Geology topics

Marie Noele Croteau

Publications and source records attributed to Marie Noele Croteau.

At least 19 recordsLinked to original sources

USGS2026

Polystyrene microplastics alter the accumulation and elimination dynamics of silver nanoparticles in Daphnia magna

Rationale Microplastics (MPs) can interact with engineered nanomaterials and alter their environmental fate and bioavailability. However, their influence on the bioaccumulation dynamics of silver nanoparticles (AgNPs) in aquatic filter feeders under environmentally relevant conditions remains poorly understood. We hypothesized that polystyrene microplastics (PS-MPs) alter the uptake, elimination and overall bioaccumulation dynamics of AgNPs in Daphnia magna . Methodology Adult D. magna were exposed to isotopically labeled citrate-coated 109 AgNPs in the presence and absence of PS-MPs. Waterborne uptake, dietary uptake, assimilation efficiency, food ingestion and elimination were quantified experimentally and incorporated into a biodynamic model to predict steady-state silver (Ag) concentrations under environmentally relevant exposure scenarios. Results PS-MPs increased waterborne Ag accumulation by approximately eightfold compared with AgNPs exposure alone. However, Ag elimination was substantially faster, with 98% of accumulated Ag eliminated after five days of depuration compared with 66% without PS-MPs. PS-MPs also reduced food ingestion rates (IRs), while assimilation efficiency remained largely unchanged. Biodynamic modeling predicted that steady-state Ag accumulation was approximately fivefold greater in the presence of PS-MPs, with waterborne exposure becoming the dominant accumulation pathway. Discussion These findings suggest that PS-MPs alter bioaccumulation dynamics of AgNPs in filter-feeding organisms by enhancing organism-associated Ag during waterborne exposure while accelerating Ag elimination, likely through particle-associated transport and gut egestion. Collectively, these results underscore the complexity of Ag bioaccumulation processes when MPs and AgNPs interact and highlight the importance of studies conducted under environmentally relevant conditions.

Environmental Chemistry↗

USGS2025

Dietary bioavailability of uranium to a model freshwater invertebrate

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.

Environmental Science and Technology↗

USGS2025

Metal-rich lacustrine sediments from legacy mining perpetuate copper exposure to aquatic-riparian food webs

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 ∼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.

Michigan↗

USGS2024

A multidisciplinary approach that considers occurrence, geochemistry, bioavailability, and toxicity to prioritize critical minerals for environmental research

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.

Environmental Science & Technology↗

USGS2024

Dissolved arsenic concentrations in surface waters within the upper portions of the Klamath River Basin, Oregon and California

Arsenic toxicity is an environmental health problem. Levels of arsenic in surface waters at some locations in the Klamath River Basin in southern Oregon and northern California can exceed the U.S. Environmental Protection Agency (EPA) standard for drinking water. There are both anthropogenic and natural sources of arsenic. The Klamath River Basin consists primarily of volcanic deposits and contains an underground geothermal system with hot springs and warm water wells, all known natural sources of arsenic. Anthropogenic sources of arsenic are related to the agricultural use of herbicides, fungicides, and insecticides. Surface water arsenic levels can also be affected by fertilizer amendments, evaporative concentration, oxygen-level depletion, and various geochemical transformations that can increase arsenic mobilization. In this study by the U.S. Geological Survey and the Bureau of Reclamation, dissolved concentrations of arsenic, copper, and lead were measured in surface waters at 39 unique sites within the upper portions of the Klamath River Basin between 2018 and 2022. In every year, except 2022, sites were sampled four times between April and November. Surface-water arsenic concentrations varied up to four-orders of magnitude among sites. Median arsenic concentration was lowest at Cherry Creek (0.03 micrograms per liter [μg/L]) and highest at Wood Kimball Spring (36.7 μg/L), two sites located north of Upper Klamath Lake. The highest arsenic concentrations (17.4±4.9 μg/L, n =3) were found in drain sites (defined here as a waterbody returning used irrigation water) while the lowest arsenic concentrations were found in an artesian well (0.8 μg/L, n =1). The elevated arsenic concentrations of the drain sites suggest that arsenic might be concentrated or mobilized by agricultural activities, water re-use practices, and (or) by geochemical processes occurring around water stored in drains (that is, in the water column and across sediment water boundaries). A source of arsenic in drain water in the Klamath Strait Drain area includes water used for irrigation originating from Ady Canal. Other potential sources include groundwater, geothermal water, and local soils and sediments. Seasonal differences in surface-water arsenic concentrations were detected at 13 sites, 10 of which had higher arsenic concentrations in summer than in either spring or fall. The sites sampled around Upper Klamath Lake, the impounded rivers, one of the two canal sites, and 5 of the 14 river sites had higher surface-water arsenic concentrations in the summer than in either spring or fall. Surface-water arsenic concentrations from groundwater sources (that is, springs and in the artesian well) did not vary significantly among seasons (p-values greater than 0.1). Median surface-water concentrations of copper and lead ranged from 0.03 to 3.7 μg/L, and from 0.013 to 0.175 μg/L ( n =2–18), respectively. Dissolved concentrations of both metals were below acute toxicity endpoints reported by the EPA for freshwater animals. Surface-water arsenic concentrations varied independently from corresponding changes in surface-water lead or copper concentrations. However, arsenic concentrations measured in bed-sediment samples collected from a subset of sites located north of Upper Klamath Lake correlated strongly and significantly with the corresponding sedimentary lead concentrations ( p =0.015). Aqueous arsenic speciation measured in a subset of sites in 2019 and 2022 showed that all the arsenic existed as arsenic (V), the most oxidized arsenic species, and presumably, the least toxic. The highest proportions of arsenite (As(III)), the presumably most toxic arsenic species, relative to total arsenic concentrations were found at drain sites. Our assessment of dissolved arsenic concentrations in various surface-water bodies in the Upper Klamath River Basin reveals geographical areas of consistently low (below 2.1 μg/L), moderate (below 10 μg/L) and high (above 10 μg/L) surface-water arsenic concentrations. South of Upper Klamath Lake, surface-water arsenic concentrations were consistently higher than 20 μg/L at two drain sites located in an area of predominant agricultural land use with extensive water re-use practices. North of Upper Klamath Lake, surface-water arsenic concentrations greater than 20 μg/L were consistently measured at sites with limited nearby agricultural activities, suggesting a geogenic source. The consistently high arsenic levels from the Wood River at Jackson F. Kimball State Park, Fort Creek, and Crooked Creek, which are sites located at or near headwater spring sources, suggest a natural background source of arsenic. Water flowing downstream from this area could be a potential source of arsenic to Upper Klamath Lake and the Upper Klamath River.

California, Oregon↗

USGS2024

Balancing natural resource use and extraction of uranium and other elements in the Grand Canyon region

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.

Arizona↗

USGS2023

Aquatic insect accumulation of uranium at spring outflows in the Grand Canyon region as influenced by aqueous and sediment geochemistry and biological factors: Implications for monitoring

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, UO 2 (CO 3 ) 2 –2 , and UO 2 (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.

Arizona↗

USGS2023

Near-field receiving-water monitoring of trace metals and a benthic community near the Palo Alto Regional Water Quality Control Plant in south San Francisco Bay, California—2020

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.

California↗

USGS2021

Water chemistry, exposure routes and metal forms determine the bioaccumulation dynamics of silver (ionic and nanoparticulate) in Daphnia magna

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) 109 Ag in D. magna exposed to environmentally relevant 109 Ag 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 109 Ag were bioavailable to D. magna after exposure. Water chemistry affected 109 Ag influx from 109 AgNP but not from 109 AgNO 3 . Silver retention was greater for citrate-coated 109 AgNP than dissolved 109 Ag, indicating a greater potential for bioaccumulation from nanoparticulate Ag. Feeding inhibition was observed at higher dietary 109 Ag 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.

Environmental Toxicology and Chemistry↗

USGS2021

Near-field receiving-water monitoring of trace metals and a benthic community near the Palo Alto Regional Water Quality Control Plant in south San Francisco Bay, California—2019

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.

California↗

USGS2021

Effect of nanoparticle size and natural organic matter composition on the bioavailability of polyvinylpyrrolidone- coated platinum nanoparticles to a model freshwater invertebrate

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.

Environ. Sci. Technol.↗

USGS2020

Uranium bioaccumulation dynamics in the mayfly Neocloeon triangulifer and application to site-specific prediction

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.

Environmental Science & Technology↗

USGS2020

Concentrations and size distribution of TiO2 and Ag engineered particles in five wastewater treatment plants in the United States

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 an 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 TiO 2 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 TiO 2 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 TiO 2 engineered particles (in μg TiO 2 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 μg 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 TiO 2 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 TiO 2 . Nearly all Ag (>99%) and 55 to 100% of TiO 2 particles discharged to surface water with WWTP effluent are within the nanosize range. This study provides evidence that TiO 2 and Ag engineered nanomaterials enter aquatic systems with WWTP effluents, and that their concentrations are expected to increase with the increased applications of TiO 2 and Ag engineered nanomaterials in consumer products.

California, Massachusetts, South Carolina↗

USGS2019

Three-layered silver nanoparticles to trace dissolution and association to a green alga

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 (kuw) for total Ag (AgNP+D), NPs (AgNP) and AuNP were similar and 2.2-fold higher than the one from AgD exposure, suggesting predominant association of the particles over the dissolved form. Second, model calculations based upon Ag fluxes suggested that only 6-33% of algal burden was from AgD. Thirdly, the significantly lower AgNP/Au ratio measured with the algae after exposure (2.1 ± 0.1) compared to the AgNP/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.

Nanotoxicology↗

USGS2019

Competitive interactions among H, CU, and Zn ion moderate aqueous uptake of Cu and Zn by an aquatic insect

The absorption of aqueous copper (Cu) and zinc (Zn) by aquatic insects, a group widely used to assess water quality, is unresolved. This study examined interactions among Cu, Zn, and protons that potentially moderate Cu and Zn uptake by the acid-tolerant stonefly Zapada sp. Saturation uptake kinetics was imposed to identify competitive mechanisms. Decreasing pH reduced the maximum transport capacity, Jmax, in both metals, had little effect on the Cu dissociation constant, KD, and increased the Zn KD. Partial noncompetitive (Cu) and partial mixed competitive (Zn) inhibitor models most closely tracked the observed Cu and Zn influx across pH treatments. The estimated values for acid dissociation constants for the binary (proton-receptor) and ternary (proton-metal-receptor) complexes indicated the strong inhibitory effect of protons on Cu and Zn. In neutral pH water, Cu inhibited Zn uptake, but Zn had little effect on Cu uptake. The mechanism of Cu-Zn interaction was not identified. Results from separate Zn experiments suggested that the insect’s developmental stage may affect the apparent Jmax. The study underscores some of the challenges of modeling metal bioaccumulation and informs future research directions.

Environmental Pollution↗

USGS2018

Nanomaterials in the environment: Behavior, fate, bioavailability, and effects—An updated review

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.

Environmental Toxicology and Chemistry↗

USGS2018

A biodynamic understanding of dietborne and waterborne Ag uptake from Ag NPs in the sediment-dwelling oligochaete, Tubifex tubifex

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 AgNO 3 , respectively. Worms accumulated Ag from AgNO 3 more efficiently than from Ag NPs during waterborne exposure. The Ag uptake rate constants from water were 8.2 L/g/d for AgNO 3 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 (~50%) during depuration (i.e. after 17 days) was only observed for worms exposed to waterborne AgNO 3 (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 AgNO 3 and Ag NPs, respectively. Avoidance was only observed for worms exposed to sediment amended with AgNO 3 . 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 AgNO 3 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 .

NanoImpact↗

USGS2017

Assessing the dietary bioavailability of metals associated with natural particles: Extending the use of the reverse labeling approach to zinc

We extend the use of a novel tracing technique to quantify the bioavailability of zinc (Zn) associated with natural particles using snails enriched with a less common Zn stable isotope. Lymnaea stagnalis is a model species that has relatively fast Zn uptake rates from the dissolved phase, enabling their rapid enrichment in 67 Zn during the initial phase of labeling. Isotopically enriched snails were subsequently exposed to algae mixed with increasing amounts of metal-rich particles collected from two acid mine drainage impacted rivers. Zinc bioavailability from the natural particles was inferred from calculations of 66 Zn assimilation into the snail’s soft tissues. Zinc assimilation efficiency (AE) varied from 28% for the Animas River particles to 45% for the Snake River particles, indicating that particle-bound, or sorbed Zn, was bioavailable from acid mine drainage wastes. The relative binding strength of Zn sorption to the natural particles was inversely related to Zn bioavailability; a finding that would not have been possible without using the reverse labeling approach. Differences in the chemical composition of the particles suggest that their geochemical properties may influence the extent of Zn bioavailability.

Environmental Science & Technology↗