Here we review present understanding of sources and trends in human exposure to poly- and perfluoroalkyl substances (PFASs) and epidemiologic evidence for impacts on cancer, immune function, metabolic outcomes, and neurodevelopment. More than 4000 PFASs have been manufactured by humans and hundreds have been detected in environmental samples. Direct exposures due to use in products can be quickly phased out by shifts in chemical production but exposures driven by PFAS accumulation in the ocean and marine food chains and contamination of groundwater persist over long timescales. Serum concentrations of legacy PFASs in humans are declining globally but total exposures to newer PFASs and precursor compounds have not been well characterized. Human exposures to legacy PFASs from seafood and drinking water are stable or increasing in many regions, suggesting observed declines reflect phase-outs in legacy PFAS use in consumer products. Many regions globally are continuing to discover PFAS contaminated sites from aqueous film forming foam (AFFF) use, particularly next to airports and military bases. Exposures from food packaging and indoor environments are uncertain due to a rapidly changing chemical landscape where legacy PFASs have been replaced by diverse precursors and custom molecules that are difficult to detect. Multiple studies find significant associations between PFAS exposure and adverse immune outcomes in children. Dyslipidemia is the strongest metabolic outcome associated with PFAS exposure. Evidence for cancer is limited to manufacturing locations with extremely high exposures and insufficient data are available to characterize impacts of PFAS exposures on neurodevelopment. Preliminary evidence suggests significant health effects associated with exposures to emerging PFASs. Lessons learned from legacy PFASs indicate that limited data should not be used as a justification to delay risk mitigation actions for replacement PFASs.

Drinking water contamination with poly- and perfluoroalkyl substances (PFASs) poses risks to the developmental, immune, metabolic, and endocrine health of consumers. We present a spatial analysis of 2013–2015 national drinking water PFAS concentrations from the U.S. Environmental Protection Agency’s (US EPA) third Unregulated Contaminant Monitoring Rule (UCMR3) program. The number of industrial sites that manufacture or use these compounds, the number of military fire training areas, and the number of wastewater treatment plants are all significant predictors of PFAS detection frequencies and concentrations in public water supplies. Among samples with detectable PFAS levels, each additional military site within a watershed’s eight-digit hydrologic unit is associated with a 20% increase in PFHxS, a 10% increase in both PFHpA and PFOA, and a 35% increase in PFOS. The number of civilian airports with personnel trained in the use of aqueous film-forming foams is significantly associated with the detection of PFASs above the minimal reporting level. We find drinking water supplies for 6 million U.S. residents exceed US EPA’s lifetime health advisory (70 ng/L) for PFOS and PFOA. Lower analytical reporting limits and additional sampling of smaller utilities serving <10000 individuals and private wells would greatly assist in further identifying PFAS contamination sources.

Understanding the biogeochemical cycling of mercury is critical for explaining the presence of mercury in remote regions of the world, such as the Arctic and the Himalayas, as well as local concentrations. While we have good knowledge of present-day fluxes of mercury to the atmosphere, we have little knowledge of what emission levels were like in the past. Here we

Elevated mercury (Hg) in marine and terrestrial ecosystems is a global health concern because of the formation of toxic methylmercury. Humans have emitted Hg to the atmosphere for millennia, and this Hg has deposited and accumulated into ecosystems globally. Here we present a global biogeochemical model with fully coupled atmospheric, terrestrial, and oceanic Hg reservoirs to better understand human influence on Hg cycling and timescales for responses. We drive the model with a historical inventory of anthropogenic emissions from 2000 BC to present. Results show that anthropogenic perturbations introduced to surface reservoirs (atmosphere, ocean, or terrestrial) accumulate and persist in the subsurface ocean for decades to centuries. The simulated present‐day atmosphere is enriched by a factor of 2.6 relative to 1840 levels, consistent with sediment archives, and by a factor of 7.5 relative to natural levels (2000 BC). Legacy anthropogenic Hg re‐emitted from surface reservoirs accounts for 60% of present‐day atmospheric deposition, compared to 27% from primary anthropogenic emissions, and 13% from natural sources. We find that only 17% of the present‐day Hg in the surface ocean is natural and that half of its anthropogenic enrichment originates from pre‐1950 emissions. Although Asia is presently the dominant contributor to primary anthropogenic emissions, only 17% of the surface ocean reservoir is of Asian anthropogenic origin, as compared to 30% of North American and European origin. The accumulated burden of legacy anthropogenic Hg means that future deposition will increase even if primary anthropogenic emissions are held constant. Aggressive global Hg emission reductions will be necessary just to maintain oceanic Hg concentrations at present levels.

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.

Abstract. Atmospheric deposition of Hg(II) represents a major input of mercury to surface environments. The phase of Hg(II) (gas or particle) has important implications for deposition. We use long-term observations of reactive gaseous mercury (RGM, the gaseous component of Hg(II)), particle-bound mercury (PBM, the particulate component of Hg(II)), fine particulate matter (PM 2.5 ), and temperature (T ) at five sites in North America to derive an empirical gas-particle partitioning relationship log 10 (K −1 ) = (10±1)-(2500±300)/T where K = (PBM/PM 2.5 )/RGM with PBM and RGM in common mixing ratio units, PM 2.5 in µg m −3 , and T in K. This relationship is within the range of previous work but is based on far more extensive data from multiple sites. We implement this empirical relationship in the GEOS-Chem global 3-D Hg model to partition Hg(II) between the gas and particle phases. The resulting gas-phase fraction of Hg(II) ranges from over 90 % in warm air with little aerosol to less than 10 % in cold air with high aerosol. Hg deposition to high latitudes increases because of more efficient scavenging of particulate Hg(II) by precipitating snow. Model comparison to Hg observations at the North American surface sites suggests that subsidence from the free troposphere (warm air, low aerosol) is a major factor driving the seasonality of RGM, while elevated PBM is mostly associated with high aerosol loads. Simulation of RGM and PBM at these sites is improved by including fast in-plume reduction of Hg(II) emitted from coal combustion and by assuming that anthropogenic particulate Hg(p) behaves as semivolatile Hg(II) rather than as a refractory particulate component. We improve the simulation of Hg wet deposition fluxes in the US relative to a previous version of GEOS-Chem; this largely reflects independent improvement of the washout algorithm. The observed wintertime minimum in wet deposition fluxes is attributed to inefficient snow scavenging of gas-phase Hg(II).

Anthropogenic activities have enriched mercury in the biosphere by at least a factor of three, leading to increases in total mercury (Hg) in the surface ocean. However, the impacts on ocean fish and associated trends in human exposure as a result of such changes are less clear. Here we review our understanding of global mass budgets for both inorganic and methylated Hg species in ocean seawater. We consider external inputs from atmospheric deposition and rivers as well as internal production of monomethylmercury (CH3Hg) and dimethylmercury ((CH3)2Hg). Impacts of large-scale ocean circulation and vertical transport processes on Hg distribution throughout the water column and how this influences bioaccumulation into ocean food chains are also discussed. Our analysis suggests that while atmospheric deposition is the main source of inorganic Hg to open ocean systems, most of the CH3Hg accumulating in ocean fish is derived from in situ production within the upper waters (<1000 m). An analysis of the available data suggests that concentrations in the various ocean basins are changing at different rates due to differences in atmospheric loading and that the deeper waters of the oceans are responding slowly to changes in atmospheric Hg inputs. Most biological exposures occur in the upper ocean and therefore should respond over years to decades to changes in atmospheric mercury inputs achieved by regulatory control strategies. Migratory pelagic fish such as tuna and swordfish are an important component of CH3Hg exposure for many human populations and therefore any reduction in anthropogenic releases of Hg and associated deposition to the ocean will result in a decline in human exposure and risk.

[1] We develop a mechanistic representation of land-atmosphere cycling in a global 3-D ocean-atmosphere model of mercury (GEOS-Chem). The resulting land-oceanatmosphere model is used to construct preindustrial and present biogeochemical cycles of mercury, to examine the legacy of past anthropogenic emissions, to map anthropogenic enrichment factors for deposition, and to attribute mercury deposition in the United States. Land emission in the model includes prompt recycling of recently deposited mercury (600 Mg a À1 for present day), soil volatilization (550 Mg a À1), and evapotranspiration (550 Mg a À1). The spatial distribution of soil concentrations is derived from local steady state between land emission and deposition in the preindustrial simulation, augmented for the present day by a 15% increase in the soil reservoir distributed following the pattern of anthropogenic deposition. Mercury deposition and hence emission are predicted to be highest in the subtropics. Our atmospheric lifetime of mercury against deposition (0.50 year) is shorter than past estimates because of our accounting of Hg(0) dry deposition, but recycling from surface reservoirs results in an effective lifetime of 1.6 years against transfer to long-lived reservoirs in the soil and deep ocean. Present-day anthropogenic enrichment of mercury deposition exceeds a factor of 5 in continental source regions. We estimate that 68% of the deposition over the United States is anthropogenic, including 20% from North American emissions (20% primary and <1% recycled through surface reservoirs), 31% from emissions outside North America (22% primary and 9% recycled), and 16% from the legacy of anthropogenic mercury accumulated in soils and the deep ocean.