Rivers are an important source of mercury (Hg) to marine ecosystems. Based on an analysis of compiled observations, we estimate global present-day Hg discharges from rivers to ocean margins are 27 ± ...13 Mmol a–1 (5500 ± 2700 Mg a–1), of which 28% reaches the open ocean and the rest is deposited to ocean margin sediments. Globally, the source of Hg to the open ocean from rivers amounts to 30% of atmospheric inputs. This is larger than previously estimated due to accounting for elevated concentrations in Asian rivers and variability in offshore transport across different types of estuaries. Riverine inputs of Hg to the North Atlantic have decreased several-fold since the 1970s while inputs to the North Pacific have increased. These trends have large effects on Hg concentrations at ocean margins but are too small in the open ocean to explain observed declines of seawater concentrations in the North Atlantic or increases in the North Pacific. Burial of Hg in ocean margin sediments represents a major sink in the global Hg biogeochemical cycle that has not been previously considered. We find that including this sink in a fully coupled global biogeochemical box model helps to balance the large anthropogenic release of Hg from commercial products recently added to global inventories. It also implies that legacy anthropogenic Hg can be removed from active environmental cycling on a faster time scale (centuries instead of millennia). Natural environmental Hg levels are lower than previously estimated, implying a relatively larger impact from human activity.
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IJS, KILJ, NUK, PNG, UL, UM
Humans are exposed to poly- and perfluoroalkyl substances (PFASs) from diverse sources and this has been associated with negative health impacts. Advances in analytical methods have enabled routine ...detection of more than 15 PFASs in human sera, allowing better profiling of PFAS exposures. The composition of PFASs in human sera reflects the complexity of exposure sources but source identification can be confounded by differences in toxicokinetics affecting uptake, distribution, and elimination. Common PFASs, such as perfluorooctanoic acid (PFOA), perfluorooctane sulfonic acid (PFOS) and their precursors are ubiquitous in multiple exposure sources. However, their composition varies among sources, which may impact associated adverse health effects.
We use available PFAS concentrations from several demographic groups in a North Atlantic seafood consuming population (Faroe Islands) to explore whether chemical fingerprints in human sera provide insights into predominant exposure sources. We compare serum PFAS profiles from Faroese individuals to other North American populations to investigate commonalities in potential exposure sources. We compare individuals with similar demographic and physiological characteristics and samples from the same years to reduce confounding by toxicokinetic differences and changing environmental releases.
Using principal components analysis (PCA) confirmed by hierarchical clustering, we assess variability in serum PFAS concentrations across three Faroese groups. The first principal component (PC)/cluster consists of C9-C12 perfluoroalkyl carboxylates (PFCAs) and is consistent with measured PFAS profiles in consumed seafood. The second PC/cluster includes perfluorohexanesulfonic acid (PFHxS) and the PFOS precursor N-ethyl perfluorooctane sulfonamidoacetate (N-EtFOSAA), which are directly used or metabolized from fluorochemicals in consumer products such as carpet and food packaging. We find that the same compounds are associated with the same exposure sources in two North American populations, suggesting generalizability of results from the Faroese population.
We conclude that PFAS homologue profiles in serum provide valuable information on major exposure sources. It is essential to compare samples collected at similar time periods and to correct for demographic groups that are highly affected by differences in physiological processes (e.g., pregnancy). Information on PFAS homologue profiles is crucial for attributing adverse health effects to the proper mixtures or individual PFASs.
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DOBA, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
Rivers discharge 28 ± 13 Mmol yr−1 of mercury (Hg) to ocean margins, an amount comparable to atmospheric deposition to the global oceans. Most of the Hg discharged by rivers is sequestered by burial ...of benthic sediment in estuaries or the coastal zone, but some is evaded to the atmosphere and some is exported to the open ocean. We investigate the fate of riverine Hg by developing a new global 3‐D simulation for Hg in the Massachusetts Institute of Technology ocean general circulation model. The model includes plankton dynamics and carbon respiration (DARWIN project model) coupled to inorganic Hg chemistry. Results are consistent with observed spatial patterns and magnitudes of surface ocean Hg concentrations. We use observational constraints on seawater Hg concentrations and evasion to infer that most Hg from rivers is sorbed to refractory organic carbon and preferentially buried. Only 6% of Hg discharged by rivers (1.8 Mmol yr−1) is transported to the open ocean on a global basis. This fraction varies from a low of 2.6% in East Asia due to the barrier imposed by the Korean Peninsula and Japanese archipelago, up to 25% in eastern North America facilitated by the Gulf Stream. In the Arctic Ocean, low tributary particle loads and efficient degradation of particulate organic carbon by deltaic microbial communities favor a more labile riverine Hg pool. Evasion of Hg to the Arctic atmosphere is indirectly enhanced by heat transport during spring freshet that accelerates sea ice melt and ice rafting. Discharges of 0.23 Mmol Hg yr−1 from Arctic rivers can explain the observed summer maximum in the Arctic atmosphere, and this magnitude of releases is consistent with recent observations. Our work indicates that rivers are major contributors to Hg loads in the Arctic Ocean.
Key Points
Most of river Hg discharged to ocean is refractory
Long‐range transport of riverine Hg is enhanced by major ocean currents
Circumpolar rivers carry more reactive Hg
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Mercury (Hg) stable isotope signatures are widely used to understand Hg cycling in the environment. Sample preparation methods for determining Hg isotope ratios by CV-MC-ICP-MS vary widely among ...laboratory facilities and sample types. Here, we present a novel and rapid method for preparing solid samples prior to determining Hg isotope composition. We use a direct Hg analyzer (that measures total Hg) for sample combustion, amalgamation and analysis. During the thermal release of Hg from the amalgamator and following detection, the analyte gas enters a trapping solution consisting of 10% HCl/BrCl (5:1, vol/vol). We find Hg blank values are less than 1% of the Hg introduced during sample analysis, Hg detection is not altered by modifying the system, and more than 90% of the introduced Hg is recovered in the trapping solution. Hg isotope results are statistically indistinguishable from accepted values for previously published certified reference materials and uncertainty of 2σ (0.05–0.12‰) is similar to the solution standard RM8610 (2σ = 0.09‰). This new method allows for solid sample preparation for Hg isotope analysis in under 15 min. It has the additional advantage of minimizing use of sample mass during simultaneous detection and preparation.
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•Preconcentration of Hg during total Hg analysis reduces preparation time and sample mass required.•Sample preparation for Hg isotope analysis only takes ∼8 min.•Hg isotope analysis of SRMs matches literature data with good reproducibility.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Per- and polyfluoroalkyl substances (PFAS) are a diverse class of highly persistent anthropogenic chemicals that are detectable in the serum of most humans. PFAS exposure has been associated with ...many adverse effects on human health including immunotoxicity, increased risk of certain cancers, and metabolic disruption. PFAS binding to the most abundant blood serum proteins (human serum albumin HSA and globulins) is thought to affect transport to active sites, toxicity, and elimination half-lives. However, few studies have investigated the competitive binding of PFAS to these proteins in human serum. Here, we use C18 solid-phase microextraction fibers to measure HSA–water and globulin–water distribution coefficients (D HSA/w, D glob/w) for PFAS with carbon chains containing 4 to 13 perfluorinated carbons (ηpfc = 4–13) and several functional head-groups. PFAS with ηpfc < 7 were highly bound to HSA relative to globulins, whereas PFAS with ηpfc ≥ 7 showed a greater propensity for binding to globulins. Experimentally measured D HSA/w and D glob/w and concentrations of serum proteins successfully predicted the variability in PFAS binding in human serum. We estimated that the unbound fraction of serum PFAS varied by up to a factor of 2.5 among individuals participating in the 2017–2018 U.S. National Health and Nutrition Examination Survey. These results suggest that serum HSA and globulins are important covariates for epidemiological studies aimed at understanding the effects of PFAS exposure.
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IJS, KILJ, NUK, PNG, UL, UM
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
Per- and polyfluoroalkyl substances (PFAS) are a class of thousands of persistent, organic fluorinated chemicals added to materials and products mainly to repel stains and water. PFAS have been ...associated with many adverse human health effects. We aimed to determine whether buildings with “healthier” materialsdefined here as reportedly free of all PFASexhibit lower PFAS in dust. In addition to analyzing targeted PFAS with available commercial standards, we measured extractable organic fluorine (EOF) as a novel proxy that includes both known and unknown types of PFAS. We measured at least 15 targeted PFAS (n = 24), EOF (n = 24), and total fluorine (TF; n = 14) in dust collected from university common spaces and classrooms, half of which had “healthier” furniture and carpet. We observed lower PFAS contamination in buildings with “healthier” materials: “healthier” rooms had a 66% lower median summed PFAS and a 49% lower Kaplan–Meier estimated mean EOF level in dust in comparison to conventional rooms. The summed targeted PFAS were significantly correlated with EOF but accounted for up to only 9% of EOF, indicating the likely presence of unidentified PFAS. EOF levels explained less than 1% of TF in dust. We emphasize the need to use chemical class-based methods (e.g., EOF) for evaluating class-based solutions and to expand non-PFAS solutions for other building materials.
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IJS, KILJ, NUK, PNG, UL, UM
Per- and polyfluoroalkyl substances (PFAS) are a class of over 4700 fluorinated compounds used in industry and consumer products. Studies have highlighted the use of aqueous film-forming foams ...(AFFFs) as an exposure source for firefighters, but little is known about PFAS occurrence inside fire stations, where firefighters spend most of their shifts. In this study, we aimed to characterize PFAS concentrations and sources inside fire stations. We measured 24 PFAS (using LC-MS/MS) and total fluorine (using particle-induced gamma ray emission) in dust from multiple rooms of 15 Massachusetts stations, many of which (60%) no longer use PFAS-containing AFFF at all and the rest of which only use it very rarely. Compared to station living rooms, turnout gear locker rooms had higher dust levels of total fluorine (p < 0.0001) and three PFAS: perfluorohexanoate (PFHxA), perfluoroheptanoate (PFHpA), and perfluorodecanoate (PFDoDA) (p < 0.05). These PFAS were also found on six wipes of station turnout gear. By contrast, the dominant PFAS in living rooms was N-ethyl perfluorooctane sulfonamidoacetic acid (N-MeFOSAA), a precursor to perfluorooctane sulfonate (PFOS) that still persists despite phase-outs almost two decades ago. The Σ
PFAS accounted for less than 2% of fluorine in dust (n = 39), suggesting the potential presence of unknown PFAS. Turnout gear may be an important PFAS source in stations due to intentional additives and/or contamination from firefighting activities.
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EMUNI, FIS, FZAB, GEOZS, GIS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
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.
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
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