Anne L. Soerensen

Mercury biogeochemical cycling in the ocean and policy implications

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.

An Improved Global Model for Air-Sea Exchange of Mercury: High Concentrations over the North Atlantic

We develop an improved treatment of the surface ocean in the GEOS-Chem global 3-D biogeochemical model for mercury (Hg). We replace the globally uniform subsurface ocean Hg concentrations used in the original model with basin-specific values based on measurements. Updated chemical mechanisms for Hg⁰/Hg(II) redox reactions in the surface ocean include both photochemical and biological processes, and we improved the parametrization of particle-associated Hg scavenging. Modeled aqueous Hg concentrations are consistent with limited surface water observations. Results more accurately reproduce high-observed MBL concentrations over the North Atlantic (NA) and the associated seasonal trends. High seasonal evasion in the NA is driven by inputs from Hg enriched subsurface waters through entrainment and Ekman pumping. Globally, subsurface waters account for 40% of Hg inputs to the ocean mixed layer, and 60% is from atmospheric deposition. Although globally the ocean is a net sink for 3.8 Mmol Hg y⁻¹, the NA is a net source to the atmosphere, potentially due to enrichment of subsurface waters with legacy Hg from historical anthropogenic sources.

Multi-Decadal Decline of Mercury in the North Atlantic Atmosphere Explained by Changing Subsurface Seawater Concentrations

decline of 0.046 0.010 ng m 3 a 1 (2.5% a 1 )o ver the NA (steeper than at Northern Hemispheric land sites) but no significant decline over the SA. Surface water Hg 0 measurements in the NA show a decline of 5.7% a 1 since 1999, and limited subsurface ocean data show an 80% decline from 1980 to present. We use a coupled global atmosphere-ocean model to show that the decline in NA atmospheric concentrations can be explained by decreasing oceanic evasion from the NA driven by declining subsurface water Hg concentrations. We speculate that this large historical decline of Hg in the NA Ocean could have been caused by decreasing Hg inputs from rivers and wastewater and by changes in the oxidant chemistry of the atmospheric marine boundary layer. Citation: Soerensen, A. L., D. J. Jacob, D.G.Streets, M.L.I.Witt, R. Ebinghaus,R.P.Mason, M.Andersson, and E. M. Sunderland (2012), Multi-decadal decline of mercury in the North Atlantic atmosphere explained by changing subsurface seawater concentrations, Geophys. Res. Lett., 39, L21810, doi:10.1029/ 2012GL053736.

Global Concentrations of Gaseous Elemental Mercury and Reactive Gaseous Mercury in the Marine Boundary Layer

Gaseous elemental mercury (GEM) and reactive gaseous mercury (RGM) were measured during an eight month circumnavigation to obtain knowledge of their worldwide distributions in the marine boundary layer (MBL). Background GEM concentrations were found to be 1.32 ± 0.2 ng/m(3) (summer) and 2.62 ± 0.4 ng/m(3) (spring) in the northern hemisphere and 1.27 ± 0.2 ng/m(3) (spring and summer) in the southern hemisphere. Radiation and relative humidity are shown to control diurnal cycles of RGM. During the cruise the ship passed areas of clean MBL air, air influenced by biomass burning (South Atlantic) and air with high concentrations of GEM and RGM of unknown origin (Antarctic). High GEM concentrations above the Atlantic indicate that emission from the ocean can be an important GEM source. Our data combined with data from earlier cruises provides adequate information to establish a seasonal cycle for the Atlantic. Results show a cycle similar to that found at Mace Head, Ireland but with larger amplitude. We have improved the basic knowledge of mean GEM and RGM concentrations in the MBL worldwide and shown how natural sources and reemissions can affect GEM concentrations in the MBL.

Drivers of Surface Ocean Mercury Concentrations and Air–Sea Exchange in the West Atlantic Ocean

Accurately characterizing net evasion of elemental mercury (Hg(0)) from marine systems is essential for understanding the global biogeochemical mercury (Hg) cycle and the pool of divalent Hg (Hg(II)) available for methylation. Few high resolution measurements of Hg(0) are presently available for constraining global and regional flux estimates and for understanding drivers of spatial and temporal variability in evasion. We simultaneously measured high-resolution atmospheric and surface seawater Hg(0) concentrations as well as the total Hg distribution during six cruises in the West Atlantic Ocean between 2008 and 2010 and examined environmental factors affecting net Hg(0) formation and evasion. We observed the lowest fraction of Hg as Hg(0) (7.8 ± 2.4%) in the near-coastal and shelf areas that are influenced by riverine inputs. Significantly higher %Hg(0) observed in open ocean areas (15.8 ± 3.9%) may reflect lower dissolved organic carbon (DOC) in offshore environments, which is known to affect both the reducible Hg(II) pool and redox kinetics. Calculated Hg(0) evasion changed by more than a factor of 3 between cruises (range: 2.1 ± 0.7 to 6.8 ± 5.1 ng m(-2) h(-1)), driven mainly by variability in Hg(0) and wind speed. Our results suggest that further mechanistic understanding of the role of DOC on Hg redox kinetics in different types of marine environments is needed to explain variability in Hg(0) concentrations and improve global estimates of air-sea exchange.

Freshwater discharges drive high levels of methylmercury in Arctic marine biota

Significance Estuaries are the predominant hunting and fishing territory for northern indigenous populations whose way of life is threatened by both climate change and industrial development. Direct measurements and modeling conducted as part of this study show enhanced production of methylmercury, a potent neurotoxin, and uptake by plankton in stratified oxic seawater. Enhanced climate-driven stratification of ocean margin areas with sea-ice melt will likely elevate biological methylmercury concentrations in the Arctic. Elevated biological methylmercury levels will be exacerbated by hydroelectric development planned throughout many northern regions. Our experimental measurements indicate that, over the next decade, regional increases in methylmercury concentrations resulting from flooding associated with hydroelectric development will be greater than those expected from climate change. 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.

A mass budget for mercury and methylmercury in the Arctic Ocean

Elevated biological concentrations of methylmercury (MeHg), a bioaccumulative neurotoxin, are observed throughout the Arctic Ocean, but major sources and degradation pathways in seawater are not well understood. We develop a mass budget for mercury species in the Arctic Ocean based on available data since 2004 and discuss implications and uncertainties. Our calculations show that high total mercury (Hg) in Arctic seawater relative to other basins reflect large freshwater inputs and sea ice cover that inhibits losses through evasion. We find that most net MeHg production (20 Mg a−1) occurs in the subsurface ocean (20–200 m). There it is converted to dimethylmercury (Me2Hg: 17 Mg a−1), which diffuses to the polar mixed layer and evades to the atmosphere (14 Mg a−1). Me2Hg has a short atmospheric lifetime and rapidly degrades back to MeHg. We postulate that most evaded Me2Hg is redeposited as MeHg and that atmospheric deposition is the largest net MeHg source (8 Mg a−1) to the biologically productive surface ocean. MeHg concentrations in Arctic Ocean seawater are elevated compared to lower latitudes. Riverine MeHg inputs account for approximately 15% of inputs to the surface ocean (2.5 Mg a−1) but greater importance in the future is likely given increasing freshwater discharges and permafrost melt. This may offset potential declines driven by increasing evasion from ice-free surface waters. Geochemical model simulations illustrate that for the most biologically relevant regions of the ocean, regulatory actions that decrease Hg inputs have the capacity to rapidly affect aquatic Hg concentrations.

Elemental mercury concentrations and fluxes in the tropical atmosphere and ocean.

Air-sea exchange of elemental mercury (Hg(0)) is a critical component of the global biogeochemical Hg cycle. To better understand variability in atmospheric and oceanic Hg(0), we collected high-resolution measurements across large gradients in seawater temperature, salinity, and productivity in the Pacific Ocean (20°N-15°S). We modeled surface ocean Hg inputs and losses using an ocean general circulation model (MITgcm) and an atmospheric chemical transport model (GEOS-Chem). Observed surface seawater Hg(0) was much more variable than atmospheric concentrations. Peak seawater Hg(0) concentrations (∼ 130 fM) observed in the Pacific intertropical convergence zone (ITCZ) were ∼ 3-fold greater than surrounding areas (∼ 50 fM). This is similar to observations from the Atlantic Ocean. Peak evasion in the northern Pacific ITCZ was four times higher than surrounding regions and located at the intersection of high wind speeds and elevated seawater Hg(0). Modeling results show that high Hg inputs from enhanced precipitation in the ITCZ combined with the shallow ocean mixed layer in this region drive elevated seawater Hg(0) concentrations. Modeled seawater Hg(0) concentrations reproduce observed peaks in the ITCZ of both the Atlantic and Pacific Oceans but underestimate its magnitude, likely due to insufficient deep convective scavenging of oxidized Hg from the upper troposphere. Our results demonstrate the importance of scavenging of reactive mercury in the upper atmosphere driving variability in seawater Hg(0) and net Hg inputs to biologically productive regions of the tropical ocean.

A decline in Arctic Ocean mercury suggested by differences in decadal trends of atmospheric mercury between the Arctic and northern midlatitudes

Atmospheric mercury (Hg) in the Arctic shows much weaker or insignificant annual declines relative to northern midlatitudes over the past decade (2000-2009) but with strong seasonality in trends. W ...

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.