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At least 343 records · Page 19Linked to original sources

Evaluation of the use of performance reference compounds in an oasis-HLB adsorbent based passive sampler for improving water concentration estimates of polar herbicides in freshwater

Passive samplers such as the Polar Organic Chemical Integrative Sampler (POCIS) are useful tools for monitoring trace levels of polar organic chemicals in aquatic environments. The use of performance reference compounds (PRC) spiked into the POCIS adsorbent for in situ calibration may improve the semiquantitative nature of water concentration estimates based on this type of sampler. In this work, deuterium labeled atrazine-desisopropyl (DIA-d5) was chosen as PRC because of its relatively high fugacity from Oasis HLB (the POCIS adsorbent used) and our earlier evidence of its isotropic exchange. In situ calibration of POCIS spiked with DIA-d5was performed, and the resulting time-weighted average concentration estimates were compared with similar values from an automatic sampler equipped with Oasis HLB cartridges. Before PRC correction, water concentration estimates based on POCIS data sampling ratesfrom a laboratory calibration exposure were systematically lower than the reference concentrations obtained with the automatic sampler. Use of the DIA-d5 PRC data to correct POCIS sampling rates narrowed differences between corresponding values derived from the two methods. Application of PRCs for in situ calibration seems promising for improving POCIS-derived concentration estimates of polar pesticides. However, careful attention must be paid to the minimization of matrix effects when the quantification is performed by HPLC-ESI-MS/MS. ?? 2010 American Chemical Society.

Environmental Science & Technology

Cyprosulfamide: Analysis of the herbicide safener and two of its degradates in surface water and groundwater from the Midwestern United States

Herbicide safeners are commonly included in herbicide formulations to selectively protect crops from herbicide toxicity but are poorly understood in terms of their environmental occurrence and fate. This study established an analytical method for a newer safener, cyprosulfamide, and two of its degradates, cyprosulfamide desmethyl and N -cyclopropyl-4-sulfamoylbenzamide, in water via solid-phase extraction and liquid chromatography with tandem mass spectroscopy. To evaluate the potential for off-field transport and transformation of cyprosulfamide, the method was used to analyze groundwater and surface water samples collected near cornfields in the midwestern United States where cyprosulfamide had been applied. All three compounds were detected in surface water samples ( N = 34); N -cyclopropyl-4-sulfamoylbenzamide was most frequently detected (56%), followed by cyprosulfamide (25%) and cyprosulfamide desmethyl (19%). Maximum concentrations ranged from 22.0 to 5185.9 ng/L, with the highest concentrations and detection rates during the growing season. None of our target analytes were detected in groundwater.

ACS Agricultural Science and Technology

Environmental DNA monitoring of invasive Central American boas in St. Croix at Salt River Bay National Historical Park and Ecological Preserve (SARI)

Invasive Central American boas ( Boa imperator ) have established a reproducing population on the western side of St. Croix, U.S. Virgin Islands but prevalence throughout the island is largely unknown. The large snakes threaten endemic and endangered species through competition and predation, jeopardizing island biodiversity. Environmental DNA (eDNA) methods were used to investigate occurrence and focal areas for management efforts in the Salt River Bay National Historical Park and Ecological Preserve (SARI). To validate a previously developed assay, we collected tissue samples and 13 × 60 mL water samples from a captive boa enclosure in St. Croix. We implemented this assay for both a pilot and main field sampling effort. The pilot in December 2023 resulted in analysis of 7 × 60 mL water samples per site from SARI (3 sites) and from the western forests where boas are established (1 site). The main sampling event in July 2024 collected 15 × 60 mL water samples per site within SARI (11 sites) and western forests (4 sites). Pilot sample replicates were filtered individually, while main samples were consolidated into groups, resulting in seven replicates for pilot sites and five replicates for main event sites, totaling 103 environmental samples. eDNA was isolated using a modified phenol-chloroform isolation method to remove PCR inhibitors, and target eDNA was amplified using droplet digital PCR technology. Water samples from the captive boa amplified target eDNA in 12 of 13 samples, indicating assay effectiveness ex-situ. Low concentrations of eDNA (below the 95% limit of detection) were amplified in 4 of 5 sites in the western forest and in 8 of 14 sites within the National Historic Park. Overall, boa eDNA concentrations were consistently low, as expected in water samples targeting a semi-arboreal snake species with a low rate of eDNA shedding. Further optimization of methods could enable recovery of greater eDNA concentrations in future studies. Additional eDNA method testing and ground-truthing may help to improve the assessment of invasive Boa imperator in St. Croix.

Science Report

Science needs for determining the effects of climate change on harmful algal blooms in the southeastern United States

The Southeastern United States has many lakes, streams, and reservoirs that serve as important drinking water sources with recreational, agricultural, and ecological uses. However, harmful algal blooms (HABs) are becoming more common in these waters, causing health issues for humans and animals. HABs have been listed as a contaminant of emerging concern, and the magnitude, frequency, and duration of HABs appear to be increasing at the global scale. While it is well known that nutrients stimulate algae growth, it is not clear how climate change and other parameters stimulate the development of toxin production by HABs. The scientific literature describes parameters, such as storm occurrence, temperature, dissolved metals, erosion of soils, increasing length of growing season, discharge, and hydroperiod, that may affect algae growth and toxin production. Climate and hydrologic models address many of the physical and environmental parameters that influence HABs, but no climate models directly address HABs. This report compiles information from the existing literature pertaining to HABs and the modeling and forecasting of HABS. This compilation is done through the incorporation of climate change models. HAB research that involves climate change will require multiple disciplines that bring together ecologists, hydrologists, climatologists, engineers, economists, and new technology. Resource managers could use geographic data about the occurrence and distribution of HABs to develop models that identify waterbodies more vulnerable to HAB events. Development of such models will require teams capable of integrating biological, chemical, and physical factors. Model development will require additional research that can resolve anthropogenic and climate-related environmental factors to identify trends in freshwater HABs. The complexity and interconnectedness of the parameters that influence HAB occurrences will make model development challenging and require rigorous regional calibration.

Open-File Report

The U.S. Geological Survey Ecosystem Science Strategy, 2012-2022 - Advancing discovery and application through collaboration

Ecosystem science is critical to making informed decisions about natural resources that can sustain our Nation’s economic and environmental well-being. Resource managers and policy-makers are faced with countless decisions each year at local, state, tribal, territorial, and national levels on issues as diverse as renewable and non-renewable energy development, agriculture, forestry, water supply, and resource allocations at the urban-rural interface. The urgency for sound decision-making is increasing dramatically as the world is being transformed at an unprecedented pace and in uncertain directions. Environmental changes are associated with natural hazards, greenhouse gas emissions, and increasing demands for water, land, food, energy, mineral, and living resources. At risk is the Nation’s environmental capital, the goods and services provided by resilient ecosystems that are vital to the health and well-being of human societies. Ecosystem science—the study of systems of organisms interacting with their environment and the consequences of natural and human-induced change on these systems—is necessary to inform decision-makers as they develop policies to adapt to these changes. This Ecosystems Science Strategy is built on a framework that includes basic and applied science. It highlights the critical roles that USGS scientists and partners can play in building scientific understanding and providing timely information to decision-makers. The strategy underscores the connection between scientific discoveries and the application of new knowledge. The strategy integrates ecosystem science and decision-making, producing new scientific outcomes to assist resource managers and providing public benefits. The USGS is uniquely positioned to play an important role in ecosystem science. With its wide range of expertise, the agency can bring holistic, cross-scale, interdisciplinary capabilities to the design and conduct of monitoring, research, and modeling and to new technologies for data collection, management, and visualization. Collectively, these capabilities can be used to reveal ecological patterns and processes, explain how and why ecosystems change, and forecast change over different spatial and temporal scales. USGS science can provide managers with options and decision-support tools to use resources sustainably. The USGS has long-standing, collaborative relationships with the DOI and other partners in the natural sciences, in both conducting science and its application. The USGS engages these partners in cooperative investigations that otherwise would lack the necessary support or be too expensive for a single bureau to conduct. The heart of this strategy is a framework and vision for USGS ecosystems science that focuses on five long-term goals, which are seen as interconnected and reinforcing components: • Improve understanding of ecosystem structure, function, and processes. The focus for this goal is an understanding of how ecosystems work, including the dynamics of species, their populations, interactions, and genetics, and how they change across spatial and temporal scales. • Advance understanding of how drivers influence ecosystem change. The challenges here are explaining the drivers of ecosystem change, their spatio-temporal patterns, their uncertainties and interactions, and their influence on ecosystem processes and dynamics. • Improve understanding of the services that ecosystems provide to society. Here the emphasis is on the measurement of environmental capital and ecosystem services, and the identification of sources and patterns of change in space and time. • Develop tools, technologies, and capacities to inform decision-making about ecosystems. This includes developing new technologies and approaches for conducting applications-oriented ecosystem science. A principal challenge will be how to quantify uncertainty and incorporate it in decision analysis. • Apply science to enhance strategies for management, conservation, and restoration of ecosystems. These challenges include development of novel approaches to monitoring, assessment, and restoration of ecosystems; new methods to address species of concern and communities at risk; and innovations in decision analysis and support to address imminent ecosystem changes or those that are underway. Closely integrated with the five goals are four strategic approaches that provide the path forward for the USGS Ecosystems Mission Area. These approaches cross-cut all of the goals and are seen as essential to the implementation of this strategy: • Assess information needs for ecosystem science through enhanced partnerships. Work with the DOI and other agencies and institutions to identify, design, and implement priority decision-driven ecological research. • Promote the use of interdisciplinary ecosystem science. Design and conduct interdisciplinary process-oriented research in ecosystem science. • Enhance modeling and forecasting. Build models to forecast ecosystem change, assess future management scenarios, and reduce uncertainties through an adaptive learning process. • Support decision-making. Use quantitative approaches to assess the vulnerabilities of ecosystems, habitats, and species, and evaluate strategies for adaptation, restoration, and sustainable management. Following the strategic approaches are a set of proposed actions that represent a sampling of specific activities that align with this strategy and that address the Nation’s most pressing environmental needs. The strategy emphasizes coordination of activities across the USGS mission areas pursuant to these goals. Ecosystem science is inherently interdisciplinary and requires a broad perspective that incorporates the biological and physical sciences, climate science, information technology, and scientific capacity in mission areas across the Bureau. With its emphasis on coordination, this strategy can provide a critical underpinning for integrated science efforts with scientists from multiple mission areas of the USGS working together. Of course, the USGS will continue to conduct both discipline-specific and interdisciplinary investigations, and both will continue to be vital parts of the ecosystem science portfolio. Finally, the strategy stresses the importance of coordination with other Federal agencies and organizations in the natural resources community. The USGS collaborates with resource agencies in the DOI and other organizations throughout the world to meet societal needs for species and ecosystem management. Working with these agencies and organizations, the USGS will play a key role over the next decade in advancing the scientific foundation for sustaining the natural resources that diverse, productive, resilient ecosystems provide.

Open-File Report

Widespread use of the nitrification inhibitor nitrapyrin: Assessing benefits and costs to agriculture, ecosystems, and environmental health

Agricultural production and associated applications of nitrogen (N) fertilizers have increased dramatically in the last century, and current projections to 2050 show that demands will continue to increase as the human population grows. Applied in both organic and inorganic fertilizer forms, N is an essential nutrient in crop productivity. Increased fertilizer applications, however, create the potential for more N loss before plant uptake. One strategy for minimizing N loss is the use of enhanced efficiency fertilizers, fortified with a nitrification inhibitor, such as nitrapyrin. In soils and water, nitrapyrin inhibits the activity of ammonia monooxygenase, a microbial enzyme that catalyzes the first step of nitrification from ammonium to nitrite. Potential benefits of using nitrification inhibitors range from reduced nitrate leaching and nitrous oxide emissions to increased crop yield. The extent of these benefits, however, depends on environmental conditions and management practices. Thus, such benefits are not always realized. Additionally, nitrapyrin has been shown to transport off-field, and it is unknown what effects environmental nitrapyrin could have on nontarget organisms and the ecological nitrogen cycle. Here, we review the agronomic and environmental benefits and costs of nitrapyrin use and present a series of research questions and considerations to be addressed with future nitrification inhibitor research.

Environmental Science and Technology

Degradation of crude 4-MCHM (4-methylcyclohexanemethanol) in sediments from Elk River, West Virginia

In January 2014, approximately 37 800 L of crude 4-methylcyclohexanemethanol (crude MCHM) spilled into the Elk River, West Virginia. To understand the long-term fate of 4-MCHM, we conducted experiments under environmentally relevant conditions to assess the potential for the 2 primary compounds in crude MCHM (1) to undergo biodegradation and (2) for sediments to serve as a long-term source of 4-MCHM. We developed a solid phase microextraction (SPME) method to quantify the cis - and trans -isomers of 4-MCHM. Autoclaved Elk River sediment slurries sorbed 17.5% of cis -4-MCHM and 31% of trans -4-MCHM from water during the 2-week experiment. Sterilized, impacted, spill-site sediment released minor amounts of cis - and up to 35 μg/L of trans -4-MCHM into water, indicating 4-MCHM was present in sediment collected 10 months post spill. In anoxic microcosms, 300 μg/L cis - and 150 μg/L trans -4-MCHM degraded to nondetectable levels in 8–13 days in both impacted and background sediments. Under aerobic conditions, 4-MCHM isomers degraded to nondetectable levels within 4 days. Microbial communities at impacted sites differed in composition compared to background samples, but communities from both sites shifted in response to crude MCHM amendments. Our results indicate that 4-MCHM is readily biodegradable under environmentally relevant conditions.

West Virginia

Molecular weight, polydispersity, and spectroscopic properties of aquatic humic substances

The number- and weight-averaged molecular weights of a number of aquatic fulvic acids, a commercial humic acid, and unfractionated organic matter from four natural water samples were measured by high-pressure size exclusion chromatography (HPSEC). Molecular weights determined in this manner compared favorably with those values reported in the literature. Both recent literature values and our data indicate that these substances are smaller and less polydisperse than previously believed. Moreover, the molecular weights of the organic matter from three of the four natural water samples compared favorably to the fulvic acid samples extracted from similar environments. Bulk spectroscopic properties of the fulvic substances such as molar absorptivity at 280 nm and the E4/E6 ratio were also measured. A strong correlation was observed between molar absorptivity, total aromaticity, and the weight average molecular weights of all the humic substances. This observation suggests that bulk spectroscopic properties can be used to quickly estimate the size of humic substances and their aromatic contents. Both parameters are important with respect to understanding humic substance mobility and their propensity to react with both organic and inorganic pollutants.

Environmental Science & Technology

Differences in dissolved cadmium and zinc uptake among stream insects: Mechanistic explanations

This study examined the extent to which dissolved Cd and Zn uptake rates vary in several aquatic insect taxa commonly used as indicators of ecological health. We further attempted to explain the mechanisms underlying observed differences. By comparing dissolved Cd and Zn uptake rates in several aquatic insect species, we demonstrated that species vary widely in these processes. Dissolved uptake rates were not related to gross morphological features such as body size or gill size-features that influence water permeability and therefore have ionoregulatory importance. However, finer morphological features, specifically, the relative numbers of ionoregulatory cells (chloride cells), appeared to be related to dissolved metal uptake rates. This observation was supported by Michaelis-Menten type kinetics experiments, which showed that dissolved Cd uptake rates were driven by the numbers of Cd transporters and not by the affinities of those transporters to Cd. Calcium concentrations in exposure media similarly affected Cd and Zn uptake rates in the caddisfly Hydropsyche californica. Dissolved Cd and Zn uptake rates strongly co-varied among species, suggesting that these metals are transported by similar mechanisms.

Environmental Science & Technology

Environmental policy analysis, peer reviewed: Reservoir sediment cores show US lead declines

As a result of the Clean Air Act, lead (Pb) emissions to the atmosphere have been greatly reduced since the mid-1970s. As part of its National Water Quality Assessment, the U.S. Geological Survey has been using paleolimnological techniques to assess past trends in hydrophobic contaminants. In urban-suburban environments, reservoir sediment cores show prominent peaks in Pb distributions that correlate well with the rise and fall of leaded gasoline. However, Pb concentrations in sediments are approximately double those of baseline values prior to the 1950s and 1960s. It is apparent that significant concentrations of anthropogenic Pb still exist in soils and aquatic sediments and that it will take many years to reduce these concentrations to prepollution values, even if there are no new sources of Pb pollution.

Environmental Science & Technology

Enhanced dissolution of cinnabar (mercuric sulfide) by dissolved organic matter isolated from the Florida Everglades

Organic matter isolated from the Florida Everglades caused a dramatic increase in mercury release (up to 35 μM total dissolved mercury) from cinnabar (HgS), a solid with limited solubility. Hydrophobic (a mixture of both humic and fulvic) acids dissolved more mercury than hydrophilic acids and other nonacid fractions of dissolved organic matter (DOM). Cinnabar dissolution by isolated organic matter and natural water samples was inhibited by cations such as Ca 2+ . Dissolution was independent of oxygen content in experimental solutions. Dissolution experiments conducted in DI water (pH = 6.0) had no detectable (<2.5 nM) dissolved mercury. The presence of various inorganic (chloride, sulfate, or sulfide) and organic ligands (salicylic acid, acetic acid, EDTA, or cysteine) did not enhance the dissolution of mercury from the mineral. Aromatic carbon content in the isolates (determined by 13 C NMR) correlated positively with enhanced cinnabar dissolution. ζ-potential measurements indicated sorption of negatively charged organic matter to the negatively charged cinnabar (pH pzc = 4.0) at pH 6.0. Possible mechanisms of dissolution include surface complexation of mercury and oxidation of surface sulfur species by the organic matter.

Florida

The U.S. Geological Survey Land Remote Sensing Program

In 2002, the U. S. Geological Survey (USGS) launched a program to enhance the acquisition, preservation, and use of remotely sensed data for USGS science programs, as well as for those of cooperators and customers. Remotely sensed data are fundamental tools for studying the Earth's land surface, including coastal and near-shore environments. For many decades, the USGS has been a leader in providing remotely sensed data to the national and international communities. Acting on its historical topographic mapping mission, the USGS has archived and distributed aerial photographs of the United States for more than half a century. Since 1972, the USGS has acquired, processed, archived, and distributed Landsat and other satellite and airborne remotely sensed data products to users worldwide. Today, the USGS operates and manages the Landsats 5 and 7 missions and cooperates with the National Aeronautics and Space Administration (NASA) to define and implement future satellite missions that will continue and expand the collection of moderate-resolution remotely sensed data. In addition to being a provider of remotely sensed data, the USGS is a user of these data and related remote sensing technology. These data are used in natural resource evaluations for energy and minerals, coastal environmental surveys, assessments of natural hazards (earthquakes, volcanoes, and landslides), biological surveys and investigations, water resources status and trends analyses and studies, and geographic and cartographic applications, such as wildfire detection and tracking and as a source of information for The National Map. The program furthers these distinct but related roles by leading the USGS activities in providing remotely sensed data while advancing applications of such data for USGS programs and a wider user community.

Fact Sheet

Tracing the cycling and fate of the explosive 2,4,6-trinitrotoluene in coastal marine systems with a stable isotopic tracer, 15N-[TNT]

2,4,6-Trinitrotoluene (TNT) has been used as a military explosive for over a hundred years. Contamination concerns have arisen as a result of manufacturing and use on a large scale; however, despite decades of work addressing TNT contamination in the environment, its fate in marine ecosystems is not fully resolved. Here we examine the cycling and fate of TNT in the coastal marine systems by spiking a marine mesocosm containing seawater, sediments, and macrobiota with isotopically labeled TNT ( 15 N-[TNT]), simultaneously monitoring removal, transformation, mineralization, sorption, and biological uptake over a period of 16 days. TNT degradation was rapid, and we observed accumulation of reduced transformation products dissolved in the water column and in pore waters, sorbed to sediments and suspended particulate matter (SPM), and in the tissues of macrobiota. Bulk δ 15 N analysis of sediments, SPM, and tissues revealed large quantities of 15 N beyond that accounted for in identifiable derivatives. TNT-derived N was also found in the dissolved inorganic N (DIN) pool. Using multivariate statistical analysis and a 15 N mass balance approach, we identify the major transformation pathways of TNT, including the deamination of reduced TNT derivatives, potentially promoted by sorption to SPM and oxic surface sediments.

Environmental Science & Technology

Direct photolysis rates and transformation pathways of the lampricides TFM and niclosamide in simulated sunlight

The lampricides 3-trifluoromethyl-4-nitrophenol (TFM) and 2′,5-dichloro-4′-nitrosalicylanilide (niclosamide) are directly added to many tributaries of the Great Lakes that harbor the invasive parasitic sea lamprey. Despite their long history of use, the fate of lampricides is not well understood. This study evaluates the rate and pathway of direct photodegradation of both lampricides under simulated sunlight. The estimated half-lives of TFM range from 16.6 ± 0.2 h (pH 9) to 32.9 ± 1.0 h (pH 6), while the half-lives of niclosamide range from 8.88 ± 0.52 days (pH 6) to 382 ± 83 days (pH 9) assuming continuous irradiation over a water depth of 55 cm. Both compounds degrade to form a series of aromatic intermediates, simple organic acids, ring cleavage products, and inorganic ions. Experimental data were used to construct a kinetic model which demonstrates that the aromatic products of TFM undergo rapid photolysis and emphasizes that niclosamide degradation is the rate-limiting step to dehalogenation and mineralization of the lampricide. This study demonstrates that TFM photodegradation is likely to occur on the time scale of lampricide applications (2–5 days), while niclosamide, the less selective lampricide, will undergo minimal direct photodegradation during its passage to the Great Lakes.

Environmental Science & Technology

Hydrocarbons in upland groundwater, Marcellus Shale Region, Northeastern Pennsylvania and Southern New York, USA

Water samples from 50 domestic wells located <1 km (proximal) and >1 km (distal) from shale-gas wells in upland areas of the Marcellus Shale region were analyzed for chemical, isotopic, and groundwater-age tracers. Uplands were targeted because natural mixing with brine and hydrocarbons from deep formations is less common in those areas compared to valleys. CH 4 -isotope, predrill CH 4 -concentration, and other data indicate that one proximal sample (5% of proximal samples) contains thermogenic CH 4 (2.6 mg/L) from a relatively shallow source (Catskill/Lock Haven Formations) that appears to have been mobilized by shale-gas production activities. Another proximal sample contains five other volatile hydrocarbons (0.03–0.4 μg/L), including benzene, more hydrocarbons than in any other sample. Modeled groundwater-age distributions, calibrated to 3 H, SF 6 , and 14 C concentrations, indicate that water in that sample recharged prior to shale-gas development, suggesting that land-surface releases associated with shale-gas production were not the source of those hydrocarbons, although subsurface leakage from a nearby gas well directly into the groundwater cannot be ruled out. Age distributions in the samples span ∼20 to >10000 years and have implications for relating occurrences of hydrocarbons in groundwater to land-surface releases associated with recent shale-gas production and for the time required to flush contaminants from the system.

New York, Pennsylvania

Rapid arsenite oxidation by Thermus aquaticus and Thermus thermophilus: Field and laboratory investigations

Thermus aquaticus and Thermus thermophilus, common inhabitants of terrestrial hot springs and thermally polluted domestic and industrial waters, have been found to rapidly oxidize arsenite to arsenate. Field investigations at a hot spring in Yellowstone National Park revealed conserved total arsenic transport and rapid arsenite oxidation occurring within the drainage channel. This environment was heavily colonized by Thermus aquaticus. In laboratory experiments, arsenite oxidation by cultures of Thermus aquaticus YT1 (previously isolated from Yellowstone National Park) and Thermus thermophilus HB8 was accelerated by a factor of over 100 relative to abiotic controls. Thermus aquaticus and Thermus thermophilus may therefore play a large and previously unrecognized role in determining arsenic speciation and bioavailability in thermal environments.

Environmental Science & Technology

Bioaccumulation and transfer of per- and polyfluoroalkyl substances (PFAS) in a stream and riparian food web contaminated by food processing wastewater

We evaluated the bioaccumulation and transfer of per- and polyfluoroalkyl substances (PFAS) in a stream food web contaminated by a food processing facility. Abiotic (i.e., water, sediment, and foam) and biotic (i.e., algae, aquatic insect larvae and adults, fish, and riparian spiders) matrices were sampled upstream and downstream of the facility’s wastewater outfall. Compared with upstream, PFAS concentrations were 600-fold higher in downstream water (mean ∑ 40 PFAS 3.67 ng mL –1 ± 0.48 (standard error)) and reflected inputs from the outfall, with 6:2 fluorotelomer sulfonate (6:2 FTS) dominating the PFAS profile. Within the aquatic food web, perfluorooctanesulfonate (PFOS) was the most biomagnified, and 6:2 FTS was the most biodiluted. In contrast, insect-mediated transfer of PFAS to riparian spiders showed trophic enrichment of 6:2 FTS and dilution of PFOS. We observed significant positive associations between phospholipid membrane-water partition coefficient (log K MW ) and perfluoroalkyl carboxylate (PFCA) chain length on bioaccumulation across most biological matrices, demonstrating that these chemical parameters are predictive of PFAS bioaccumulation potential in the field. Our research reveals important differences in aquatic versus terrestrial exposure for certain PFAS and that biological processes (e.g., trophic interactions and metamorphosis) and chemical properties (e.g., chain length, log K MW , and concentration) control PFAS uptake, bioaccumulation, and transfer in linked freshwater and terrestrial ecosystems.

Environmental Science & Technology

Modeling precipitation and sorption of elements during mixing of river water and porewater in the Coeur d'Alene River basin

Reddish brown flocs form along the edge of the Coeur d'Alene River when porewater drains into river water during the annual lowering of water level in the basin. The precipitates are efficient scavengers of dissolved elements and have characteristics that may make metals associated with them bioavailable. This work characterizes the geochemistry of the porewater and models the formation and composition of the flocs. Porewater is slightly acidic, has suboxic to anoxic characteristics, tends to have higher alkalinity, and contains elevated concentrations of many constituents relative to river water. Laboratory mixing experiments involving porewater and river water were done to produce the precipitates. Thermodynamic predictions using PHREEQC indicate that predicted amounts of ferrihydrite and gibbsite agree with removal of Fe and Al. Predictions of element removal by adsorption onto ferrihydrite are consistent with observed removal using a combination of surface complexation constants for the generalized two-layer model (As and Se), alternative surface constants derived from experiments at high sorbate-to-sorbent ratios (Cd, Co, Cu, Ni, Pb, and Zn), and adjusted surface constants to fit experimental data (Cr, Mo, and Sb). This new set of surface complexation constants needs further testing in other contaminated systems.

Idaho