Poly- and Perfluoroalkyl Substances in Seawater and Plankton from the Northwestern Atlantic Margin

The ocean is thought to be the terminal sink for poly- and perfluoroalkyl substances (PFAS) that have been produced and released in large quantities for more than 60 years. Regulatory actions have curbed production of legacy compounds such as perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), but impacts of regulations on PFAS releases to the marine environment are poorly understood. Here, we report new data for 21 targeted PFAS in seawater and plankton from the coast, shelf, and slope of the Northwestern Atlantic Ocean. We find strong inverse correlations between salinity and concentrations of most PFAS, indicating that ongoing continental discharges are the major source to the marine environment. For legacy PFAS such as PFOS and PFOA, a comparison of inland and offshore measurements from the same year (2014) suggests that there are ongoing releases to the marine environment from sources such as submarine groundwater discharges. Vertical transport of most PFAS associated with settling particles from the surface (10 m) to deeper waters is small compared to advective transport except for perfluorodecanoic acid (PFDA; 35% of vertical flux) and precursor compounds to PFOS (up to 86%). We find higher than expected bioaccumulation factors (BAFs = Cplankton/Cwater) for perfluorinated carboxylic acids (PFCAs) with five and six carbons (log BAF = 2.9–3.4) and linear PFOS (log BAF = 2.6–4.3) in marine plankton compared to PFCAs with 7–11 carbons. We postulate that this reflects additional contributions from precursor compounds. Known precursor compounds detected here have among the highest BAFs (log BAF \u3e 3.0) for all PFAS in this study, suggesting that additional research on the bioaccumulation potential of unknown organofluorine compounds is urgently needed

Mercury Exposure from Domestic and Imported Estuarine and Marine Fish in the U.S. Seafood Market

BACKGROUND: Methylmercury exposure causes a variety of adverse effects on human health. Per capita estimates of mercury exposure are critical for risk assessments and for developing effective risk management strategies. OBJECTIVE: This study investigated the impact of natural stochasticity in mercury concentrations among fish and shellfish harvested from the Atlantic Ocean, Pacific Ocean, and foreign shores on estimated mercury exposures. METHODS: Mercury concentrations and seafood consumption are grouped by supply region (Atlantic Ocean, Pacific Ocean, and foreign shores). Distributions of intakes from this study are compared with values obtained using national FDA (Food and Drug Administration) mercury survey data to assess the significance of geographic variability in mercury concentrations on exposure estimates. RESULTS: Per capita mercury intake rates calculated using FDA mercury data differ significantly from those based on mercury concentration data for each supply area and intakes calculated for the 90th percentile of mercury concentrations. CONCLUSIONS: Differences in reported mercury concentrations can significantly affect per capita mercury intake estimates, pointing to the importance of spatially refined mercury concentration data. This analysis shows that national exposure estimates are most influenced by reported concentrations in imported tuna, swordfish, and shrimp; Pacific pollock; and Atlantic crabs. Collecting additional mercury concentration data for these seafood categories would improve the accuracy of national exposure estimates

North Atlantic Deep Water formation inhibits high Arctic contamination by continental perfluorooctane sulfonate discharges

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 phase-out 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 Subarctic 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

Legacy Impacts of All-Time Anthropogenic Emissions on the Global Mercury Cycle

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.Engineering and Applied Science

A Data-Driven Design Evaluation Tool for Handheld Device Soft Keyboards

Thumb interaction is a primary technique used to operate small handheld devices such as smartphones. Despite the different techniques involved in operating a handheld device compared to a personal computer, the keyboard layouts for both devices are similar. A handheld device keyboard that considers the physical capabilities of the thumb may improve user experience. We developed and applied a design evaluation tool for different geometries of the QWERTY keyboard using a performance evaluation model. The model utilizes previously collected data on thumb motor performance and posture for different tap locations and thumb movement directions. We calculated a performance index (PITOT, 0 is worst and 2 is best) for 663 designs consisting in different combinations of three variables: the keyboard's radius of curvature (R) (mm), orientation (O) (°), and vertical location on the screen (L). The current standard keyboard performed poorly (PITOT = 0.28) compared to other designs considered. Keyboard location (L) contributed to the greatest variability in performance out of the three design variables, suggesting that designers should modify this variable first. Performance was greatest for designs in the middle keyboard location. In addition, having a slightly upward curve (R = −20 mm) and orientated perpendicular to the thumb's long axis (O = −20°) improved performance to PITOT = 1.97. Poorest performances were associated with placement of the keyboard's spacebar in the bottom right corner of the screen (e.g., the worst was for R = 20 mm, O = 40°, L = Bottom (PITOT = 0.09)). While this evaluation tool can be used in the design process as an ergonomic reference to promote user motor performance, other design variables such as visual access and usability still remain unexplored

Decadal Changes in the Edible Supply of Seafood and Methylmercury Exposure in the United States

Background: Methylmercury (MeHg) exposure is associated with adverse effects on neurodevelopment and cardiovascular health. Previous work indicates most MeHg is from marine fish sold in the commercial market, but does not fully resolve supply regions globally. This information is critical for linking changes in environmental MeHg levels to human exposure in the U.S. population. Objectives: We used available data to estimate the geographic origins of seafood consumed in the United States (major ocean basins, coastal fisheries, aquaculture, freshwater) and how shifts in edible supply affected MeHg exposures between 2000–2002 and 2010–2012. Methods: Source regions for edible seafood and MeHg exposure in the United States were characterized from national and international landing, export and import data from the Food and Agricultural Organization of the United Nations and the U.S. National Marine Fisheries Service. Results: Our analysis suggests 37% of U.S. population-wide MeHg exposure is from mainly domestic coastal systems and 45% from open ocean ecosystems. We estimate that the Pacific Ocean alone supplies more than half of total MeHg exposure. Aquaculture and freshwater fisheries together account for an estimated 18% of total MeHg intake. Shifts in seafood types and supply regions between 2000–2002 and 2010–2012 reflect changes in consumer preferences (e.g., away from canned light meat tuna), global ecosystem shifts (e.g., northern migration of cod stocks), and increasing supply from aquaculture (e.g., shrimp and salmon). Conclusion: Our findings indicate global actions that reduce anthropogenic Hg emissions will be beneficial for U.S. seafood consumers because open ocean ecosystems supply a large fraction of their MeHg exposure. However, our estimates suggest that domestic actions can provide the greatest benefit for coastal seafood consumers. https://doi.org/10.1289/EHP264

Modelling the mercury stable isotope distribution of Earth surface reservoirs: Implications for global Hg cycling

Mercury (Hg) stable isotopes are useful to understand Hg biogeochemical cycling because physical, chemical and biological processes cause characteristic Hg isotope mass-dependent (MDF) and mass-independent (MIF) fractionation. Here, source Hg isotope signatures and process-based isotope fractionation factors are integrated into a fully coupled, global atmospheric-terrestrial-oceanic box model of MDF (delta Hg-202), odd-MIF (Delta Hg-199) and even-MIF (Delta Hg-200). Using this bottom-up approach, we find that the simulated Hg isotope compositions are inconsistent with the observations. We then fit the Hg isotope enrichment factors for MDF, odd-MIF and even-MIF to observational Hg isotope constraints. The MDF model suggests that atmospheric Hg-0 photo-oxidation should enrich heavy Hg isotopes in the reactant Hg-0, in contrast to the experimental observations of Hg-0 photo-oxidation by Br. The fitted enrichment factor of terrestrial Hg-0 emission in the odd-MIF model (5 parts per thousand) is likely biased high, suggesting that the terrestrial Hg-0 emission flux (160 Mg yr(-1)) used in our standard model is underestimated. In the even-MIF model, we find that a small positive atmospheric Hg-0 photo-oxidation enrichment factor (0.22 parts per thousand) along with enhanced atmospheric Hg-II photo-reduction and atmospheric Hg-0 dry deposition (foliar uptake) fluxes to the terrestrial reservoir are needed to match Delta Hg-200 observations. Marine Hg isotope measurements are needed to further expand the use of Hg isotopes in understanding global Hg cycling. (C) 2018 Elsevier Ltd. All rights reserved

Global 3-D Land-Ocean-Atmosphere Model for Mercury: Present-Day Versus Preindustrial Cycles and Anthropogenic Enrichment Factors for Deposition

We develop a mechanistic representation of land-atmosphere cycling in a global 3-D ocean-atmosphere model of mercury (GEOS-Chem). The resulting land-ocean-atmosphere 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−1 for present day), soil volatilization (550 Mg a−1), and evapotranspiration (550 Mg a−1). 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.Earth and Planetary SciencesEngineering and Applied Science

Vertical Profiles, Sources and Transport of PFASs in the Arctic Ocean

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: \u3c5 – 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 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 \u3c5-41 pg/L). Modeled deep water concentrations below 200 m (5-15 pg/L) were slightly higher than measurements (\u3c5 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 projected to continue increasing to 2038

Anthropogenic Impacts on Global Storage and Emissions of Mercury from Terrestrial Soils: Insights from a New Global Model

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 $\sim20\%$ 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 $\sim80$ years. Our analysis suggests that reductions in anthropogenic emissions would lead to immediate and large reductions in secondary soil mercury emissions.Engineering and Applied Science