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Andrea K. Tokranov

Publications and source records attributed to Andrea K. Tokranov.

13 recordsLinked to original sources

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↗

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↗

Insights and strategic opportunities from the USGS 2024 Per- and Polyfluoroalkyl Substances (PFAS) Interagency Workshop

Introduction In 2021, the U.S. Geological Survey (USGS) published Circular 1490 titled, “Integrated Science for the Study of Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) in the Environment: A Strategic Science Vision for the U.S. Geological Survey” (Tokranov and others, 2021). Circular 1490 was created to be a resource for USGS scientists prioritizing and planning research related to per- and polyfluoroalkyl substances (PFAS) and to be a guide for developing partnerships with other scientists, State and Federal agencies, and stakeholders engaged in PFAS research and management and mitigation of the environmental and human-health effects of PFAS. This USGS PFAS Strategic Science Vision document was intended to be the foundation for a “living strategic vision,” periodically providing updates on the state of USGS PFAS research, emerging PFAS data gaps and needs, and progress on interagency and stakeholder PFAS partnerships and priorities. To meet this objective, the USGS planned to host an Interagency and Stakeholder PFAS Workshop every 2–3 years. During September 10–12, 2024, the USGS hosted the first Interagency and Stakeholder PFAS Workshop in Reston, Virginia. The Workshop brought together experts from other Federal agencies (U.S. Environmental Protection Agency, National Institute of Environmental Health Sciences, Food and Drug Administration, Department of Defense [Air Force, Army]), State agencies (Washington Fish and Wildlife, Virginia Department of Transportation), and academia (Harvard University, University of Maryland) to address key challenges relating to the measurement and modeling of PFAS and the implications for environmental health. Participants engaged in in-depth discussions centered around six pivotal topics related to PFAS: (1) sampling protocols, methods and interpretation; (2) environmental sources, source apportionment, and occurrence; (3) environmental fate and transport; (4) human and wildlife exposure routes and risk; (5) bioconcentration, bioaccumulation, and biomagnification; and (6) ecotoxicology and effects. Each topic had three breakout sessions. A recurrent theme of workshop discussions was how data on a nationwide scale for PFAS occurrence in various environmental matrices, including air, water, food crops, biota, soil, and streambed sediment could help to advance scientific understanding. Participants noted significant geospatial data gaps, particularly in the midwestern and southern United States and the Pacific Northwest. PFAS data collection tends to be more robust along the eastern seaboard and in California. Participants stressed how enhancing the integration of large and small datasets across various agencies could help to support national scale understanding of PFAS. To address these gaps, attendees suggested leveraging datasets from Federal entities like the USGS and the U.S. Department of Defense, State agencies, and municipal utility services to develop predictive contaminant detection and transport models. Improved coordination between water quality programs and USGS research could help to facilitate access to valuable data, leading to comprehensive databases that inform PFAS point (wastewater treatment plants and landfills) and nonpoint (runoff from land, atmospheric deposition, food packaging) sources, environmental transport mechanisms, environmental detection and concentrations, potential exposure routes, and health effects on different biota, including humans. A specific request was made to develop a map demarking the depth of modern (1953 or later) groundwater, which is susceptible to surface-derived anthropogenic (that is, human-made) contamination, based on tritium-age dating. Emphasis was placed on incorporation of hydrology, groundwater flow paths, groundwater–surface water interactions, and landscape factors in predictive statistical models as a step to improve contaminant source identification and tracking. Molecular fingerprinting approaches garnered attention as techniques to link specific PFAS mixtures detected in a sample to environmental sources and levels in biota (Dávila-Santiago and others, 2022). Integrating data from abiotic (that is, water, soil, and air) and biotic (that is, living organisms) systems identified as a research opportunity. For example, understanding the composition of soils and sediments, which include a mixture of mineral, plant, and animal components, could advance understanding of exposure pathways. The discussions highlighted opportunities to explore and understand the potential redistribution and biotic exposures of PFAS from biosolid and wastewater treatment plant effluent land application practices, in addition to atmospheric releases and discharges from landfill and wastewater treatment plants. Participants identified research gaps surrounding how these sources may contribute to contamination and may affect surrounding ecosystems, including a better definition of anthropogenic background concentrations. Moving forward, the collection of co-occurrence data was noted as a means to improve understanding of complex mixtures and to leverage companion modeling efforts focused on areas with high and low contamination levels to identify areas of concern and unaffected resources. Participants emphasized how centralized USGS databases and the establishment of sample-metadata archives can help to ensure that samples are preserved and accessible for future research. In conclusion, the workshop participants identified opportunities to bridge data gaps and improve measurement techniques, modeling frameworks, databases, and communication, to enhance the understanding of PFAS and their effects on environmental and human health. Upon completion of the workshop, participants indicated an interest in developing strategic data collection, modeling, and analytical approaches to address these challenges.

Open-File Report↗

Groundwater flowpath characteristics drive variability in per- and polyfluoroalkyl substances (PFAS) loading across a stream-wetland system

Groundwater-dependent ecosystems in areas with industrial land use are at risk of exposure to a PFAS chemicals. We investigated one such system with several known PFAS source areas, where high and low permeability sediments (glacial) coupled with groundwater-lake and groundwater/surface-water interactions created complex ‘source to seep’ dynamics. Using heat-tracing and chemical methods, numerous preferential groundwater discharge zones were identified and sampled across the upper Quashnet River stream-wetland system in Mashpee, MA, USA, downgradient of Joint Base Cape Cod (JBCC). Surface-water and groundwater samples were analyzed for 40 PFAS compounds between March and October 2022. Samples were collected from groundwater seeps identified as preferential discharge points (PDPs), wells upgradient of the stream-wetland system, contributing flow-through kettle lakes, and along Quashnet River surface-waters. PFAS from sampled waters contained perfluorinated carboxylates (PFPea, PFHxA, PFNA), perfluorinated sulfonates (PFBS, PFPeS, PFHxS, PFOS), fluorotelomer sulfonates (6:2, 8:2 FtS), and perfluoroalkyl sulfonamides (PFOSA). Samples from PDPs and wells had measured PFAS concentrations ranging from non-detect to 4677 ng/L ng/L (mean = 418 ng/L, std. = 709 ng/L), and a range of deuterium excess values (3.2 to 15.9 per mil) indicative of varying degrees of groundwater-lake interaction prior to groundwater flowpath emergence at PDPs. Correlations ( p < 0.01) between deuterium excess, %PFAS precursors, and terminal PFAS compounds highlighted potential precursor transformations associated with lake-groundwater exchange along flowpaths sourcing PDPs. However, some seepages had higher total PFAS concentrations (>1000 ng/L) than upgradient kettle lakes despite showing lake (evaporative) isotopic signatures, indicating the potential for groundwater flowpath convergence at wetland discharge zones and the influence of lakebed PFAS precursor reactions. Results from these synoptic surveys address gaps in the existing PFAS literature by demonstrating the importance of subsurface fate and transport on PFAS compound concentrations and mass loading in preferential groundwater discharge zones.

Massachusetts↗

Anaerobic biodegradation of perfluorooctane sulfonate (PFOS) and microbial community composition in soil amended with a dechlorinating culture and chlorinated solvents

Perfluorooctane sulfonate (PFOS), one of the most frequently detected per - and polyfluoroalkyl substances (PFAS) occurring in soil, surface water, and groundwater near sites contaminated with aqueous film-forming foam (AFFF), has proven to be recalcitrant to many destructive remedies, including chemical oxidation. We investigated the potential to utilize microbially mediated reduction (bioreduction) to degrade PFOS and other PFAS through addition of a known dehalogenating culture, WBC-2, to soil obtained from an AFFF-contaminated site. A substantial decrease in total mass of PFOS (soil and water) was observed in microcosms amended with WBC-2 and chlorinated volatile organic compound (cVOC) co-contaminants — 46.4 ± 11.0 % removal of PFOS over the 45-day experiment. In contrast, perfluorooctanoate (PFOA) and 6:2 fluorotelomer sulfonate (6:2 FTS) concentrations did not decrease in the same microcosms. The low or non-detectable concentrations of potential metabolites in full PFAS analyses, including after application of the total oxidizable precursor assay, indicated that defluorination occurred to non-fluorinated compounds or ultrashort-chain PFAS. Nevertheless, additional research on the metabolites and degradation pathways is needed. Population abundances of known dehalorespirers did not change with PFOS removal during the experiment, making their association with PFOS removal unclear. An increased abundance of sulfate reducers in the genus Desulfosporosinus (Firmicutes) and Sulfurospirillum (Campilobacterota) was observed with PFOS removal, most likely linked to initiation of biodegradation by desulfonation. These results have important implications for development of in situ bioremediation methods for PFAS and advancing knowledge of natural attenuation processes.

Science of the Total Environment↗

Predictions of groundwater PFAS occurrence at drinking water supply depths in the United States

Per- and polyfluoroalkyl substances (PFAS), known colloquially as “forever chemicals”, have been associated with adverse human health effects and have contaminated drinking water supplies across the United States owing to their long-term and widespread use. People in the United States may unknowingly be drinking water that contains PFAS because of a lack of systematic analysis, particularly in domestic water supplies. We present an extreme gradient boosting model for predicting the occurrence of PFAS in groundwater at the depths of drinking water supply for the conterminous United States. Our model results indicate that 71 to 95 million people in the conterminous United States potentially rely on groundwater with detectable concentrations of PFAS for their drinking-water supplies prior to any treatment.

conterminous United States↗

Centurial persistence of forever chemicals at military fire training sites

Drinking water contamination by per- and polyfluoroalkyl substances (PFAS) is widespread near more than 300 United States (U.S.) military bases that used aqueous film-forming foams (AFFF) for fire training and firefighting activities. Much of the PFAS at these sites consist of precursors that can transform into terminal compounds of known health concern but are omitted from standard analytical methods. Here, we estimate the expected duration and contribution of precursor biotransformation to groundwater PFAS contamination at an AFFF-contaminated military base on Cape Cod, Massachusetts, United States, by optimizing a geochemical box model using measured PFAS concentrations from a multidecadal time series of groundwater and a soil survey in the source zone. A toolbox of analytical techniques used to reconstruct the mass budget of PFAS showed that precursors accounted for 46 ± 8% of the extractable organofluorine (a proxy for total PFAS) across years. Terminal PFAS still exceed regulatory limits by 2000-fold decades after AFFF use ceased. Measurements and numerical modeling show that sulfonamido precursors are retained in the vadose zone and their slow biotransformation into perfluoroalkyl sulfonates (half-life > 66 yr) sustains groundwater concentrations of perfluorobutane sulfonate (PFBS) and perfluorohexane sulfonate (PFHxS). The estimated PFAS reservoir in the vadose zone and modeled flux into groundwater suggest PFAS contamination above regulatory guidelines will persist for centuries without remediation.

Massachusetts↗

Perfluoroalkyl and polyfluoroalkyl substances in groundwater used as a source of drinking water in the eastern United States

In 2019, 254 samples were collected from five aquifer systems to evaluate per- and polyfluoroalkyl substance (PFAS) occurrence in groundwater used as a source of drinking water in the eastern United States. The samples were analyzed for 24 PFAS, major ions, nutrients, trace elements, dissolved organic carbon (DOC), volatile organic compounds (VOCs), pharmaceuticals, and tritium. Fourteen of the 24 PFAS were detected in groundwater, with 60% and 20% of public-supply and domestic wells, respectively, containing at least one PFAS detection. Concentrations of tritium, chloride, sulfate, DOC, and manganese+iron; percent urban land use within 500 m of the wells; and VOC and pharmaceutical detection frequencies were significantly higher in samples containing PFAS detections than in samples with no detections. Boosted Regression Tree models that consider 57 chemical and land-use variables show that tritium concentration, distance to the nearest fire-training area, percentage of urban land use, and DOC and VOC concentrations are the top five predictors of PFAS detections, consistent with hydrologic position, geochemistry, and land use being important controls on PFAS occurrence in groundwater. Model results indicate it may be possible to predict PFAS detections in groundwater using existing data sources.

Glacial aquifer, Mississippi Embayment aquifer, So↗

Integrated science for the study of perfluoroalkyl and polyfluoroalkyl substances (PFAS) in the environment—A strategic science vision for the U.S. Geological Survey

Concerns related to perfluoroalkyl and polyfluoroalkyl substances (PFAS) in sources of drinking water and in natural and engineered environments have captured national attention over the last few decades. This report provides an overview of the science gaps that exist in the fields of study related to PFAS that are relevant to the U.S. Geological Survey mission and identifies opportunities where the U.S. Geological Survey can help address these gaps on the basis of the agency’s capabilities and expertise. The integrated science activities envisioned in this document can be designed to address science needs at local, regional, and national scales and varying timeframes as stakeholders are engaged and their needs evolve. This document is intended as an information resource for U.S. Geological Survey scientists who are prioritizing and planning research related to PFAS and may be useful for developing partnerships and collaborations with other scientists, agencies, and stakeholders.

Circular↗

Per- and polyfluoroalkyl substances (PFAS) in New Hampshire soils and biosolids

The U.S. Geological Survey, in cooperation with the New Hampshire Department of Environmental Services, is undertaking a study on per- and polyfluoroalkyl substances (PFAS) in soils and biosolids. The study will characterize PFAS concentrations in shallow soil and selected biosolids throughout the State of New Hampshire, conduct laboratory experiments to improve understanding of how mobile PFAS are in the environment, and implement a site-specific field study of PFAS transport from soil to water.

New Hampshire↗

Isolating the AFFF signature in coastal watersheds using oxidizable PFAS precursors and unexplained organofluorine

Water supplies for millions of U.S. individuals exceed maximum contaminant levels for per- and polyfluoroalkyl substances (PFAS). Contemporary and legacy use of aqueous film forming foams (AFFF) is a major contamination source. However, diverse PFAS sources are present within watersheds, making it difficult to isolate their predominant origins. Here we examine PFAS source signatures among six adjacent coastal watersheds on Cape Cod, MA, U.S.A. using multivariate clustering techniques. A distinct signature of AFFF contamination enriched in precursors with six perfluorinated carbons (C6) was identified in watersheds with an AFFF source, while others were enriched in C4 precursors. Principal component analysis of PFAS composition in impacted watersheds showed a decline in precursor composition relative to AFFF stocks and a corresponding increase in terminal perfluoroalkyl sulfonates with < C6 but not those with ≥ C6. Prior work shows that in AFFF stocks, all extractable organofluorine (EOF) can be explained by targeted PFAS and precursors inferred using Bayesian inference on the total oxidizable precursor assay. Using the same techniques for the first time in impacted watersheds, we find that only 24%–63% of the EOF can be explained by targeted PFAS and oxidizable precursors. Our work thus indicates the presence of large non-AFFF organofluorine sources in these coastal watersheds.

Massachusetts↗

Surface-water/groundwater boundaries affect seasonal PFAS concentrations and PFAA precursor transformations​

Elevated concentrations of per- and polyfluoroalkyl substances (PFAS) in drinking-water supplies are a major concern for human health. It is therefore essential to understand factors that affect PFAS concentrations in surface water and groundwater and the transformation of perfluoroalkyl acid (PFAA) precursors that degrade into terminal compounds. Surface-water/groundwater exchange can occur along the flow path downgradient from PFAS point sources and biogeochemical conditions can change rapidly at these exchange boundaries. Here, we investigate the influence of surface-water/groundwater boundaries on PFAS transport and transformation. To do this, we conducted an extensive field-based analysis of PFAS concentrations in water and sediment from a flow-through lake fed by contaminated groundwater and its downgradient surface-water/groundwater boundary (defined as ≤100 cm below the lake bottom). PFAA precursors comprised 45 ± 4.6% of PFAS (PFAA precursors + 18 targeted PFAA) in the predominantly oxic lake impacted by a former fire-training area and historical wastewater discharges. In shallow porewater downgradient from the lake, this percentage decreased significantly to 25 ± 11%. PFAA precursor concentrations decreased by 85% between the lake and 84–100 cm below the lake bottom. PFAA concentrations increased significantly within the surface-water/groundwater boundary and in downgradient groundwater during the winter months despite lower stable concentrations in the lake water source. These results suggest that natural biogeochemical fluctuations associated with surface-water/groundwater boundaries may lead to PFAA precursor loss and seasonal variations in PFAA concentrations. Results of this work highlight the importance of dynamic biogeochemical conditions along the hydrological flow path from PFAS point sources to potentially affected drinking water supplies.

Massachusetts↗

Hillslope groundwater discharges provide localized ecosystem buffers from regional PFAS contamination in a gaining coastal stream

Emerging groundwater contaminants such as per- and polyfluoroalkyl substances (PFAS) may impact surface-water quality and groundwater-dependent ecosystems of gaining streams. Although complex near-surface hydrogeology of stream corridors challenges sampling efforts, recent advances in heat tracing of discharge zones enable efficient and informed data collection. For this study we used a combination of streambed temperature push-probe and thermal infrared methods to guide a discharge-zone-oriented sample collection along approximately 6 km of a coastal trout stream on Cape Cod, MA where groundwater discharge constitutes approximately 95% of total streamflow. Eight surface-water locations and discharging groundwater from 24 streambed and bank seepages were analyzed for dissolved oxygen, specific conductance, stable water isotopes, and a range of PFAS compounds which are contaminants of emerging concern in aquatic environments. The results indicate a complex system of groundwater discharge source flowpaths, where the sum of concentrations of six PFAS compounds (Environmental Protection Agency third Unregulated Contaminant Monitoring Rule UCMR 3) showed a median concentration of 52 331 (SD) ng/L with two higher outliers and three discharges with non-detection of PFAS. Higher UCMR 3 PFAS concentration was related -0.66 (Spearman Rank, p<0.001) to discharging groundwater that showed an evaporative signature (deuterium excess), indicating flow through at least one upgradient kettle lake. Therefore, more regional groundwater flowpaths originating from outside the local river corridor tended to show higher PFAS concentrations as evaluated at their respective discharge zones. Conversely, UCMR 3 PFAS concentrations were typically low at discharges that did not indicate evaporation and were adjacent to steep hillslopes and, therefore, were classified as locally recharged groundwater. Previous research at this stream found that the native brook trout favor discharge points of groundwater recharged on local hillslopes for spawning, likely in response to generally higher levels of dissolved oxygen compared to discharge zones located further away from hillslopes. Our study shows that the trout may thereby be avoiding emerging contaminants such as PFAS in groundwater recharged farther from the stream.

Massachusetts↗