Four Decades of Spatiotemporal Variability of Per- and Polyfluoroalkyl Substances (PFASs) in the Baltic Sea.

Temporal and spatial variability of per- and polyfluoroalkyl substances (PFASs) in herring, cod, eelpout, and guillemot covering four decades and more than 1000 km in the Baltic Sea was investigated to evaluate the effect of PFAS regulations and residence times of PFASs. Overall, PFAS concentrations responded rapidly to recent regulations but with some notable basin- and homologue-specific variability. The well-ventilated Kattegat and Bothnian Bay showed a faster log-linear decrease for most PFASs than the Baltic Proper, which lacks a significant loss mechanism. PFOS and FOSA, for example, have decreased with 0-7% y-1 in the Baltic Proper and 6-16% y-1 in other basins. PFNA and partly PFOA are exceptions and continue to show stagnant or increasing concentrations. Further, we found that Bothnian Bay herring contained the highest concentrations of >C12 perfluoroalkyl carboxylic acids (PFCAs), likely from rivers with high loads of dissolved organic carbon. In the Kattegat, low PFAS concentrations, but a high FOSA fraction, could be due to influence from the North Sea inflow below the halocline and possibly a local source of FOSA and/or isomer-specific biotransformation. This study represents the most comprehensive spatial and temporal investigation of PFASs in Baltic wildlife while providing new insights into cycling of PFASs within the Baltic Sea ecosystem.

Long-term dataset for contaminants in fish, mussels, and bird eggs from the Baltic Sea.

Widespread persistent contaminants are a global environmental problem. In the Baltic Sea, wildlife contamination was first noticed in the 1960s, prompting the Swedish Environmental Protection Agency to establish a comprehensive Swedish National Monitoring Programme for Contaminants in Marine Biota (MCoM) in 1978 run by the Swedish Museum of Natural History. Eight species have been analysed, four fish species (Atlantic herring, Atlantic cod, European perch, viviparous eelpout), one bivalve species (blue mussel), and egg from three bird species (common guillemot, common tern, Eurasian oystercatcher). Here, we present a dataset containing MCoM data from its start until 2021. It includes 36 sets of time-series, each analysed for more than 100 contaminants. The longest time-series is for common guillemot and starts in 1968. We describe the structure of MCoM including historic changes to the number of stations, sample treatment, analytical methods, instruments, and laboratories. The MCoM data is available at the Bolin Centre repository and on GitHub through our R package mcomDb. The latter will be updated yearly with new MCoM records.

Cross-shelf processes of terrigenous organic matter drive mercury speciation on the east siberian shelf in the Arctic Ocean.

The cross-shelf distributions of total mercury (THg), methylmercury (MeHg) and organic and inorganic matter, as well as the presence of the hgcA gene were investigated on the East Siberian Shelf (ESS) to understand the processes underlying the speciation of sedimentary Hg. Samples were collected from 12 stations grouped into four zones based on water depth: inner shelf (5 stations), mid-shelf (3 stations), outer shelf (2 stations), and slope (2 stations). The THg concentration in the surface sediment increased from the inner shelf (0.25 ± 0.023 nmol g-1) toward the slope (0.52 nmol g-1), and, when normalized to total organic carbon content, the THg showed a positive correlation with the clay-to-sand ratio (r2 = 0.48, p = 0.012) and degree of chemical weathering (r2 = 0.79, p = 0.0001). The highest MeHg concentrations (3.0 ± 1.8 pmol g-1), as well as peaks in the S/C ratio (0.012 ± 0.002) of sediment-leached organic matter, were found on the mid-shelf, suggesting that the activities of sulfate reducers control the net Hg(II) methylation rates in the sediment. This was supported by results from a principal component analysis (PCA) performed with Hg species concentrations and sediment-leached organic matter compositions. The site-specific variation in MeHg showed the highest similarity with that of CHONS compounds in the PCA, where Deltaproteobacteria were projected to be putative Hg(II) methylators in the gene analysis. In summary, the hydrodynamic sorting of lithogenic particles appears to govern the cross-shelf distribution of THg, and in situ methylation is considered a major source of MeHg in the ESS sediment.

Mercury Sources and Fate in a Large Brackish Ecosystem (the Baltic Sea) Depicted by Stable Isotopes.

Identifying Hg sources to aquatic ecosystems and processes controlling the levels of monomethylmercury (MMHg) is critical for developing efficient policies of Hg emissions reduction. Here we measured Hg concentrations and stable isotopes in sediment, seston, and fishes from the various basins of the Baltic Sea, a large brackish ecosystem presenting extensive gradients in salinity, redox conditions, dissolved organic matter (DOM) composition, and biological activities. We found that Hg mass dependent fractionation (Hg-MDF) values in sediments mostly reflect a mixing between light terrestrial Hg and heavier industrial sources, whereas odd Hg isotope mass independent fractionation (odd Hg-MIF) reveals atmospheric inputs. Seston presents intermediate Hg-MDF and odd Hg-MIF values falling between sediments and fish, but in northern basins, high even Hg-MIF values suggest the preferential accumulation of wet-deposited Hg. Odd Hg-MIF values in fish indicate an overall low extent of MMHg photodegradation due to limited sunlight exposure and penetration but also reveal large spatial differences. The photodegradation extent is lowest in the central basin with recurrent algal blooms due to their shading effect and is highest in the northern, least saline basin with high concentrations of terrestrial DOM. As increased loads of terrestrial DOM are expected in many coastal areas due to global changes, its impact on MMHg photodegradation needs to be better understood and accounted for when predicting future MMHg concentrations in aquatic ecosystems.

Per- and polyfluoroalkyl substances (PFAS) in white-tailed sea eagle eggs from Sweden: temporal trends (1969-2021), spatial variations, fluorine mass balance, and suspect screening.

Temporal and spatial trends of 15 per- and polyfluoroalkyl substances (PFAS) were determined in white-tailed sea eagle (WTSE) eggs (Haliaeetus albicilla) from two inland and two coastal regions of Sweden between 1969 and 2021. PFAS concentrations generally increased from ∼1969 to ∼1990s-2010 (depending on target and site) and thereafter plateaued or declined, with perfluorooctane sulfonamide (FOSA) and perfluorooctane sulfonate (PFOS) declining faster than most perfluoroalkyl carboxylic acids (PFCAs). The net result was a shift in the PFAS profile from PFOS-dominant in 1969-2010 to an increased prevalence of PFCAs over the last decade. Further, during the entire period higher PFAS concentrations were generally observed in coastal populations, possibly due to differences in diet and/or proximity to more densely populated areas. Fluorine mass balance determination in pooled samples from three of the regions (2019-2021) indicated that target PFAS accounted for the vast majority (i.e. 81-100%) of extractable organic fluorine (EOF). Nevertheless, high resolution mass-spectrometry-based suspect screening identified 55 suspects (31 at a confidence level [CL] of 1-3 and 24 at a CL of 4-5), of which 43 were substances not included in the targeted analysis. Semi-quantification of CL ≤ 2 suspects increased the identified EOF to >90% in coastal samples. In addition to showing the impact of PFAS regulation and phase-out initiatives, this study demonstrates that most extractable organofluorine in WTSE eggs is made up of known (legacy) PFAS, albeit with low levels of novel substances.

Fish tissue conversion factors for mercury, cadmium, lead and nine per- and polyfluoroalkyl substances for use within contaminant monitoring.

Fish tissue levels have to comply with environmental quality standards (EQSs) within the European Water Framework Directive. However, within monitoring, contaminants are sometimes measured in a different tissue than the tissue for which the environmental (whole fish) or human (fillet (equivalent to muscle tissue)) quality standard is set. Tissue conversion factors (k), describing the relationship between concentrations in different tissues, can be used to obtain a quality standard for the appropriate tissue. Several different approaches have been suggested for the calculation of k. For monitoring purposes, we propose the use of a simple, easy reproducible approach that assumes proportionality between two tissue, or tissue and whole fish, concentrations. This allows for an easy comparison of studies and adoption of ks into independent monitoring programs. Here, we determined ks for three metals (mercury (Hg), lead (Pb), cadmium (Cd)) and nine per- and polyfluoroalkyl substances (PFAS) including perfluorooctanesulfonic acid (PFOS) across six marine and freshwater fish species from Northern European lakes and the Baltic Sea. We found significant species differences for Hg for kmuscle/whole fish, for Cd and Pb for kliver/whole fish and for Cd for kliver/muscle. For perfluoroalkyl carboxylic acids (PFCA), we found a chain length dependence with lowest kliver/muscle at low and high chain lengths (C8, C13) and highest for median chain lengths (C9-C12). Further, there were differences between fish species with kliver/muscle for PFOS almost doubling from eelpout (10.3) to herring (19.2) and increasing up to a factor 4 between eelpout and herring for other PFASs. FOSA had two distinctive groups, herring with a kliver/muscle of 48.7 and a second group with ks of 2.3 to 5.9 for all other fish species. Our results suggest that differences in the tissue somatic index, and contaminant uptake, tissue transfer and metabolism result in the need for species-specific ks within monitoring.

Expression Levels of hgcAB Genes and Mercury Availability Jointly Explain Methylmercury Formation in Stratified Brackish Waters.

Neurotoxic methylmercury (MeHg) is formed by microbial methylation of inorganic divalent Hg (HgII) and constitutes severe environmental and human health risks. The methylation is enabled by hgcA and hgcB genes, but it is not known if the associated molecular-level processes are rate-limiting or enable accurate prediction of MeHg formation in nature. In this study, we investigated the relationships between hgc genes and MeHg across redox-stratified water columns in the brackish Baltic Sea. We showed, for the first time, that hgc transcript abundance and the concentration of dissolved HgII-sulfide species were strong predictors of both the HgII methylation rate and MeHg concentration, implying their roles as principal joint drivers of MeHg formation in these systems. Additionally, we characterized the metabolic capacities of hgc+ microorganisms by reconstructing their genomes from metagenomes (i.e., hgc+ MAGs), which highlighted the versatility of putative HgII methylators in the water column of the Baltic Sea. In establishing relationships between hgc transcripts and the HgII methylation rate, we advance the fundamental understanding of mechanistic principles governing MeHg formation in nature and enable refined predictions of MeHg levels in coastal seas in response to the accelerating spread of oxygen-deficient zones.

Spatial and temporal variations in riverine mercury in the Mackenzie River Basin, Canada, from community-based water quality monitoring data.

Arctic rivers deliver ~40 t yr-1 of mercury (Hg) to the Arctic Ocean, ~6 % of which is from the Mackenzie River Basin (MRB), a region warming at ~3 times the mean hemispheric rate. How this will affect Hg transfer to ecosystems of the Beaufort Sea is a worrying issue. To help address this question, we analyzed >500 measurements of Hg and other water properties from 22 rivers collected in 2012-2018 by communities of the MRB. This new dataset provides a more comprehensive view of riverine Hg variations across the basin than was previously available. We find that rivers issued from mountains in the western MRB contribute the largest share of Hg in the Mackenzie River, 60-95 % of it being carried as fine suspended solids and probably sourced from riverbank erosion and thaw slumps. In contrast, lowland rivers of the central and eastern MRB contribute larger shares of dissolved Hg (up to 78 %), likely from recent atmospheric deposition through precipitation. Using load modelling constrained by the new water quality dataset, we estimate that the three largest western tributaries (Liard, Peel and Arctic Red rivers) of the Mackenzie contribute 60 % of the annual MRB THg export and DHg export to the Beaufort Sea during freshet, as well as 51 % of DHg export, while supplying 60 % of freshet discharge. Load modelling also reveals a sustained decline in DHg loads of ~13 kg yr-1 between 2001 and 2016 in the lower Mackenzie River, which likely reflect a decreasing trend in atmospheric Hg deposition over most of northwestern Canada during this period. This study highlights the value of community-based water quality monitoring in helping to support assessments of riverine Hg in the MRB in support of the Minamata Convention on Mercury.

What are the likely changes in mercury concentration in the Arctic atmosphere and ocean under future emissions scenarios?

Arctic mercury (Hg) concentrations respond to changes in anthropogenic Hg emissions and environmental change. This manuscript, prepared for the 2021 Arctic Monitoring and Assessment Programme Mercury Assessment, explores the response of Arctic Ocean Hg concentrations to changing primary Hg emissions and to changing sea-ice cover, river inputs, and net primary production. To do this, we conduct a model analysis using a 2015 Hg inventory and future anthropogenic Hg emission scenarios. We model future atmospheric Hg deposition to the surface ocean as a flux to the surface water or sea ice using three scenarios: No Action, New Policy (NP), and Maximum Feasible Reduction (MFR). We then force a five-compartment box model of Hg cycling in the Arctic Ocean with these scenarios and literature-derived climate variables to simulate environmental change. No Action results in a 51% higher Hg deposition rate by 2050 while increasing Hg concentrations in the surface water by 22% and <9% at depth. Both "action" scenarios (NP and MFR), implemented in 2020 or 2035, result in lower Hg deposition ranging from 7% (NP delayed to 2035) to 30% (MFR implemented in 2020) by 2050. Under this last scenario, ocean Hg concentrations decline by 14% in the surface and 4% at depth. We find that the sea-ice cover decline exerts the strongest Hg reducing forcing on the Arctic Ocean while increasing river discharge increases Hg concentrations. When modified together the climate scenarios result in a ≤5% Hg decline by 2050 in the Arctic Ocean. Thus, we show that the magnitude of emissions-induced future changes in the Arctic Ocean is likely to be substantial compared to climate-induced effects. Furthermore, this study underscores the need for prompt and ambitious action for changing Hg concentrations in the Arctic, since delaying less ambitious reduction measures-like NP-until 2035 may become offset by Hg accumulated from pre-2035 emissions.

Selenium concentration in herring from the Baltic Sea tracks decadal and spatial trends in external sources.

Selenium (Se) has a narrow range between nutritionally optimal and toxic concentrations for many organisms, including fish and humans. However, the degree to which humans are affecting Se concentrations in coastal food webs with diffuse Se sources is not well described. Here we examine large-scale drivers of spatio-temporal variability in Se concentration in herring from the Baltic Sea (coastal sea) to explore the anthropogenic impact on a species from the pelagic food web. We analyze data from three herring muscle time series covering three decades (1979-2010) and herring liver time series from 20 stations across the Baltic Sea covering a fourth decade (2009-2019). We find a 0.7-2.0% per annum (n = 26-30) Se decline in herring muscle samples from 0.34 ± 0.02 µg g-1 ww in 1979-1981 to 0.18 ± 0.03 µg g-1 ww in 2008-2010. This decrease continues in the liver samples during the fourth decade (6 of 20 stations show significant decrease). We also find increasing North-South and East-West gradients in herring Se concentrations. Using our observations, modelled Se deposition (spatio-temporal information) and estimated Se river discharge (spatial information), we show that the spatial variability in herring Se tracks the variability in external source loads. Further, between 1979 and 2010 we report a ∼5% per annum decline in direct Se deposition and a more gradual, 0.7-2.0% per annum, decline in herring Se concentrations. The slower rate of decrease for herring can be explained by stable or only slowly decreasing riverine inputs of Se to the Baltic Sea as well as recycling of Se within the coastal system. Both processes can reduce the effect of the trend predicted from direct Se deposition. We show that changing atmospheric emissions of Se may influence Se concentrations of a pelagic fish species in a coastal area through direct deposition and riverine inputs from the terrestrial landscape.

Sources of riverine mercury across the Mackenzie River Basin; inferences from a combined HgC isotopes and optical properties approach.

The Arctic environment harbors a complex mosaic of mercury (Hg) and carbon (C) reservoirs, some of which are rapidly destabilizing in response to climate warming. The sources of riverine Hg across the Mackenzie River basin (MRB) are uncertain, which leads to a poor understanding of potential future release. Measurements of dissolved and particulate mercury (DHg, PHg) and carbon (DOC, POC) concentration were performed, along with analyses of Hg stable isotope ratios (incl. ∆199Hg, δ202Hg), radiocarbon content (∆14C) and optical properties of DOC of river water. Isotopic ratios of Hg revealed a closer association to terrestrial Hg reservoirs for the particulate fraction, while the dissolved fraction was more closely associated with atmospheric deposition sources of shorter turnover time. There was a positive correlation between the ∆14C-OC and riverine Hg concentration for both particulate and dissolved fractions, indicating that waters transporting older-OC (14C-depleted) also contained higher levels of Hg. In the dissolved fraction, older DOC was also associated with higher molecular weight, aromaticity and humic content, which are likely associated with higher Hg-binding potential. Riverine PHg concentration increased with turbidity and SO4 concentration. There were large contrasts in Hg concentration and OC age and quality among the mountain and lowland sectors of the MRB, which likely reflect the spatial distribution of various terrestrial Hg and OC reservoirs, including weathering of sulfate minerals, erosion and extraction of coal deposits, thawing permafrost, forest fires, peatlands, and forests. Results revealed major differences in the sources of particulate and dissolved riverine Hg, but nonetheless a common positive association with older riverine OC. These findings reveal that a complex mixture of Hg sources, supplied across the MRB, will contribute to future trends in Hg export to the Arctic Ocean under rapid environmental changes.

Interval breast cancer rates for digital breast tomosynthesis versus digital mammography population screening: An individual participant data meta-analysis.

BACKGROUND: Digital breast tomosynthesis (DBT) improves breast cancer (BC) detection compared to mammography, however, it is unknown whether this reduces interval cancer rate (ICR) at follow-up. METHODS: Using individual participant data (IPD) from DBT screening studies (identified via periodic literature searches July 2016 to November 2019) we performed an IPD meta-analysis. We estimated ICR for DBT-screened participants and the difference in pooled ICR for DBT and mammography-only screening, and compared interval BC characteristics. Two-stage meta-analysis (study-specific estimation, pooled synthesis) of ICR included random-effects, adjusting for study and age, and was estimated in age and density subgroups. Comparative screening sensitivity was calculated using screen-detected and interval BC data. FINDINGS: Four prospective DBT studies, from European population-based programs, contributed IPD for 66,451 DBT-screened participants: age-adjusted pooled ICR was 13.17/10,000 (95%CI: 8.25-21.02). Pooled ICR was higher in the high-density (21.08/10,000; 95%CI: 6.71-66.27) than the low-density (8.63/10,000; 95%CI: 5.25-14.192) groups (P = 0.03) however estimates did not differ across age-groups (P = 0.32). Based on two studies that also provided data for 153,800 mammography screens (age-adjusted ICR 17.69/10,000; 95%CI: 13.22-23.66), DBT's pooled ICR was 16.83/10,000 (95%CI: 11.89-23.82). Comparative meta-analysis showed a non-significant difference in ICR (-0.44/10,000; 95%CI: -11.00-10.11) and non-significant difference in screening sensitivity (6.79%; 95%CI: -0.73-14.87%) between DBT and DM but a significant pooled difference in cancer detection rate of 33.49/10,000 (95%CI: 23.88-43.10). Distribution of interval BC prognostic characteristics did not differ between screening modalities except that those occurring in DBT-screened participants were significantly more likely to be negative for axillary-node metastases (P = 0.005). INTERPRETATION: Although heterogeneity in ICR estimates and few datasets limit recommendations, there was no difference between DBT and mammography in pooled ICR despite DBT increasing cancer detection.

Deltaproteobacteria and Spirochaetes-Like Bacteria Are Abundant Putative Mercury Methylators in Oxygen-Deficient Water and Marine Particles in the Baltic Sea.

Methylmercury (MeHg), a neurotoxic compound biomagnifying in aquatic food webs, can be a threat to human health via fish consumption. However, the composition and distribution of the microbial communities mediating the methylation of mercury (Hg) to MeHg in marine systems remain largely unknown. In order to fill this knowledge gap, we used the Baltic Sea Reference Metagenome (BARM) dataset to study the abundance and distribution of the genes involved in Hg methylation (the hgcAB gene cluster). We determined the relative abundance of the hgcAB genes and their taxonomic identity in 81 brackish metagenomes that cover spatial, seasonal and redox variability in the Baltic Sea water column. The hgcAB genes were predominantly detected in anoxic water, but some hgcAB genes were also detected in hypoxic and normoxic waters. Phylogenetic analysis identified putative Hg methylators within Deltaproteobacteria, in oxygen-deficient water layers, but also Spirochaetes-like and Kiritimatiellaeota-like bacteria. Higher relative quantities of hgcAB genes were found in metagenomes from marine particles compared to free-living communities in anoxic water, suggesting that such particles are hotspot habitats for Hg methylators in oxygen-depleted seawater. Altogether, our work unveils the diversity of the microorganisms with the potential to mediate MeHg production in the Baltic Sea and pinpoint the important ecological niches for these microorganisms within the marine water column.

Mass Budget of Methylmercury in the East Siberian Sea: The Importance of Sediment Sources.

Biological concentrations of methylmercury (MeHg) are elevated throughout the Arctic Ocean; however, to date, the major sources and the spatial variability of MeHg are not well quantified. To identify the major inputs and outputs of MeHg to the Arctic shelf water column, we measured MeHg concentrations in the seawater and sediment samples from the East Siberian Sea collected from August to September 2018. We found that the MeHg concentrations in seawater and pore water were higher on the slope than on the shelf, while the MeHg concentrations in the sediment were higher on the shelf than on the slope. We created a mass budget for MeHg and found that the benthic diffusion and resuspension largely exceed other sources, such as atmospheric deposition and river water input. The major sinks of MeHg in the water column were dark demethylation and evasion. When we extrapolated our findings on benthic diffusion to the entire Arctic shelf system, the annual MeHg diffusion from the shelf sediments was estimated to be 23,065 ± 939 mol yr-1, about 2 times higher than previously proposed river discharges. Our study suggests that the MeHg input from shelf sediments in the Arctic Ocean is significant and has been previously underestimated.

Mercury-methylating bacteria are associated with copepods: A proof-of-principle survey in the Baltic Sea.

Methylmercury (MeHg) is a potent neurotoxin that biomagnifies in marine food webs. Inorganic mercury (Hg) methylation is conducted by heterotrophic bacteria inhabiting sediment or settling detritus, but endogenous methylation by the gut microbiome of animals in the lower food webs is another possible source. We examined the occurrence of the bacterial gene (hgcA), required for Hg methylation, in the guts of dominant zooplankters in the Northern Baltic Sea. A qPCR assay targeting the hgcA sequence in three main clades (Deltaproteobacteria, Firmicutes and Archaea) was used in the field-collected specimens of copepods (Acartia bifilosa, Eurytemora affinis, Pseudocalanus acuspes and Limnocalanus macrurus) and cladocerans (Bosmina coregoni maritima and Cercopagis pengoi). All copepods were found to carry hgcA genes in their gut microbiome, whereas no amplification was recorded in the cladocerans. In the copepods, hgcA genes belonging to only Deltaproteobacteria and Firmicutes were detected. These findings suggest a possibility that endogenous Hg methylation occurs in zooplankton and may contribute to seasonal, spatial and vertical MeHg variability in the water column and food webs. Additional molecular and metagenomics studies are needed to identify bacteria carrying hgcA genes and improve their quantification in microbiota.

Uptake Kinetics of Methylmercury in a Freshwater Alga Exposed to Methylmercury Complexes with Environmentally Relevant Thiols.

Cellular uptake of dissolved methylmercury (MeHg) by phytoplankton is the most important point of entry for MeHg into aquatic food webs. However, the process is not fully understood. In this study we investigated the influence of chemical speciation on rate constants for MeHg accumulation by the freshwater green microalga Selenastrum capricornutum. We used six MeHg-thiol complexes with moderate but important structural differences commonly found in the environment. Rate constants for MeHg interactions with cells were determined for the MeHg-thiol treatments and a control assay containing the thermodynamically less stable MeHgOH complex. We found both elevated amounts of MeHg associated with whole cells and higher MeHg association rate constants in the control compared to the thiol treatments. Furthermore, the association rate constants were lower when algae were exposed to MeHg complexes with thiols of larger size and more "branched" chemical structure compared to complexes with simpler structure. The results further demonstrated that the thermodynamic stability and chemical structure of MeHg complexes in the medium is an important controlling factor for the rate of MeHg interactions with the cell surface, but not for the MeHg exchange rate across the membrane. Our results are in line with uptake mechanisms involving formation of MeHg complexes with cell surface ligands prior to internalization.

A Coupled Global Atmosphere-Ocean Model for Air-Sea Exchange of Mercury: Insights into Wet Deposition and Atmospheric Redox Chemistry.

Air-sea exchange of mercury (Hg) is the largest flux between Earth system reservoirs. Global models simulate air-sea exchange based either on an atmospheric or ocean model simulation and treat the other media as a boundary condition. Here we develop a new modeling capability (NJUCPL) that couples GEOS-Chem (atmospheric model) and MITgcm (ocean model) at the native hourly model time step. The coupled model is evaluated against high-frequency simultaneous measurements of elemental mercury (Hg0) in both the atmosphere and surface ocean obtained during five published cruises in the Atlantic, Pacific, and Southern Oceans. Results indicate that the calculated global Hg net evasion flux is 12% higher for the online model than the offline model. We find that the coupled online model captures the spatial pattern of the observations; specifically, it improves the representation of peak seawater Hg0 (Hg0aq) concentration associated with enhanced precipitation in the intertropical convergence zone in both the Atlantic and the Pacific Oceans. We investigate the causes of the observed Hg0aq peaks with two sensitivity simulations and show that the high Hg0aq concentrations are associated with elevated convective cloud mass flux and bromine concentrations in the tropical upper troposphere. Observations of elevated Hg0aq concentrations in the western tropical Pacific Ocean merit further study involving BrO vertical distribution and cloud resolving models.

Methylmercury Mass Budgets and Distribution Characteristics in the Western Pacific Ocean.

Methylmercury (MeHg) accumulation in marine organisms poses serious ecosystem and human health risk, yet the sources of MeHg in the surface and subsurface ocean remain uncertain. Here, we report the first MeHg mass budgets for the Western Pacific Ocean estimated based on cruise observations. We found the major net source of MeHg in surface water to be vertical diffusion from the subsurface layer (1.8-12 nmol m-2 yr-1). A higher upward diffusion in the North Pacific (12 nmol m-2 yr-1) than in the Equatorial Pacific (1.8-5.7 nmol m-2 yr-1) caused elevated surface MeHg concentrations observed in the North Pacific. We furthermore found that the slope of the linear regression line for MeHg versus apparent oxygen utilization in the Equatorial Pacific was about 2-fold higher than that in the North Pacific. We suggest this could be explained by redistribution of surface water in the tropical convergence-divergence zone, supporting active organic carbon decomposition in the Equatorial Pacific Ocean. On the basis of this study, we predict oceanic regions with high organic carbon remineralization to have enhanced MeHg concentrations in both surface and subsurface waters.

Eutrophication Increases Phytoplankton Methylmercury Concentrations in a Coastal Sea-A Baltic Sea Case Study.

Eutrophication is expanding worldwide, but its implication for production and bioaccumulation of neurotoxic monomethylmercury (MeHg) is unknown. We developed a mercury (Hg) biogeochemical model for the Baltic Sea and used it to investigate the impact of eutrophication on phytoplankton MeHg concentrations. For model evaluation, we measured total methylated Hg (MeHgT) in the Baltic Sea and found low concentrations (39 ± 16 fM) above the halocline and high concentrations in anoxic waters (1249 ± 369 fM). To close the Baltic Sea MeHgT budget, we inferred an average normoxic water column HgII methylation rate constant of 2 × 10-4 d-1. We used the model to compare Baltic Sea's present-day (2005-2014) eutrophic state to an oligo/mesotrophic scenario. Eutrophication increases primary production and export of organic matter and associated Hg to the sediment effectively removing Hg from the active biogeochemical cycle; this results in a 27% lower present-day water column Hg reservoir. However, increase in organic matter production and remineralization stimulates microbial Hg methylation resulting in a seasonal increase in both water and phytoplankton MeHg reservoirs above the halocline. Previous studies of systems dominated by external MeHg sources or benthic production found eutrophication to decrease MeHg levels in plankton. This Baltic Sea study shows that in systems with MeHg production in the normoxic water column eutrophication can increase phytoplankton MeHg content.

Freshwater discharges drive high levels of methylmercury in Arctic marine biota.

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.