Growing evidence that certain poly- and perfluoroalkyl substances (PFASs) are associated with negative human health effects prompted the U.S. Environmental Protection Agency to issue lifetime ...drinking water health advisories for perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) in 2016. Given that groundwater is a major source of drinking water, the main objective of this work was to investigate geochemical and hydrological processes governing the subsurface transport of PFASs at a former fire training area (FTA) on Cape Cod, Massachusetts, where PFAS-containing aqueous film-forming foams were used historically. A total of 148 groundwater samples and 4 sediment cores were collected along a 1200-m-long downgradient transect originating near the FTA and analyzed for PFAS content. The results indicate that unsaturated zones at the FTA and at hydraulically downgradient former domestic wastewater effluent infiltration beds both act as continuous PFAS sources to the groundwater despite 18 and 20 years of inactivity, respectively. Historically different PFAS sources are evident from contrasting PFAS composition near the water table below the FTA and wastewater-infiltration beds. Results from total oxidizable precursor assays conducted using groundwater samples collected throughout the plume suggest that some perfluoroalkyl acid precursors at this site are transporting with perfluoroalkyl acids.
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IJS, KILJ, NUK, PNG, UL, UM
Fish harvested from the Pacific Ocean are a major contributor to human methylmercury (MeHg) exposure. Limited oceanic mercury (Hg) data, particularly MeHg, has confounded our understanding of ...linkages between sources, methylation sites, and concentrations in marine food webs. Here we present methylated (MeHg and dimethylmercury (Me2Hg)) and total Hg concentrations from 16 hydrographic stations in the eastern North Pacific Ocean. We use these data in combination with information from previous cruises and coupled atmospheric‐oceanic modeling results to better understand controls on Hg concentrations, distribution, and bioavailability. Total Hg concentrations (average 1.14 ± 0.38 pM) are elevated relative to previous cruises. Modeling results agree with observed increases and suggest that at present atmospheric Hg deposition rates, basin‐wide Hg concentrations will double relative to circa 1995 by 2050. Methylated Hg accounts for up to 29% of the total Hg in subsurface waters (average 260 ± 114 fM). We observed lower ambient methylated Hg concentrations in the euphotic zone and older, deeper water masses, which likely result from decay of MeHg and Me2Hg when net production is not occurring. We found a significant, positive linear relationship between methylated Hg concentrations and rates of organic carbon remineralization (r2 = 0.66, p < 0.001). These results provide evidence for the importance of particulate organic carbon (POC) transport and remineralization on the production and distribution of methylated Hg species in marine waters. Specifically, settling POC provides a source of inorganic Hg(II) to microbially active subsurface waters and can also provide a substrate for microbial activity facilitating water column methylation.
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Elevated levels of neurotoxic methylmercury in Arctic food-webs pose health risks for indigenous populations that consume large quantities of marine mammals and fish. Estuaries provide critical ...hunting and fishing territory for these populations, and, until recently, benthic sediment was thought to be the main methylmercury source for coastal fish. New hydroelectric developments are being proposed in many northern ecosystems, and the ecological impacts of this industry relative to accelerating climate changes are poorly characterized. Here we evaluate the competing impacts of climate-driven changes in northern ecosystems and reservoir flooding on methylmercury production and bioaccumulation through a case study of a stratified sub-Arctic estuarine fjord in Labrador, Canada. Methylmercury bioaccumulation in zooplankton is higher than in midlatitude ecosystems. Direct measurements and modeling show that currently the largest methylmercury source is production in oxic surface seawater. Water-column methylation is highest in stratified surface waters near the river mouth because of the stimulating effects of terrestrial organic matter on methylating microbes. We attribute enhanced biomagnification in plankton to a thin layer of marine snow widely observed in stratified systems that concentrates microbial methylation and multiple trophic levels of zooplankton in a vertically restricted zone. Large freshwater inputs and the extensive Arctic Ocean continental shelf mean these processes are likely widespread and will be enhanced by future increases in water-column stratification, exacerbating high biological methylmercury concentrations. Soil flooding experiments indicate that near-term changes expected from reservoir creation will increase methylmercury inputs to the estuary by 25–200%, overwhelming climate-driven changes over the next decade.
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BFBNIB, NMLJ, NUK, PNG, SAZU, UL, UM, UPUK
Per- and polyfluoroalkyl substances (PFAS) are a diverse class of fluorinated anthropogenic chemicals that include perfluoroalkyl acids (PFAA), which are widely used in modern commerce. Many products ...and environmental samples contain abundant precursors that can degrade into terminal PFAA associated with adverse health effects. Fish consumption is an important dietary exposure source for PFAS that bioaccumulate in food webs. However, little is known about bioaccumulation of PFAA precursors. Here, we identify and quantify PFAS in recreational fish species collected from surface waters across New Hampshire, US, using a toolbox of analytical methods. Targeted analysis of paired water and tissue samples suggests that many precursors below detection in water have a higher bioaccumulation potential than their terminal PFAA. Perfluorobutane sulfonamide (FBSA), a short-chain precursor produced by electrochemical fluorination, was detected in all fish samples analyzed for this compound. The total oxidizable precursor assay interpreted using Bayesian inference revealed fish muscle tissue contained additional, short-chain precursors in high concentration samples. Suspect screening analysis indicated these were perfluoroalkyl sulfonamide precursors with three and five perfluorinated carbons. Fish consumption advisories are primarily being developed for perfluorooctane sulfonate (PFOS), but this work reinforces the need for risk evaluations to consider additional bioaccumulative PFAS, including perfluoroalkyl sulfonamide precursors.
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IJS, KILJ, NUK, PNG, UL, UM
Rapid declines in legacy poly- and perfluoroalkyl substances (PFASs) have been reported in human populations globally following changes in production since 2000. However, changes in exposure sources ...are not well understood. Here, we report serum concentrations of 19 PFASs (∑19PFAS) measured in children between 1993 and 2012 from a North Atlantic fishing community (Faroe Islands). Median ∑19PFAS concentrations in children (ages 5–13 years) peaked in 2000 (47.7 ng mL–1) and declined significantly by 14.4% year–1 until 2012. Principal component analysis (PCA) identified two groups of PFASs that likely reflect exposures from diverse consumer products and a third group that consisted of perfluorocarboxylic acids (PFCAs) with nine or more carbons (C ≥ 9). These C ≥ 9 PFASs are strongly associated with mercury in children’s hair, a well-established proxy for seafood consumption, especially perfluoroundecanoic acid (PFUnDA, r = 0.72). Toxicokinetic modeling shows PFAS exposures from seafood have become increasingly important (53% of perfluorooctanesulfonate, PFOS, in 2012), despite a decline in whale consumption in recent years. We infer that even in a major seafood-consuming population, declines in legacy PFAS exposure after 2000 were achieved by the rapid phase out of PFOS and its precursors in consumer products. These results emphasize the importance of better understanding exposures to replacement PFASs in these sources.
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IJS, KILJ, NUK, PNG, UL, UM
Methylmercury (MeHg) is the only species of mercury (Hg) to biomagnify in aquatic food-webs to levels that are a widespread concern for human and ecological health. Here we investigate the ...association between dissolved organic matter (DOM) in seawater and Hg speciation and uptake using experimental data and field measurements from Long Island Sound (LIS) and the Northwestern Atlantic continental margin. We measured differences in DOM composition across sampling stations using excitation emission matrix fluorescence spectroscopy and further separated DOM into terrestrial and marine components using Parallel Factor Analysis (PARAFAC). Highest MeHg concentrations were found in the estuarine stations (LIS) with highest DOM concentrations due to enhanced external inputs from the watershed and rivers. For stations on the shelf and slope, MeHg in plankton increased linearly with a decreasing fraction of fluorescence attributable to DOM components with a terrestrial rather than marine origin. These results are corroborated by experimental data showing higher MeHg uptake by cells in the presence of predominantly marine DOM compared to terrestrial DOM. Highest fractions of dissolved gaseous mercury were also found at stations with the highest marine DOM content, suggesting a greater reducible fraction of divalent inorganic Hg. These data suggest DOM composition is a critical driver of Hg reactivity and bioavailability in offshore marine waters.
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IJS, KILJ, NUK, PNG, UL, UM
We develop a mechanistic global model of soil mercury storage and emissions that ties the lifetime of mercury in soils to the lifetime of the organic carbon pools it is associated with. We explore ...the implications of considering terrestrial mercury cycling in the framework of soil carbon cycling and suggest possible avenues of future research to test our assumptions and constrain this type of model. In our simulation, input of mercury to soil is by atmospheric deposition, in part through leaf uptake and subsequent litter fall, and is moderated by surface photoreduction and revolatilization. Once bound to organic carbon, mercury is transferred along a succession of short‐lived to long‐lived carbon pools and is ultimately reemitted by respiration of these pools. We examine the legacy of anthropogenic influence on global mercury storage and emissions and estimate that storage of mercury in organic soils has increased by ∼20% since preindustrial times, while soil emissions have increased by a factor of 3 (2900 Mg yr−1 versus 1000 Mg yr−1). At steady state, mercury accumulates in the most recalcitrant soil carbon pools and has an overall lifetime against respiration of 630 years. However, the impact of anthropogenic emissions since preindustrial times has been concentrated in more labile pools, so that the mean lifetime of present‐day anthropogenic mercury in all pools is ∼80 years. Our analysis suggests that reductions in anthropogenic emissions would lead to immediate and large reductions in secondary soil mercury emissions.
We present a new chemical mechanism for Hg0/HgI/HgII atmospheric cycling, including recent laboratory and computational data, and implement it in the GEOS-Chem global atmospheric chemistry model for ...comparison to observations. Our mechanism includes the oxidation of Hg0 by Br and OH, subsequent oxidation of HgI by ozone and radicals, respeciation of HgII in aerosols and cloud droplets, and speciated HgII photolysis in the gas and aqueous phases. The tropospheric Hg lifetime against deposition in the model is 5.5 months, consistent with observational constraints. The model reproduces the observed global surface Hg0 concentrations and HgII wet deposition fluxes. Br and OH make comparable contributions to global net oxidation of Hg0 to HgII. Ozone is the principal HgI oxidant, enabling the efficient oxidation of Hg0 to HgII by OH. BrHgIIOH and HgII(OH)2, the initial HgII products of Hg0 oxidation, respeciate in aerosols and clouds to organic and inorganic complexes, and volatilize to photostable forms. Reduction of HgII to Hg0 takes place largely through photolysis of aqueous HgII–organic complexes. 71% of model HgII deposition is to the oceans. Major uncertainties for atmospheric Hg chemistry modeling include Br concentrations, stability and reactions of HgI, and speciation and photoreduction of HgII in aerosols and clouds.
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IJS, KILJ, NUK, PNG, UL, UM
Perfluorooctane sulfonate (PFOS) is an aliphatic fluorinated compound with eight carbon atoms that is extremely persistent in the environment and can adversely affect human and ecological health. The ...stability, low reactivity, and high water solubility of PFOS combined with the North American phaseout in production around the year 2000 make it a potentially useful new tracer for ocean circulation. Here we characterize processes affecting the lifetime and accumulation of PFOS in the North Atlantic Ocean and transport to sensitive Arctic regions by developing a 3‐D simulation within the MITgcm. The model captures variability in measurements across biogeographical provinces (R2 = 0.90, p = 0.01). In 2015, the North Atlantic PFOS reservoir was equivalent to 60% of cumulative inputs from the North American and European continents (1400 Mg). Cumulative inputs to the Arctic accounted for 30% of continental discharges, while the remaining 10% was transported to the tropical Atlantic and other regions. PFOS concentrations declined rapidly after 2002 in the surface mixed layer (half‐life: 1–2 years) but are still increasing below 1000 m depth. During peak production years (1980–2000), plumes of PFOS‐enriched seawater were transported to the sub‐Arctic in energetic surface ocean currents. However, Atlantic Meridional Overturning Circulation (AMOC) and deep ocean transport returned a substantial fraction of this northward transport (20%, 530 Mg) to southern latitudes and reduced cumulative inputs to the Arctic (730 Mg) by 70%. Weakened AMOC due to climate change is thus likely to increase the magnitude of persistent bioaccumulative pollutants entering the Arctic Ocean.
Plain Language Summary
Perfluorooctane sulfonate (PFOS) is a persistent anthropogenic compound that has been released to the environment in large quantities and adversely affects human and ecological health. Its production was phased out in North America in 2000, but the ocean is the terminal PFOS sink. This study develops a new model for PFOS cycling in the North Atlantic Ocean and transport to sensitive Arctic regions based on best understanding of ocean physics and ecology. Results suggest that in 2015, 60% of cumulative PFOS discharges from North America and Europe were still present in the North Atlantic and 30% had entered the Arctic Ocean. Most of the remaining fraction was transported to the South Atlantic. The lifetime of PFOS in the surface ocean is less than 5 years due to rapid penetration into deeper waters where it persists for decades or longer before being transported to other basins. During peak production years, most continental PFOS pollution was transported to the sub‐Arctic but large‐scale overturning of the North Atlantic Ocean reduced the total burden entering the high Arctic by 70%. Climate‐driven changes in ocean circulation that are weakening this process may thus increase the vulnerability of the Arctic to continental pollution.
Key Points
Perfluorooctane sulfonate (PFOS) shows promise as a new ocean tracer but is also a potent toxicant
PFOS concentrations in the upper North Atlantic Ocean peaked between 2002 and 2005 but are still increasing in the deep ocean.
Sinking, convection, and southward transport of subpolar surface waters greatly reduces PFOS inputs to the high Arctic
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
The relative importance of atmospheric versus oceanic transport for poly- and perfluorinated alkyl substances (PFASs) reaching the Arctic Ocean is not well understood. Vertical profiles from the ...Central Arctic Ocean and shelf water, snow and meltwater samples were collected in 2012; 13 PFASs (C6–C12 PFCAs; C6, 8, 10 PFSAs; MeFOSAA and EtFOSAA; and FOSA) were routinely detected (range: <5–343 pg/L). PFASs were only detectable above 150 m depth in the polar mixed layer (PML) and halocline. Enhanced concentrations were observed in snow and meltpond samples, implying atmospheric deposition as an important source of PFASs. Model results suggested atmospheric inputs to account for 34–59% (∼11–19 pg/L) of measured PFOA concentrations in the PML (mean 32 ± 15 pg/L). Modeled surface and halocline measurements for PFOS based on North Atlantic inflow (11–36 pg/L) agreed with measurements (mean, 17, range <5–41 pg/L). Modeled deep water concentrations below 200 m (5–15 pg/L) were slightly higher than measurements (<5 pg/L), suggesting the lower bound of PFAS emissions estimates from wastewater and rivers may provide the best estimate of inputs to the Arctic. Despite low concentrations in deep water, this reservoir is expected to contain most of the PFOS mass in the Arctic (63–180 Mg) and is projected to continue increasing to 2038.
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IJS, KILJ, NUK, PNG, UL, UM
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