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Using a time-of-travel sampling approach to quantify per- and polyfluoroalkyl substances (PFAS) stream loading and source inputs in a mixed-source, urban catchment

Understanding per- and polyfluoroalkyl substances (PFAS) mass distribution in surface and groundwater systems can support source prioritization, load reduction, and water management. Thirteen sites within an urban catchment were sampled utilizing a time-of-travel sampling approach to minimize the influence of subdaily fluctuations in mass from PFAS point sources and to quantify PFAS and ancillary chemical loads from various PFAS sources. A larger increase in perfluoroalkyl sulfonate (PFSA) loads (8 to 11 μg/s, up to 618%) than in perfluoroalkyl carboxylate (PFCA) loads (no change to 3.4 μg/s, up to 122%) was observed at sites below tributaries influenced by military bases with known groundwater discharge. Point discharges from two sewage treatment plants (STPs) resulted in increases in PFCA and PFSA loads that were similar (6 and 10 μg/s respectively) below the first STP and greater for PFCA compared to PFSA loads (23 and 13 μg/s respectively) below the second STP. Overall, percent increases in total PFAS load ranged from 20 to 277% for military base inputs and 44 to 77% for STP inputs. A focus catchment that represents only 14% (76.9 km 2 ) of the drainage area at the most downstream site (544 km 2 ) accounted for about 70% of PFSA and 40% of PFCA loads observed at the most downstream site. Results show that by using a time-of-travel sampling approach in mixed, urban settings with several PFAS sources, it is possible to quantify stream loads from individual PFAS sources, thereby improving source attribution and providing actionable data for water-resource managers.

ACS ES&T Water

Detection of viral, bacterial, and protozoan pathogens and microbial source tracking markers in paired large- and small-volume water samples

When sampling for waterborne microbes, researchers may need to diverge from recommended sample volumes due to logistical constraints, novel targets, or challenging matrices, with little guidance about the potential impact on results. In field studies, we measured bacteria, viruses, and protozoa (15 quantitative polymerase chain reaction assays) in paired large- and small-volume samples to evaluate method performance and relevant factors. Concordance between methods was low. Large-volume ultrafiltration yielded more detections than small-volume sampling, especially for pathogens in groundwater. Greater microbial concentrations were associated with more frequent detections in small-volume samples and greater concordance between paired samples. Large-volume samples appeared to be more susceptible to diminished sensitivity from complex sample matrices. In laboratory studies, recovery of microbes was poorer for large- than small-volume methods, although large-volume methods more reliably detected low-concentration targets. Large-volume samples were less stable than small-volume samples during storage. Overall, large-volume sampling was superior for detecting pathogens but may underestimate concentrations; small-volume sampling was more prone to false negatives but was adequate when concentrations were relatively high, like we observed for microbial source tracking in surface waters.

Wisconsin

Microplastics undergo fragmentation during pressurized membrane filtration

Low-micrometer microplastics (<10 μm) have been detected in drinking water, driving growing interest in using pressure-driven membrane filtration to remove these particles and ensure drinking water safety. However, little attention is paid to the fate of microplastics concentrated in the filtration byproduct. In this study, using well-defined polystyrene (PS) and poly(methyl methacrylate) microspheres as model particles, we observed microplastic fragmentation during nanofiltration and the subsequent release of smaller fragments. After operating for 3 h at 20 bar, 67.9 ± 8.0% of the PS spheres in the concentrate, based on particles counted in selected fields of view, were transformed into fractured particles. The characteristic Raman band signals of microplastics were significantly weakened after fragmentation, leading to detection challenges. To address this, a data processing algorithm was developed to identify PS fragments as small as 1 μm. Preliminary statistical analysis reveals that within the tested pressure range, operation time has a stronger influence on fragmentation than pressure magnitude alone and that fragmentation is further governed by the intrinsic mechanical properties of the tested model polymers. This work provides direct evidence that pressure-driven membrane processes induce microplastic fragmentation and highlights the environmental risks associated with the discharge of fragmented microplastics into the concentrate.

Environmental Science & Technology Letters

Examining the compositional selectivity of hydrocarbon oxidation products using liquid–liquid extraction and solid-phase extraction techniques

The effect of extraction methods on detecting hydrocarbon oxidation products (HOPs) in groundwater remains unclear. HOPs are polar, water-soluble byproducts of petroleum biodegradation. Our previous work showed that liquid–liquid extraction (LLE), a method commonly used in regulatory monitoring, has a significantly lower extraction efficiency for HOPs compared to solid-phase extraction (SPE). In this study, we evaluate the analytical limitations and compositional selectivity of LLE and SPE using groundwater samples from the Bemidji, MN, crude oil spill site. Optical properties were characterized using excitation–emission matrix spectroscopy (EEMs), and a three-component PARAFAC model was validated, showing consistent trends across both extracts and whole water samples. Ultrahigh-resolution mass spectrometry (UHR-MS) revealed that LLE selectively recovered aliphatic-like compounds but underrepresented more polar oxygenated HOPs. In contrast, SPE methods were more effective at isolating highly oxidized compound classes. These differences were consistent across a gradient of contamination. Overall, the LLE was less precise and less representative of polar HOPs, introducing bias in the characterization of HOPs. This study is the first to quantitatively demonstrate the compositional selectivity and analytical bias of LLE versus SPE for HOPs using combined EEM-PARAFAC and UHR-MS techniques, with implications for long-term monitoring and site assessment protocols.

Environmental Science and Technology

Roadway runoff induced acute mortality in juvenile coho salmon during spring storm events

Extensive mortalities of adult coho salmon ( Oncorhynchus kisutch ), often called “Urban Runoff Mortality Syndrome” (URMS), have been documented during the fall in creeks where water quality has been degraded by roadway runoff. The primary cause of mortality is 6PPD-quinone (6PPDQ; N -(1,3-dimethylbutyl)- N ′-phenyl- p -phenylenediamine quinone)–an ozone transformation product that forms on all vehicle tires. Laboratory studies have shown that juvenile coho salmon are highly sensitive to 6PPDQ exposure. Unlike adults, juveniles reside in impacted watersheds year-round, including during the spring when 6PPDQ concentrations can frequently exceed lethal thresholds during storms. To assess the potential incidence of URMS in springtime rearing habitats for juvenile coho salmon, we conducted a paired water quality and toxicology study at Miller Creek, a runoff-impacted watershed in Normandy Park, WA, USA. Using a small field facility, three naïve groups of juvenile coho salmon ( N = 720) were exposed to either creek water or groundwater ( N = 120 per treatment per storm), across three spring storms while comparing water quality and mortality end points. In creek water during exposures, peak 6PPDQ concentrations reached 73–110 ng/L, exceeding reported median lethal concentrations (LC 50 ) for coho salmon. Over each 24–73 h storm exposure period, ∼80% of Miller Creek-exposed juvenile salmon died. No mortality occurred among control fish exposed to groundwater. These results indicate previously unidentified mortality risks for juvenile life stages of coho salmon during spring storms, suggesting substantial and year-round water quality impediments to coho salmon health and recovery across roadway runoff-impacted spawning, rearing, and migratory habitats.

Washington

How do hydrological variability and human activities control the spatiotemporal changes of riverine nitrogen export in the Upper Mississippi River Basin?

Excessive nitrogen export from agricultural watersheds remains a critical water quality challenge, with the Upper Mississippi River Basin (UMRB) significantly contributing to downstream eutrophication and hypoxia in the Gulf. This study investigates the spatiotemporal dynamics of riverine nitrate plus nitrite (NO 3 – + NO 2 – -N) export across the UMRB at high spatial resolution (12-digit Hydrologic Unit Codes or HUC12 subwatershed scale) during 2001–2020 and quantifies the effects of anthropogenic activities and hydrological variability on riverine NO 3 – + NO 2 – -N export changes in the region between 2001–2005 and 2016–2020. Our results revealed hotspots of substantial increases in NO 3 – + NO 2 – -N yields across the UMRB, with distinct regional patterns in driving factors. Over the entire UMRB, NO 3 – + NO 2 – -N yields increased by 9.7 kg/ha/yr on average from 2001–2005 to 2016–2020, with anthropogenic activities contributing 4.8 kg/ha/yr and hydrological variability contributing 4.9 kg/ha/yr. The northern and western UMRB had combined influences from both anthropogenic activities and hydrological variability, while the east-central regions had predominantly hydrologically driven changes. Agricultural sources, including fertilizer, manure, and biological nitrogen fixation, collectively contributed over 80% of NO 3 – + NO 2 – -N loading throughout the basin. This framework for disentangling human and hydrological impacts provides critical insights for developing effective and targeted watershed management strategies to reduce nutrient losses and improve water quality.

Upper Mississippi River Basin

Predictions of anthropogenic background PFAS concentrations in soil and relation to bedrock lithology and groundwater quality

Detectable concentrations of per- and polyfluoroalkyl substances (PFAS) have been observed in soils in remote areas and presumably originate from atmospheric deposition. These anthropogenic background concentrations may enable some PFAS to leach to groundwater at levels that exceed regulatory criteria for drinking water. However, anthropogenic background soil concentrations and their connection to groundwater are not well characterized. We developed a boosted regression tree model to predict perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) concentrations in shallow soils across northern New England. Low soil pH was the most important predictor of elevated anthropogenic PFOS and PFOA concentrations in background soils, rather than potential PFAS sources, land use, or population density. Total organic carbon (TOC) was also an important predictor for PFOS soil concentrations. Model predictions indicate that 73% of the shallow soils within Maine, Vermont, and New Hampshire exceed New Hampshire’s Soil Remediation Standard for PFOS (0.5 ng/g) and 41% exceed the PFOA standard (0.4 ng/g). Analysis of soil model results and groundwater data suggests that areas with high soil pH are associated with higher groundwater detection frequencies, illustrating how areas with less retention in soil are, conversely, also areas with potentially greater groundwater vulnerability. Further analysis indicates that groundwater may be more vulnerable in calcareous lithologies.

Maine, New Hampshire, Vermont

King Rails in southeastern Arkansas are majority resident

King Rails ( Rallus elegans ), a declining species of secretive marsh bird, have a mixed migratory strategy, with some individuals migrating and some being year-round residents. Determining the distribution of migratory versus resident King Rails is critical to guiding habitat management and assessing risks to populations. We examined the migratory status of adult King Rails at the Choctaw West Wildlife Management Area in southeastern Arkansas, the only known site in Arkansas with multiple breeding pairs. Of the 23 adult King Rails we tagged in 2022 and 2023, two birds migrated away from the local area, one in each year. One migrated 145 km, and the other 450 km. Our findings suggest that the line between the migratory and resident range of Arkansas King Rails could be north of our site.

Arkansas

Tracing mercury from land to river: Global sources, retention, and implications for sustainability

Mercury (Hg) pollution in river systems is a global sustainability challenge. Yet the transport, transformation, and retention of Hg within global rivers remain poorly quantified, particularly in regions with sparse observations such as Southeast Asia and Africa, hindering effective pollution mitigation and reinforcing geographic inequities in scientific knowledge and environmental governance. Here, we present the first global, high-resolution simulation of riverine Hg dynamics using a process-based model that traces Hg from land-based sources through river networks to the ocean. Under a realistic scenario, we estimate that ∼1900 megagrams per year (Mg/yr) of Hg enters global rivers, including 1500 Mg/yr from human-induced sources and 400 Mg/yr from soil erosion. Nearly half of this flux (∼1000 Mg/yr) is retained in reservoirs and dams, which act as major sinks. While such retention limits downstream delivery to the oceans, it also heightens in-reservoir Hg methylation risks. By bridging the gap between Hg releases and observed riverine exports, our framework offers a scalable tool for data-limited regions, promotes data access, and supports global freshwater and pollution-management strategies.

Environmental Science & Technology

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

Remote sensing enables basin-scale inventories of coal mine methane

Underground coal mines are important global sources of methane, but emission estimates are uncertain. We show that emission estimates for individual mines from aircraft remote-sensing surveys in the United States agree within 40% with direct measurements used for national emission reporting (IPCC Tier 3 estimate). Such direct measurements are unavailable in most countries, which rely on estimated emission factors (EFs) applied to coal-production rates. We find that EFs from IPCC Tier 1 and the Model for Calculating Coal Mine Methane (MC2M) methods overestimate U.S. emissions 3-fold due to incorrect dependence on mine depth. An IPCC Tier 2 method using measured basin-specific mine gas content agrees with direct emission measurements but does not account for gob well emissions and requires gas content data that are generally unavailable. We show that aircraft remote sensing for a small sample of mines can successfully estimate basin-specific EFs for ventilation shafts and gob wells, enabling estimates of basin- and national-scale emissions. We discuss how the method can be applied with satellite remote sensing to quantify coal emissions worldwide.

Alabama, Colorado, Kentucky, New Mexico, Ohio, Pen

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

3-D geological modeling for numerical flow simulation studies of gas hydrate reservoirs at the Kuparuk State 7-11-12 Pad in the Prudhoe Bay Unit on the Alaska North Slope

Accurate reservoir evaluation requires reliable three-dimensional (3-D) geological models. This study conducted 3-D geological modeling for numerical flow simulation of the B1 sand gas hydrate reservoir at the Kuparuk State 7-11-12 pad, Prudhoe Bay Unit, Alaska North Slope. The model integrates well logs, core, and seismic data to address spatial heterogeneity in geological structures and reservoir properties. Two modeling types were performed: structural framework modeling and petrophysical property modeling. For structural framework modeling, seismic data and well log markers were used to reproduce subsurface structures characterized by a normal fault system. A volume-based modeling algorithm and stair-step gridding were applied. The resulting 3-D model comprised 2,640,000 grid cells across 264 layers, including seven fault grids. For petrophysical property modeling, total porosity was initially modeled using sequential Gaussian simulation with collocated cokriging. To reproduce the upward coarsening of the B1 sand, upscaled log-derived total porosity and a 3-D trend depicting total porosity variation were used as primary and secondary data, respectively. Gas hydrate saturation distribution was modeled similarly, with secondary data from estimated porosity distribution and seismic-derived acoustic impedance map enhancing accuracy. Results indicate higher gas hydrate saturation in the upper part of the B1 sand and areas with higher acoustic impedance. Intrinsic permeability was modeled from the total porosity and clay-bound water volume, and effective permeability was derived from the gas hydrate saturation and intrinsic permeability distributions based on the “Tokyo model”. Effective permeability distributions were influenced by the total porosity, gas hydrate saturation, and intrinsic permeability. Within the same layer, higher gas hydrate saturation leads to decreased effective permeability. In total, 100 sets of multiple scenarios were prepared, providing input data for dynamic flow simulations to evaluate the effects of lateral heterogeneity in reservoir properties and the hydraulic characteristics of faults on production behavior for preassessment before the long-term production test.

Alaska

PFAS mixture composition and internal exposure profiles shape biological responses under field-realistic exposure

Per- and polyfluoroalkyl substances (PFAS) occur as complex mixtures, yet mixture-dependent biological effects under environmentally realistic exposure conditions remain poorly understood. We conducted multiyear (2018, 2019, 2021) continuous-flow, field-based exposures of male fathead minnows ( Pimephales promelas ) using a low-PFAS reference well (REF; sum of measured PFAS (∑PFAS) 0.1–0.2 μg L –1 ) and PFAS-contaminated groundwater from a fire-training area (FTA) at Joint Base Cape Cod, Massachusetts. Dilution treatments enabled separation of concentration and mixture effects. Groundwater from well FTA1 was perfluorooctanesulfonate (PFOS) dominated (∑PFAS 10–31 μg L –1 ), whereas groundwater from well FTA2 had higher concentrations and was enriched in perfluorooctanoate (PFOA) and diverse precursors (∑PFAS ∼ 80 μg L –1 ). Despite comparable plasma ∑PFAS and PFOS in FTA1–100% and FTA2–50% on day-7, cumulative mortality reached approximately 35% in FTA2–50% and 17% in FTA2–100%, and secondary sex trait expression was reduced by approximately 65–80% relative to REF, whereas sperm motility effects were mixture- and time-dependent. Plasma PFAS profiles were dominated by perfluorohexanesulfonate (PFHxS), PFOS, and sulfonamide precursors. Liver transcriptomics from REF-acclimated fish revealed robust disruption of metabolic, mitochondrial, and endocrine pathways that link PFAS mixture chemistry and internal exposure profiles to organismal outcomes, and testis transcriptomics provided complementary insight into reproductive impairment. These results indicate that PFAS mixture composition and internal exposure profiles, including precursor-associated differences, are important determinants of ecotoxicological outcomes under field-realistic conditions.

Massachusetts

Simulation of the impacts of projected climate change on groundwater resources in the urban, semiarid Yucaipa Valley watershed, southern California using an integrated hydrologic model

Managing water resources in semiarid watersheds is challenging due to limited supply and uncertain future climate conditions. This paper examines the impact of future climate changes on an urban watershed in southern California using an integrated hydrologic model. GSFLOW modeling software is used to simulate the nonlinear relationships between climate trends and precipitation partitioning into ET, runoff, and subsurface storage. Four global circulation models (GCMs), each with two greenhouse-gas scenarios, RCP45 and RCP85 are used to project future climate conditions. GCMs include the CanESM2, CNRM-CM5, HadGEM2-ES, and MIROC5 models. The model's simulated hydrologic conditions are compared with historical data to assess changes in water budgets and groundwater supply. Results indicate decreased groundwater storage in most scenarios due to increased natural evapotranspiration, vegetation consumptive use, and streamflow out of the watershed. Only scenarios with substantially increased future precipitation show increased groundwater storage. The study also highlights increased future aridity despite the rise in precipitation and large precipitation events forecast by GCMs, which increase the risk of urban floods and decrease stream leakage and water available to vegetation.

California

Cultural benefits knowledge and social learning in Elwha River dam removal and ecosystem decision-making

In a retrospective case study of the seminal Elwha River dam removal in Washington State, USA, we explore pathways through which ecosystem services (ES) knowledge can inform environmental decision-making. We specifically investigate how knowledge of cultural benefits linked to the Elwha River ecosystem was made available. Through interviews and historical document review we identify diverse forms of cultural benefits knowledge (i.e., how individuals or groups know the contributions of an ecosystem to their identities, experiences, and capabilities), including both knowledge in the form of practices – embodied or enacted forms of knowledge, and knowledge in the form of products – quantitative or written documentation. Recognizing and learning from the diverse forms in which benefits knowledges are conveyed can support more accurate and equitable consideration of the diverse values, well-beings, and human-nature relationships linked to ecosystems. With this case study, we illuminate pathways for meaningful consideration of multiple knowledge forms, and the plural ecosystem values they convey, with relevance for environmental decision processes in the Puget Sound and beyond.

Washington

Prioritizing US Geological Survey science on salinization and salinity in candidate and selected priority river basins

The US Geological Survey (USGS) is selecting and prioritizing basins, known as Integrated Water Science basins, for monitoring and intensive study. Previous efforts to aid in this selection process include a scientifically defensible and quantitative assessment of basins facing human-caused water resource challenges (Van Metre et al. in Environmental Monitoring and Assessment , 192(7), 458 2020). In the present work, we explore this ranking process based on water quality considerations, specifically salinity and salinization. We selected top candidate basins to study salinity and salinization issues in 18 hydrologic regions that include 163 candidate basins. Our prioritization is based on quantitative assessment of sources of salinity, drivers of change, and receptors that must respond to those sources and drivers. Source terms represented in the prioritization include geology, depth to brackish groundwater, stream conductivity, chloride in precipitation, urban and agricultural land use, application of road salt as a deicer, and irrigation. Drivers represented in prioritization include changes in chemical weathering as a result of changes in rainwater chemistry. Receptors include measures of water stress, measurements of stream ecological health, and socioeconomic factors. In addition, we present research activities for the USGS on salinity and salinization that can be pursued in these basins including assessment of sources, pathways, and loadings; predicting and understanding changes in sources, peaks, and trends; understanding the components of salinity and mobilization of contaminants; understanding the relationship between salinization and changing ecosystems; and developing knowledge on the causes and distribution of groundwater salinity, brackish water resources, and challenges related to desalination.

Enviornmental Monitoring and Assessment

Future water constraints on United States lithium mining under climate change

Lithium is necessary for low-carbon technologies that combat climate change, but lithium extraction is water-intensive. Changes in temperature and precipitation arising from climate change are altering water distribution, which could further strain supplies for new mines and industry, farms, and households. Here we explored how climate change, water use, and mining siting could impact lithium mining in the United States. We analyzed whether there would be sufficient water available to support the single existing and 22 proposed U.S. lithium mines at mid-century under four socioeconomic-climate scenarios and five climate models. Though dependent on socioeconomic-climate scenario, climate model, and lithium deposit type, available water supply in most subbasins would likely be unable to support new mines’ water demands, or even non-mining water demands from other sectors. Water scarcity could hinder the ability of the United States to produce enough lithium to meet domestic demand thereby necessitating higher imports.

conterminous United States