritization approach using indium and zinc as examples. This approach facilitates prioritizing research with a focus on those critical elements that are most mobile in the environment, bioavailable, toxic, or simply lacking data in these categories.

First posted June 3, 2024 For additional information, contact: Director, Colorado Water Science CenterU.S. Geological SurveyBox 25046, Mail Stop 415Denver, CO 80225 The Grand Canyon region is an important natural, cultural, and archeological resource known worldwide. The region contains uranium resources that could be used to generate electricity. The U.S. Geological Survey (USGS), in cooperation with the National Park Service, Bureau of Land Management, and U.S. Department of Agriculture Forest Service, is conducting studies to answer questions about the environmental effects of mining uranium and other associated elements in the region.

Potential adverse ecological effects of expanded uranium (U) mining within the Grand Canyon region motivated studies to better understand U exposure and risk to endemic species. This study documents U exposures and analyzes geochemical and biological factors affecting U bioaccumulation at spring-fed systems within the Grand Canyon region. The principal objective was to determine if aqueous U was broadly indicative of U accumulated by insect larvae, a dominate fauna. Analyses focused on three widely distributed taxa: Argia sp. (a predatory damselfly), Culicidae (suspension feeding mosquitos), and Limnephilus sp. (a detritivorous caddisfly). The study showed that U accumulated by aquatic insects (and periphyton) generally correlated positively with total dissolved U, although correlations were strongest when based on modeled concentrations of the U-dicarbonato complex, UO2(CO3)2–2, and UO2(OH)2. Sediment metal concentration was a redundant indicator of U bioaccumulation. Neither insect size or U in the gut content of Limnephilus sp. substantially affected correlations between aqueous U and whole-body U concentrations. However, in Limnephilus sp., the gut and its content contained large quantities of U. Estimates of the sediment burden in the gut indicated that sediment was a minor source of U mass but contributed substantially to the total insect weight. As a result, whole-body U concentration would tend to vary inversely with the sediment burden of the gut. The correlations between aqueous U and bioaccumulated U provide an initial relational baseline against which newly acquired data could be evaluated for changes in U exposure during and after mining operations.

First posted April 24, 2023 For additional information, contact: Contact Information,Geology, Minerals, Energy, & Geophysics Science CenterMenlo Park, CaliforniaU.S. Geological SurveyBuilding 19, 350 N. Akron Rd.P.O. Box 158Moffett Field, CA 94035 Trace-metal concentrations in sediment and in the clam Limecola petalum (World Register of Marine Species, 2020; formerly reported as Macoma balthica and M. petalum), clam reproductive activity, and benthic macroinvertebrate community structure were investigated in a mudflat 1 kilometer (km) south of the discharge of the Palo Alto Regional Water Quality Control Plant (PARWQCP) in south San Francisco Bay, California. This report includes the data collected by the U.S. Geological Survey (USGS) for January 2020–December 2020 (Cain and others, 2022). These data append to long-term datasets extending back to 1974. A major focus of the report is an integrated description of the 2020 data within the context of the longer, multidecadal dataset. This dataset supports the City of Palo Alto’s Near-Field Receiving- Water Monitoring Program, initiated in 1994.Silver and copper contamination substantially decreased at the site in the 1980s following the implementation by PARWQCP of advanced wastewater-treatment and source-control measures. Since the 1990s, concentrations of these elements in surface sediments have continued to decrease, although more slowly. For example, from 1994 to 2020, the minimum annual mean silver concentration—0.20 milligram per kilogram (mg/kg)—was observed in multiple years. In 2020, silver concentrations ranged from 0.18 to 0.28 mg/kg. These concentrations are 2 to 3 times higher than the regional background concentration. Presently (2020), sediment-copper concentrations appear to be near the regional background level. Over the same period (1994–2020), sedimentary iron and zinc exhibited modest decreases. Sedimentary aluminum, chromium, mercury, nickel, and selenium have not exhibited any trend. Since 1994, silver and copper concentrations in L. petalum have varied seasonally, apparently in response to a combination of site-specific metal exposures and cyclic growth and reproduction, as reported previously. Seasonal patterns for other elements, including chromium, mercury, nickel, selenium, and zinc, generally were similar in timing and magnitude as those for silver and copper. Downward trends in the silver and zinc concentrations in L. petalum during 1994–2020 were evident and appeared to be related to the general physiological condition of the clam, indicated by a condition index.Biological effects of elevated silver and copper contamination at the Palo Alto site have been interpreted from data collected during and after the recession of these contaminants. Concentrations of both elements in the soft tissues of L. petalum decreased with sedimentary copper and silver. This pattern was associated with changes in the reproductive activity of L. petalum, as well as the structure of the benthic invertebrate community. Reproductive activity of L. petalum increased as metal concentrations in L. petalum decreased (Hornberger and others, 2000), and presently is stable with almost all animals initiating reproduction in the fall and spawning the following spring. Analyses of the benthic community structure indicate that the infaunal invertebrate community has shifted from one dominated by several opportunistic species when silver and copper exposures were highest to one in which the species abundance is more evenly distributed, a pattern that indicates a more stable community that is subjected to fewer stressors. Importantly, this long-term change is unrelated to other metals and other measured environmental factors, including salinity and sediment composition. In addition, two of the opportunistic species (Ampelisca abdita and Streblospio benedicti) that brood their young and live on the surface of the sediment in tubes have shown a continual decrease in dominance coincident with the decrease in metals. Both species had short-lived rebounds in abundance in 2008, 2009, and 2010 and showed signs of increasing abundance in 2020. Heteromastus filiformis (a subsurface polychaete worm that lives in the sediment, consumes sediment and organic particles residing in the sediment, and reproduces by laying its eggs on or in the sediment) showed a concurrent increase in dominance and, in the last several years before 2008, showed a stable population. H. filiformis abundance increased slightly from 2011 to 2012 and returned to pre-2011 numbers in 2020.The reproductive mode of most species that were present in 2020 was indicative of species that were capable of movement either as pelagic larvae or as mobile adults. Although oviparous species were lower in number in this group, the authors hypothesize that these species will return slowly as more species move back into the area. The use of functional ecology was highlighted in the 2020 benthic community data, which showed that the animals that have now returned to the mudflat are those that can respond successfully to a physical, nontoxic disturbance. Today, community data show a mix of species that consume the sediment, or filter feed, those that have pelagic larvae that must survive landing on the sediment, and those that brood their young. The long-term recovery observed after the 1970s can be ascribed to the decrease in sediment pollutants.

Treatment wetlands utilize various physical and biological processes to reduce levels of organic contaminants, metals, bacteria, and suspended solids. Silver nanoparticles (AgNPs) are one type of contaminant that can enter treatment wetlands and impact the overall treatment efficacy. Grazing by filter‐feeding zooplankton, such as Daphnia magna, is critical to treatment wetland functioning; but the effects of AgNPs on zooplankton are not fully understood, especially at environmentally relevant concentrations. We characterized the bioaccumulation kinetics of dissolved and nanoparticulate (citrate‐coated) 109Ag in D. magna exposed to environmentally relevant 109Ag concentrations (i.e., 0.2–23 nmol L−1 Ag) using a stable isotope as a tracer of Ag. Both aqueous and nanoparticulate forms of 109Ag were bioavailable to D. magna after exposure. Water chemistry affected 109Ag influx from 109AgNP but not from 109AgNO3. Silver retention was greater for citrate‐coated 109AgNP than dissolved 109Ag, indicating a greater potential for bioaccumulation from nanoparticulate Ag. Feeding inhibition was observed at higher dietary 109Ag concentrations, which could lead to reduced treatment wetland performance. Our results illustrate the importance of using environmentally relevant concentrations and media compositions when predicting Ag bioaccumulation and provide insight into potential effects on filter feeders critical to the function of treatment wetlands. Environ Toxicol Chem 2022;41:726–738. © 2021 SETAC

First posted October 8, 2021 For additional information, contact: Director,Water Resources, Earth System Processes DivisionU.S. Geological Survey411 National Center 12201 Sunrise Valley Drive Reston, VA 20192 Trace-metal concentrations in sediment and in the clam Limecola petalum (formerly reported as Macoma balthica and M. petalum), clam reproductive activity, and benthic macroinvertebrate community structure were investigated in a mudflat 1 kilometer south of the discharge of the Palo Alto Regional Water Quality Control Plant (PARWQCP) in south San Francisco Bay, Calif. This report includes the data collected by the U.S. Geological Survey (USGS) for the period January 2019 to December 2019. These data append to long-term datasets extending back to 1974. A major focus of the report is an integrated description of the 2019 data within the context of the longer, multidecadal dataset. This dataset supports the City of Palo Alto’s Near-Field Receiving-Water Monitoring Program, initiated in 1994.Significant reductions in silver and copper contamination occurred at the site in the 1980s following the implementation by PARWQCP of advanced wastewater treatment and source control measures. Since the 1990s, concentrations of these elements in surface sediments have continued to decrease, although more slowly. Silver appears to have stabilized at concentrations about twice the regional background concentration. Presently, sediment copper concentrations appear to be near the regional background level. Over the same period (1994–2019), sedimentary iron and zinc also exhibited modest declines. Sedimentary aluminum, chromium, mercury, nickel, and selenium have not exhibited any trend. Since 1994, concentrations of silver and copper in L. petalum have varied seasonally, apparently in response to a combination of site-specific metal exposures and cyclic growth and reproduction, as reported previously. Seasonal patterns for other elements, including chromium, mercury, nickel, selenium, and zinc, were generally similar in timing and magnitude as those for silver and copper. The annual growth and reproductive cycle explained a small amount of the variance in annual silver and zinc tissue metal concentrations. However, interannual trends are not apparent for any element.Biological effects of elevated silver and copper contamination at the Palo Alto site have been interpreted from data collected during and after the recession of these contaminants. Concentrations of both elements in the soft tissues of L. petalum declined with sedimentary copper and silver. This pattern was associated with changes in the reproductive activity of L. petalum, as well as the structure of the benthic invertebrate community. Reproductive activity of L. petalum increased as metal concentrations in L. petalum declined and presently is stable with almost all animals initiating reproduction in the fall and spawning the following spring. Analyses of the benthic community structure indicate that the infaunal invertebrate community has shifted from one dominated by several opportunistic species when silver and copper exposures were highest to one in which the species abundance is more evenly distributed, a pattern that indicates a more stable community that is subjected to fewer stressors. Importantly, this long-term change is unrelated to other metals and other measured environmental factors, including salinity and sediment composition. In addition, two of the opportunistic species (Ampelisca abdita and Streblospio benedicti) that brood their young and live on the surface of the sediment in tubes have shown a continual decline in dominance coincident with the decline in metals. Both species had short-lived rebounds in abundance in 2008, 2009, and 2010 and showed signs of increasing abundance in 2019. Heteromastus filiformis (a subsurface polychaete worm that lives in the sediment, consumes sediment and organic particles residing in the sediment, and reproduces by laying its eggs on or in the sediment) showed a concurrent increase in dominance and, in the last several years before 2008, showed a stable population. H. filiformis abundance increased slightly in 2011–2012 and returned to pre-2011 numbers in 2019.An unidentified disturbance occurred on the mudflat in early 2008 that resulted in the loss of the benthic animals, except for deep-dwelling animals like L. petalum. However, within two months of this event, animals returned to the mudflat. The resilience of the community suggested that the disturbance was not caused by a persistent toxin or anoxia. The reproductive mode of most species that were present in 2019 was indicative of species that were available either as pelagic larvae or as mobile adults. Although oviparous species were lower in number in this group, the authors hypothesize that these species will return slowly as more species move back into the area. The use of functional ecology was highlighted in the 2019 benthic community data, which showed that the animals that have now returned to the mudflat are those that can respond successfully to a physical, nontoxic disturbance. Today, community data show a mix of species that consume the sediment, or filter feed, those that have pelagic larvae that must survive landing on the sediment, and those that brood their young. USGS scientists view the 2008 disturbance event as a response by the infaunal community to an episodic natural stressor (possibly sediment accretion or a pulse of freshwater), in contrast to the long-term recovery from metal contamination. We will compare this recovery to the long-term recovery observed after the 1970s when the decline in sediment pollutants was the dominating factor.

The bioavailability of dissolved Pt(IV) and polyvinylpyrrolidone-coated platinum nanoparticles (PtNPs) of five different nominal hydrodynamic diameters (20, 30, 50, 75, and 95 nm) was characterized in laboratory experiments using the model freshwater snail Lymnaea stagnalis. Dissolved Pt(IV) and all nanoparticle sizes were bioavailable to L. stagnalis. Platinum bioavailability, inferred from conditional uptake rate constants, was greater for nanoparticulate than dissolved forms and increased with increasing nanoparticle hydrodynamic diameter. The effect of natural organic matter (NOM) composition on PtNP bioavailability was evaluated using six NOM samples at two nanoparticle sizes (20 and 95 nm). NOM suppressed the bioavailability of 95 nm PtNPs in all cases, and DOM reduced sulfur content exhibited a positive correlation with 95 nm PtNP bioavailability. The bioavailability of 20 nm PtNPs was only suppressed by NOM with a low reduced sulfur content. The physiological elimination of Pt accumulated after dissolved Pt(IV) exposure was slow and constant. In contrast, the elimination of Pt accumulated after PtNP exposures exhibited a triphasic pattern likely involving in vivo PtNP dissolution. This work highlights the importance of PtNP size and interfacial interactions with NOM on Pt bioavailability and suggests that in vivo PtNP transformations could yield unexpectedly higher adverse effects to organisms than dissolved exposure alone.

The growing use of engineered particles (e.g., nanosized and pigment sized particles, 1 to 100 nm and 100 to 300 nm, respectively) in a variety of consumer products increases the likelihood of their release into the environment. Wastewater treatment plants (WWTPs) are important pathways of introduction of engineered particles to the aquatic systems. This study reports the concentrations, removal efficiencies, and particle size distributions of Ag and TiO2 engineered particles in five WWTPs in three states in the United States. The concentration of Ag engineered particles was quantified as the total Ag concentration, whereas the concentration of TiO2 engineered particles was quantified using mass-balance calculations and shifts in the elemental ratio of Ti/Nb above their natural background elemental ratio. Ratios of Ti/Nb in all WWTP influents, activated sludges, and effluents were 2-12 times higher (e.g., 519 to 3243) than the natural background Ti/Nb ratio (e.g., 267 +/- 9), indicating that 49-92% of Ti originates from anthropogenic sources. The concentration of TiO2 engineered particles (in mu g TiO2 L-1) in the influent, activated sludge, and effluent varied within the ranges of 70-670, 3570-6700, and 7-30, respectively. The concentration of Ag engineered particles (in mu g Ag L-1) in the influent, activated sludge, and effluent varied within the ranges of 0.11-0.33, 1.45-1.65, and 0.01-0.04, respectively. The overall removal efficiency (e.g., effluent/influent concentrations) of TiO2 engineered particles (e.g., 90 to 96%) was higher than that for Ag engineered particles (e.g., 82 to 95%). Particles entering WWTPs are in the nanosized range for Ag (e.g., >99%) and a mixture of nanosized (e.g., 15 to 90%) and pigment sized particles (e.g., 10 to 85%) for TiO2. Nearly all Ag (>99%) and 55 to 100% of TiO2 particles discharged to surface water with WWTP effluent are within the nanosize range. This study provides evidence that TiO2 and Ag engineered nanomaterials enter aquatic systems with WWTP effluents, and that their concentrations are expected to increase with the increased applications of TiO2 and Ag engineered nanomaterials in consumer products. (C) 2020 Elsevier B.V. All rights reserved.

Little is known about the underlying mechanisms governing the bioaccumulation of uranium (U) in aquatic insects. We experimentally parameterized conditional rate constants for aqueous U uptake, dietary U uptake, and U elimination for the aquatic baetid mayfly Neocloeon triangulifer. Results showed that this species accumulates U from both the surrounding water and diet, with waterborne uptake prevailing. Elevated dietary U concentrations decreased feeding rates, presumably by altering food palatability or impairing the mayfly's digestive processes, or both. Nearly 90% of the accumulated U was eliminated within 24 h after the waterborne exposure ceased, reflecting the desorption of weakly bound U from the insect's integument. To examine whether the experimentally derived rate constants for N. triangulifer could be generalized to baetid mayflies, mayfly U concentrations were predicted using the water chemistry and U measured in periphyton from springs in Grand Canyon (United States) and were compared to U concentrations in spring-dwelling mayflies. Predicted and observed mayfly U concentrations were in good agreement. Under the modeled site-specific conditions, waterborne U uptake accounted for 52-93% of the bioaccumulated U. U accumulation was limited in these wild populations due to a combination of factors including low concentrations of bioavailable dissolved U species, slow U uptake rates from food, and fast U elimination.

Core-shell silver nanoparticles (NPs) consisting of an inner Ag core and successive layers of Au and Ag (Ag@Au@Ag) were used to measure the simultaneous association of Ag NPs and ionic Ag by the green alga Chlamydomonas (C.) reinhardtii. Dissolution of the inner Ag core was prevented by a gold (Au) layer, while the outer Ag layer was free to dissolve. In short-term experiments, we exposed C. reinhardtii to a range of environmentally realistic Ag concentrations added as AgNO3 or as NPs. Results provide three lines of evidence for the greater cell-association of NPs compared to dissolved Ag over the concentration range tested, assuming that cell-association comprises both uptake and adsorption. First, the cell-association rate constants (k(uw)) for total Ag (AgNP+D), NPs (Ag-NP) and Au-NP were similar and 2.2-fold higher than the one from Ag-D exposure, suggesting predominant association of the particles over the dissolved form. Second, model calculations based on Ag fluxes suggested that only 6-33% of algal burden was from Ag-D. Third, the significantly lower Ag-NP/Au ratio measured with the algae after exposure (2.1 +/- 0.1) compared to the Ag-NP/Au ratio of the NPs in the media (2.47 +/- 0.05) suggests cell-association of NPs depleted in Ag. Core-shell NPs provide an innovative tool to understand NP behavior and to directly delineate Ag accumulation from ion and NPs in aquatic systems.

Metal nanoparticles (Me-NPs) are increasingly used in various products, such as inks and cosmetics, enhancing the likelihood of their release into aquatic environments. An understanding of the mechanisms controlling their bioaccumulation and ecotoxicity in aquatic biota will help support environmental risk assessment. Here we characterized unidirectional parameters for uptake and elimination of silver (Ag) in the sediment-dwelling oligochaete Tubifex tubifex after waterborne (0.01-47 nmol Ag/L) and dietborne (0.4-482 nmol Ag/g dw sed.) exposures to Ag NPs and AgNO3, respectively. Worms accumulated Ag from AgNO3 more efficiently than from Ag NPs during waterborne exposure. The Ag uptake rate constants from water were 8.2 L/g/d for AgNO3 and 0.34 L/g/d for Ag NPs. Silver accumulated from both forms was efficiently retained in tissues, as no significant loss of Ag was detected after up to 20 days of depuration in clean media. High mortality (similar to 50%) during depuration (i. e. after 17 days) was only observed for worms exposed to waterborne AgNO3 (3 nmol/L). Sediment exposures to both Ag forms resulted in low accumulation, i. e., the uptake rate constants were 0.002 and 0.005 g/ g/d for AgNO3 and Ag NPs, respectively. Avoidance was only observed for worms exposed to sediment amended with AgNO3. Incorporation of the estimated rate constants into a biodynamic model predicted that sediment is likely the most important route of uptake for Ag in both forms in ecologically relevant aquatic environments. However, inference of bioavailability from our estimations of Ag assimilation efficiencies (AE) suggests that Ag (AE: 3-12% for AgNO3 and 0.1-0.8% for Ag NPs) is weakly bioavailable from sediment for this species. Thus, Ag amended to sediment as NPs might not pose greater problems than 'conventional' Ag for benthic organisms such as T. tubifex.

The present review covers developments in studies of nanomaterials (NMs) in the environment since our much cited review in 2008. We discuss novel insights into fate and behavior, metrology, transformations, bioavailability, toxicity mechanisms, and environmental impacts, with a focus on terrestrial and aquatic systems. Overall, the findings were that: 1) despite substantial developments, critical gaps remain, in large part due to the lack of analytical, modeling, and field capabilities, and also due to the breadth and complexity of the area; 2) a key knowledge gap is the lack of data on environmental concentrations and dosimetry generally; 3) substantial evidence shows that there are nanospecific effects (different from the effects of both ions and larger particles) on the environment in terms of fate, bioavailability, and toxicity, but this is not consistent for all NMs, species, and relevant processes; 4) a paradigm is emerging that NMs are less toxic than equivalent dissolved materials but more toxic than the corresponding bulk materials; and 5) translation of incompletely understood science into regulation and policy continues to be challenging. There is a developing consensus that NMs may pose a relatively low environmental risk, but because of uncertainty and lack of data in many areas, definitive conclusions cannot be drawn. In addition, this emerging consensus will likely change rapidly with qualitative changes in the technology and increased future discharges. Environ Toxicol Chem 2018;37:2029–2063. © 2018 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals, Inc. on behalf of SETAC.