Geology topics

Denis R. LeBlanc

Publications and source records attributed to Denis R. LeBlanc.

At least 19 recordsLinked to original sources

USGS2026

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↗

USGS2026

PFAS from a discrete-event terrestrial source migrates with groundwater to intertidal seepages

Groundwater transport of per- and polyfluoroalkyl substances (PFAS) from terrestrial sources to marine coastal ecosystems is a topic of growing recognition, though with few published field studies. Furthermore, most research on PFAS fate and transport dynamics has focused on source areas with long histories like fire training and manufacturing facilities; the effect of single PFAS dispersal events to the coastal environment is not well documented. We have assessed PFAS mobility in groundwater to intertidal seepages from two discrete, adjacent tanker-truck rollover events that occurred in 1997 and 2000 where aqueous film forming foams (AFFF) were applied to suppress fuel vapors. Using a combination of groundwater-flow and particle-track modeling, geophysical field characterization, and chemical sampling, we found substantial concentrations of PFAS (up to 530.5 ng/L), mainly perfluorooctane sulfonate (PFOS), in groundwater discharging to a shoreline along an embayment used for swimming and recreational shellfish harvesting. The general groundwater trajectory to the embayment was predicted by numerical particle tracking. The highest concentrations of PFAS were found in discharges near the landward side of the intertidal zone. The discharges had variable salinity at the time of sampling. Our research generated the finding that even in areas of strong, preferential groundwater discharge at low tide, there was tidal “pumping” of ocean water into the aquifer sediments during higher tides. Therefore, there are likely to be continuously variable salinity conditions at similar seepage interfaces that have not been broadly considered in previous conceptual models of PFAS fate and transport.

Massachusetts↗

USGS2026

Tracking baseflow supply dynamics using SWOT data from small groundwater-dominated lakes

In situ surface-water monitoring strategies are biased towards larger perennial streams and lakes and are generally not designed to track mechanisms of baseflow supply contributed by the dynamic storage of aquifers. Additionally, small (< 1 km 2 ) groundwater-influenced lakes and wetlands globally have little in situ monitoring infrastructure. We explored the utility of remotely sensed Surface Water Ocean Topography Satellite (SWOT) data, collected from 2023 onward, to characterise the seasonal and multi-year water-level trends of groundwater flow-through kettle lakes distributed across the permeable sediments of eastern Massachusetts, USA. This analysis indicated that water levels for kettle lakes with areas down to approximately 0.05 km 2 are resolvable in the study area. Our examination of 17 kettle lakes found that SWOT water-surface elevation data closely tracked groundwater levels in adjacent monitoring wells where available, including the timing of seasonal patterns (highest levels generally in late spring), although there was some variation between years and there was a substantial lag in the timing of high water levels for a lake located downgradient from a 30-m-thick vadose zone. Furthermore, SWOT-observed water-level increases in kettle lakes tracked with baseflow increases in two adjacent groundwater-dominated streams, as would be expected from increased hydraulic gradients. Unlike spectral remote sensing, SWOT data are generally not affected by cloud cover, resulting in a potential for groundwater-dominated lakes to be sentinels of dynamic storage patterns, including identification of baseflow drought lags, which are currently ill-defined hydrological processes. SWOT monitoring of groundwater-influenced surface waters shows potential for augmenting existing monitoring wells and streamgages as continuous monitors of groundwater levels and baseflow supply in permeable terrain.

Massachusetts↗

USGS2025

Occurrence and tissue distribution of per- and polyfluoroalkyl substances (PFAS) in fishes from waterbodies with point and non-point sources in Massachusetts, USA

Per- and polyfluoroalkyl substances (PFAS) are persistent environmental contaminants with known bioaccumulative and toxic effects in aquatic ecosystems. This study assessed site-specific differences in PFAS contamination in fish from Ashumet Pond, Sudbury River, and Great Herring Pond (reference site) in Massachusetts. Fish from Ashumet Pond exhibited the highest PFAS concentrations, particularly perfluorooctane sulfonate (PFOS), which exceeded levels in plasma almost 650 times those at the reference site. Principal component analysis identified distinct PFAS profiles at each site, reflecting localized contamination sources. Temporal analysis at Ashumet Pond revealed a substantial increase in plasma PFOS and perfluorodecanoic acid (PFDA) from 2020 to 2022. Tissue distribution analyses showed the highest PFAS concentrations in plasma, followed by liver and muscle, consistent with PFAS binding affinity for blood proteins. Species-specific differences in PFAS bioaccumulation were observed, with largemouth bass ( Micropterus nigricans ) exhibiting higher body burdens than banded killifish ( Diaphanus fundulus ), likely due to trophic position and dietary exposure. Histopathological assessments and gene transcript analyses revealed associations between PFAS exposure and inflammatory responses, oxidative stress, endocrine disruption, and immune-related pathways, with the most pronounced molecular effects observed at the downstream site of the Sudbury River. This study underscores the importance of understanding site-specific contamination sources, exposure pathways, and biological effects of PFAS in fish. These findings would benefit from additional research on sediment contamination, temporal analyses at each site, trophic transfer, and transcriptomic analyses across multiple organs to further elucidate PFAS toxicity mechanisms and guide remediation efforts.

Massachusetts↗

USGS2025

Linking stream-reach nitrogen loads and groundwater “reachsheds” to inform wastewater-nitrogen management actions, Cape Cod, Massachusetts

Study Region Cape Cod, Massachusetts, U.S.A. Study Focus Anthropogenic nitrogen (N) is a key factor in degrading groundwater and surface-water quality, particularly in coastal New England where onsite wastewater systems are prevalent. This study evaluated whether direct N-load measurements in streams on Cape Cod, Massachusetts, coupled with flow-path information from groundwater-flow models, can effectively identify potential land areas where nitrogen mitigation could substantially reduce loads to receiving waters. Nitrogen fluxes were measured along 63 stream reaches during winter and summer and paired with simulated groundwater recharge areas to identify and rank potential areas for reduction of nonpoint-source N inputs. New Hydrologic Insights for the Region Reach-scale nitrate-N loads ranged from −39.1–1182 kg-N/yr per 100 m of stream, indicating spatially variable groundwater inputs across seasons. “Reachsheds” — areas contributing groundwater recharge to specific stream reaches — were delineated using a regional groundwater-flow model. Strong correlations were found between observed N loads and land-use characteristics, especially the number of septic systems and total N inputs from the sum of considered sources. Observed N loads were moderately correlated with recharge area size and wastewater flow estimates. Correlating reach-specific groundwater N loads with land use and parcel-scale nitrogen-yield data identified reachsheds with the highest potential for N load reduction. This approach enables targeted implementation of restoration efforts to optimize nutrient management and support regional load reduction.

Massachusetts↗

USGS2025

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↗

USGS2024

Characterizing the areal extent of PFAS contamination in fish species downgradient of AFFF source zones

Most monitoring programs next to large per- and polyfluoroalkyl substances (PFAS) sources focus on drinking water contamination near source zones. However, less is understood about how these sources affect downgradient hydrological systems and food webs. Here, we report paired PFAS measurements in water, sediment, and aquatic biota along a hydrological gradient away from source zones contaminated by the use of legacy aqueous film-forming foam (AFFF) manufactured using electrochemical fluorination. Clustering analysis indicates that the PFAS composition characteristic of AFFF is detectable in water and fishes >8 km from the source. Concentrations of 38 targeted PFAS and extractable organofluorine (EOF) decreased in fishes downgradient of the AFFF-contaminated source zones. However, PFAS concentrations remained above consumption limits at all locations within the affected watershed. Perfluoroalkyl sulfonamide precursors accounted for approximately half of targeted PFAS in fish tissues, which explain >90% of EOF across all sampling locations. Suspect screening analyses revealed the presence of a polyfluoroketone pharmaceutical in fish species, and a fluorinated agrochemical in water that likely does not accumulate in biological tissues, suggesting the presence of diffuse sources such as septic system and agrochemical inputs throughout the watershed in addition to AFFF contamination. Based on these results, monitoring programs that consider all hydrologically connected regions within watersheds affected by large PFAS sources would help ensure public health protection.

Massachusetts↗

USGS2024

Bioconcentration of per- and polyfluoroalkyl substances and precursors in fathead minnow tissues environmentally exposed to aqueous film-forming foam-contaminated waters

Exposure to per- and polyfluoroalkyl substances (PFAS) has been associated with toxicity in wildlife and negative health effects in humans. Decades of fire training activity at Joint Base Cape Cod (MA, USA) incorporated the use of aqueous film-forming foam (AFFF), which resulted in long-term PFAS contamination of sediments, groundwater, and hydrologically connected surface waters. To explore the bioconcentration potential of PFAS in complex environmental mixtures, a mobile laboratory was established to evaluate the bioconcentration of PFAS from AFFF-impacted groundwater by flow-through design. Fathead minnows ( n = 24) were exposed to PFAS in groundwater over a 21-day period and tissue-specific PFAS burdens in liver, kidney, and gonad were derived at three different time points. The ∑PFAS concentrations in groundwater increased from approximately 10,000 ng/L at day 1 to 36,000 ng/L at day 21. The relative abundance of PFAS in liver, kidney, and gonad shifted temporally from majority perfluoroalkyl sulfonamides (FASAs) to perfluoroalkyl sulfonates (PFSAs). By day 21, mean ∑PFAS concentrations in tissues displayed a predominance in the order of liver > kidney > gonad. Generally, bioconcentration factors (BCFs) for FASAs, perfluoroalkyl carboxylates (PFCAs), and fluorotelomer sulfonates (FTS) increased with degree of fluorinated carbon chain length, but this was not evident for PFSAs. Perfluorooctane sulfonamide (FOSA) displayed the highest mean BCF (8700 L/kg) in day 21 kidney. Suspect screening results revealed the presence of several perfluoroalkyl sulfinate and FASA compounds present in groundwater and in liver for which pseudo-bioconcentration factors are also reported. The bioconcentration observed for precursor compounds and PFSA derivatives detected suggests alternative pathways for terminal PFAS exposure in aquatic wildlife and humans.

Environmental Toxicology and Chemistry↗

USGS2024

Spatial, seasonal, and diel controls of nitrogen-carbon-oxygen cycling during lake-water infiltration to an aquifer

Many freshwater lakes are groundwater flow-through systems. Although lakes commonly are considered to be sinks for nitrogen inputs, relatively little is known about carbon and nitrogen export from lakes to groundwater. The current study focused on lake-bottom biogeochemical processes accompanying the transport of nitrogen, dissolved oxygen (O 2 ), and dissolved organic carbon (DOC) during lake-water recharge from a groundwater flow-through lake. Lake-water and porewater (15–100 cm below lakebed) samples were collected along transects within the lake downwelling zone. Infiltrating porewater O 2 and DOC concentrations decreased with depth while nitrate (NO 3 − ) concentrations increased, indicating nitrification of organic matter within the profiles. The depth of NO 3 − production and transport was seasonally dependent. In winter, NO 3 − and O 2 were exported beyond 100-cm depth; whereas in summer, shallow nitrification zones were underlain by deeper NO 3 − reduction zones, and diel patterns of O 2 and NO 3 − penetration depths were observed. Microbial community compositions and stable isotope profiles (δ 15 N[NO 3 − ], δ 18 O[NO 3 − ], δ 18 O[O 2 ]) were consistent with apparent C–N–O reaction stoichiometries indicating O 2 reduction and nitrification in shallower porewater, followed by varying NO 3 − reduction at depth. Maximum porewater NO 3 − concentrations (∼10–20 μM) were limited by infiltrating O 2 concentrations and C/N ratios of reacting organic matter. Lake-water level variations caused changes in shoreline position and porewater velocities, while variations in lake-water temperature, DOC, and O 2 contributed to changes in reaction rates and depth of O 2 and NO 3 − penetration into the lakebed. The quality of groundwater recharged by lake water reflected temporally and spatially varying physical and biogeochemical processes in the sediment porewater.

Journal of Geophysical Research: Biogeosciences↗

USGS2023

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↗

USGS2023

Uptake of per- and polyfluoroalkyl substances by fish, mussel, and passive samplers in mobile laboratory exposures using groundwater from a contamination plume at a historical fire training area, Cape Cod, Massachusetts

Aqueous film-forming foams historically were used during fire training activities on Joint Base Cape Cod, Massachusetts, and created an extensive per- and polyfluoroalkyl substances (PFAS) groundwater contamination plume. The potential for PFAS bioconcentration from exposure to the contaminated groundwater, which discharges to surface water bodies, was assessed with mobile-laboratory experiments using groundwater from the contamination plume and a nearby reference location. The on-site continuous-flow 21-day exposures used male and female fathead minnows, freshwater mussels, polar organic chemical integrative samplers (POCIS), and polyethylene tube samplers (PETS) to evaluate biotic and abiotic uptake. The composition of the PFAS-contaminated groundwater was complex and 9 PFAS were detected in the reference groundwater and 17 PFAS were detected in the contaminated groundwater. The summed PFAS concentrations ranged from 120 to 140 ng L –1 in reference groundwater and 6100 to 15,000 ng L –1 in contaminated groundwater. Biotic concentration factors (CF b ) for individual PFAS were species, sex, source, and compound-specific and ranged from 2.9 to 1000 L kg –1 in whole-body male fish exposed to contaminated groundwater for 21 days. The fish and mussel CF b generally increased with increasing fluorocarbon chain length and were greater for sulfonates than for carboxylates. The exception was perfluorohexane sulfonate, which deviated from the linear trend and had a 10-fold difference in CF b between sites, possibly because of biotransformation of precursors such as perfluorohexane sulfonamide. Uptake for most PFAS in male fish was linear over time, whereas female fish had bilinear uptake indicated by an initial increase in tissue concentrations followed by a decrease. Uptake of PFAS was less for mussels (maximum CF b = 200) than for fish, and mussel uptake of most PFAS also was bilinear. Although abiotic concentration factors were greater than CF b , and values for POCIS were greater than for PETS, passive samplers were useful for assessing PFAS that potentially bioconcentrate in fish but are present at concentrations below method quantitation limits in water. Passive samplers also accumulate short-chain PFAS that are not bioconcentrated.

Massachusetts↗

USGS2021

Evaluating the effects of replacing septic systems with municipal sewers on groundwater quality in a densely developed coastal neighborhood, Falmouth, Massachusetts, 2016–19

Land disposal of sewage wastewater through septic systems and cesspools is a major cause of elevated concentrations of nitrogen in the shallow coastal aquifers of southern New England. The discharge of nitrogen from these sources at the coast is affecting the environmental health of coastal saltwater bodies. In response, local, State, and Federal agencies are considering expensive actions to mitigate these effects, including installing municipal sewer systems. To increase the understanding of the effects of municipal sewering on groundwater quality discharging to coastal surface waters, a network of multilevel monitoring wells was established in a densely developed coastal neighborhood on the Maravista peninsula, Falmouth, Massachusetts, which was undergoing conversion from onsite septic disposal to municipal sewering. The geohydrology of the study area on the peninsula is generally characterized as consisting of fine to coarse, well-sorted sands containing 2.9 to 9.3 meters of fresh groundwater and a flow system characterized by a groundwater divide slightly west of the center of the peninsula. The magnitude of hydraulic gradients at the water table is gently sloping, ranging from 0.000032 to 0.00059, and affected by daily and bimonthly tidal fluctuations from adjacent coastal ponds. On the western side of the divide, upgradient from Little Pond, average linear groundwater velocities and traveltimes along shallow flow paths, estimated from observed hydraulic gradients and estimated aquifer hydraulic conductivity and effective porosity, range from 0.076 to 0.094 meters per day and 7.8 to 9.7 years, respectively. The groundwater monitoring network consists of 14 profile sites on the peninsula that each include a multilevel sampler for water-quality data collection and a shallow monitoring well for groundwater-level measurements. The study area encompasses about 230 residences that transitioned from onsite septic disposal to municipal sewering between spring 2017 and summer 2019. An additional multilevel sampler that was in a residential coastal setting but not undergoing sewering also was sampled periodically as a reference site. Elevated nitrogen, as compared to typical uncontaminated, fresh groundwater in the Cape Cod aquifer, predominately as nitrate, was measured in 15 water-quality profiles at nitrate concentrations as great as 26.2 milligrams per liter as nitrogen ( n =749; mean and median values were 5.1 and 4.1 milligrams per liter as nitrogen, respectively). At all 14 profile sites and the reference profile site on a nearby peninsula, wastewater effects were denoted by increased nitrate, boron, and specific conductance, and by decreased pH and dissolved oxygen. The highest concentrations of nitrate typically occurred in the deepest one-half of the freshwater zone and in intervals of suboxic and oxic groundwater. Thickness-weighted mean and maximum nitrate concentrations, and total nitrate mass from four sampling rounds, provided a metric to evaluate expected changes at the 14 profile sites on the peninsula. Nitrate concentrations varied moderately by site between sampling rounds through both the presewering (June 2016 and April 2017) and transitional periods (April 2018 and June 2019). Nitrate concentrations greater than the U.S. Environmental Protection Agency maximum contaminant level for nitrate in drinking water (10 milligrams per liter as nitrogen), were detected at 9 of the 14 profile sites and at the reference site. The average of the mean thickness-weighted nitrate concentrations for the four full sampling rounds was greater than 5.0 milligrams per liter as nitrogen at 8 sites (7 profile sites and the reference site) and greater than 8 milligrams per liter as nitrogen at 3 profile sites. The total nitrate mass per square meter of land area at each profile site ranged from 1,830 to 36,800 milligrams per square meter. Nitrate mass flux, across a 500-meter-long section upgradient from Little Pond and covering about 15 percent of the total pond shoreline length, ranged from 124.3 to 192.6 kilograms per year for the four full sampling rounds under three groundwater-flow conditions. The expected improvements in groundwater quality in the freshwater zone should be characterized by decreases in concentrations of dissolved total and inorganic nitrogen and common ions such as boron, chloride, and fluoride. A statistical analysis using the Regional Kendall test for sampling points grouped in specific depth ranges confirmed that water-quality changes were statistically significant in at least one depth group during the 3-year sampling period (nitrate: −0.76 milligram per liter per year; specific conductance: −12.1 microsiemens per centimeter at 25 degrees Celsius per year; dissolved oxygen: 0.82 milligram per liter per year); however, the rate at which the water-quality improvements will result in decreases in nitrate mass loads to the coastal ponds primarily depends on groundwater traveltimes and the rate of flushing of wastewater constituents from the aquifer.

Massachusetts↗

USGS2021

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↗

USGS2021

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↗

USGS2021

Public and private tapwater: Comparative analysis of contaminant exposure and potential risk, Cape Cod, Massachusetts, USA

Background Humans are primary drivers of environmental contamination worldwide, including in drinking-water resources. In the United States (US), federal and state agencies regulate and monitor public-supply drinking water while private-supply monitoring is rare; the current lack of directly comparable information on contaminant-mixture exposures and risks between private- and public-supplies undermines tapwater (TW) consumer decision-making. Methods We compared private- and public-supply residential point-of-use TW at Cape Cod, Massachusetts, where both supplies share the same groundwater source. TW from 10 private- and 10 public-supply homes was analyzed for 487 organic, 38 inorganic, 8 microbial indicators, and 3 in vitro bioactivities. Concentrations were compared to existing protective health-based benchmarks, and aggregated Hazard Indices (HI) of regulated and unregulated TW contaminants were calculated along with ratios of in vitro exposure-activity cutoffs. Results Seventy organic and 28 inorganic constituents were detected in TW. Median detections were comparable, but median cumulative concentrations were substantially higher in public supply due to 6 chlorine–disinfected samples characterized by disinfection byproducts and corresponding lower heterotrophic plate counts. Public-supply applicable maximum contaminant (nitrate) and treatment action (lead and copper) levels were exceeded in private-supply TW samples only. Exceedances of health-based HI screening levels of concern were common to both TW supplies. Discussion These Cape Cod results indicate comparable cumulative human-health concerns from contaminant exposures in private- and public-supply TW in a shared source-water setting. Importantly, although this study’s analytical coverage exceeds that currently feasible for water purveyors or homeowners, it nevertheless is a substantial underestimation of the full breadth of contaminant mixtures documented in the environment and potentially present in drinking water. Conclusion Regardless of the supply, increased public engagement in source-water protection and drinking-water treatment, including consumer point-of-use treatment, is warranted to reduce risks associated with long-term TW contaminant exposures, especially in vulnerable populations.

Massachusetts↗

USGS2021

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↗

USGS2020

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↗

USGS2020

Characterizing the diverse hydrogeology underlying rivers and estuaries using new floating transient electromagnetic methodology

The hydrogeology below large surface water features such as rivers and estuaries is universally under-informed at the long reach to basin scales (tens of km+). This challenge inhibits the accurate modeling of fresh/saline groundwater interfaces and groundwater/surface water exchange patterns at management-relevant spatial extents. Here we introduce a towed, floating transient electromagnetic (TEM) system (i.e. FloaTEM) for rapid (up to 15 km/h) high resolution electrical mapping of the subsurface below large water bodies to depths often a factor of 10 greater than other towed instruments. The novel FloaTEM system is demonstrated at a range of diverse 4th through 6th-order riverine settings across the United States including 1) the Farmington River, near Hartford, Connecticut; 2) the Upper Delaware River near Barryville, New York; 3) the Tallahatchie River near Shellmound, Mississippi; and, 4) the Eel River estuary, on Cape Cod, near Falmouth, Massachusetts. Airborne frequency-domain electromagnetic and land-based towed TEM data are also compared at the Tallahatchie River site, and streambed geologic scenarios are explored with forward modeling. A range of geologic structures and pore water salinity interfaces were identified. Process-based interpretation of the case study data indicated FloaTEM can resolve varied sediment-water interface materials, such as the accumulation of fines at the bottom of a reservoir and permeable sand/gravel riverbed sediments that focus groundwater discharge. Bedrock layers were mapped at several sites, and aquifer confining units were defined at comparable resolution to airborne methods. Terrestrial fresh groundwater discharge with flowpaths extending hundreds of meters from shore was also imaged below the Eel River estuary, improving on previous hydrogeological characterizations of that nutrient-rich coastal exchange zone. In summary, the novel FloaTEM system fills a critical gap in our ability to characterize the hydrogeology below surface water features and will support more accurate prediction of groundwater/surface water exchange dynamics and fresh-saline groundwater interfaces.

Science of the Total Environment↗