A global ocean inventory of anthropogenic mercury based on water column measurements.

Mercury is a toxic, bioaccumulating trace metal whose emissions to the environment have increased significantly as a result of anthropogenic activities such as mining and fossil fuel combustion. Several recent models have estimated that these emissions have increased the oceanic mercury inventory by 36-1,313 million moles since the 1500s. Such predictions have remained largely untested owing to a lack of appropriate historical data and natural archives. Here we report oceanographic measurements of total dissolved mercury and related parameters from several recent expeditions to the Atlantic, Pacific, Southern and Arctic oceans. We find that deep North Atlantic waters and most intermediate waters are anomalously enriched in mercury relative to the deep waters of the South Atlantic, Southern and Pacific oceans, probably as a result of the incorporation of anthropogenic mercury. We estimate the total amount of anthropogenic mercury present in the global ocean to be 290 ± 80 million moles, with almost two-thirds residing in water shallower than a thousand metres. Our findings suggest that anthropogenic perturbations to the global mercury cycle have led to an approximately 150 per cent increase in the amount of mercury in thermocline waters and have tripled the mercury content of surface waters compared to pre-anthropogenic conditions. This information may aid our understanding of the processes and the depths at which inorganic mercury species are converted into toxic methyl mercury and subsequently bioaccumulated in marine food webs.

An examination of the role of particles in oceanic mercury cycling.

Recent models of global mercury (Hg) cycling have identified the downward flux of sinking particles in the ocean as a prominent Hg removal process from the ocean. At least one of these models estimates the amount of anthropogenic Hg in the ocean to be about 400 Mmol, with deep water formation and sinking fluxes representing the largest vectors by which pollutant Hg is able to penetrate the ocean interior. Using data from recent cruises to the Atlantic, we examined the dissolved and particulate partitioning of Hg in the oceanic water column as a cross-check on the hypothesis that sinking particle fluxes are important. Interestingly, these new data suggest particle-dissolved partitioning (Kd) that is approximately 20× greater than previous estimates, which thereby challenges certain assumptions about the scavenging and active partitioning of Hg in the ocean used in earlier models. For example, the new particle data suggest that regenerative scavenging is the most likely mechanism by which the association of Hg and particles occurs.This article is part of the themed issue 'Biological and climatic impacts of ocean trace element chemistry'.

Flux of Total Mercury and Methylmercury to the Northern Gulf of Mexico from U.S. Estuaries.

To better understand the source of elevated methylmercury (MeHg) concentrations in Gulf of Mexico (GOM) fish, we quantified fluxes of total Hg and MeHg from 11 rivers in the southeastern United States, including the 10 largest rivers discharging to the GOM. Filtered water and suspended particles were collected across estuarine salinity gradients in Spring and Fall 2012 to estimate fluxes from rivers to estuaries and from estuaries to coastal waters. Fluxes of total Hg and MeHg from rivers to estuaries varied as much as 100-fold among rivers. The Mississippi River accounted for 59% of the total Hg flux and 49% of the fluvial MeHg flux into GOM estuaries. While some estuaries were sources of Hg, the combined estimated fluxes of total Hg (~5200 mol y(-1)) and MeHg (~120 mol y(-1)) from the estuaries to the GOM were less than those from rivers to estuaries, suggesting an overall estuarine sink. Fluxes of total Hg from the estuaries to coastal waters of the northern GOM are approximately an order of magnitude less than from atmospheric deposition. However, fluxes from rivers are significant sources of MeHg to estuaries and coastal regions of the northern GOM.

The role of plastic debris in the biogeochemical cycle of mercury in Lake Erie and San Francisco Bay.

The accumulation of plastic debris that concentrates hydrophobic compounds and microbial communities creates the potential for altered aquatic biogeochemical cycles. This study investigated the role of plastic debris in the biogeochemical cycling of mercury in surface waters of the San Francisco Bay, Sacramento River, Lake Erie, and in coastal seawater. Total mercury and monomethylmercury were measured on plastic debris from all study sites. Plastic-bound microbial communities from Lake Erie and San Francisco Bay contained several lineages of known mercury methylating microbes, however the hgcAB gene cluster was not detected using polymerase chain reaction. These plastic-bound microbial communities also contained species that possess the mer operon, and merA genes were detected using polymerase chain reaction. In coastal seawater incubations, rapid mercury methylation percentages were greater in the presence of microplastics and demethylation percentages decreased as monomethylmercury additions adsorbed to microplastics. These findings suggest that plastic pollution has the potential to alter the biogeochemical cycling of mercury in aquatic ecosystems.

A global perspective on mercury cycling in the ocean.

Mercury (Hg) is a ubiquitous metal in the ocean that undergoes in situ chemical transformations in seawater and marine sediment. Most relevant to public health is the production of monomethyl-Hg, a neurotoxin to humans that accumulates in marine fish and mammals. Here we synthesize 30 years of Hg measurements in the ocean to discuss sources, sinks, and internal cycling of this toxic metal. Global-scale oceanographic survey programs (i.e. CLIVAR and GEOTRACES), refined protocols for clean sampling, and analytical advancements have produced over 200 high-resolution, full-depth profiles of total Hg, methylated Hg, and gaseous elemental Hg throughout the Atlantic, Pacific, Arctic, and Southern Oceans. Vertical maxima of methylated Hg were found in surface waters, near the subsurface chlorophyll maximum, and in low-oxygen thermocline waters. The greatest concentration of Hg in deep water was measured in Antarctic Bottom Water, and in newly formed Labrador Sea Water, Hg showed a decreasing trend over the past 20 years. Distribution of Hg in polar oceans was unique relative to lower latitudes with higher concentrations of total Hg near the surface and vertical trends of Hg speciation driven by water column stratification and seasonal ice cover. Global models of Hg in the ocean require a better understanding of biogeochemical controls on Hg speciation and improved accuracy of methylated Hg measurements within the international community.

Aluminum sulfate (alum) application interactions with coupled metal and nutrient cycling in a hypereutrophic lake ecosystem.

Many lake ecosystems worldwide experience severe eutrophication and associated harmful blooms of cyanobacteria due to high loadings of phosphorus (P). While aluminum sulfate (alum) has been used for decades as chemical treatment of eutrophic waters, the ecological effects of alum on coupled metal and nutrient cycling are not well known. The objective of our study was to investigate the effects of an in-situ alum treatment on aluminum and nutrient (P, N, and S) cycling in a hypereutrophic lake ecosystem. Our results indicate that the addition of alum along with sodium aluminate (as a buffer) increased dissolved aluminum and sulfate in the surface and pore waters, and altered nitrogen cycling by increasing nitrous oxide (N2O) concentrations in the surface water. The increase of aluminum and sulfate may potentially feedback to alter benthic community dynamics. These results enhance our understanding of the unintended ecological consequences of alum treatments in hypereutrophic freshwater ecosystems.

Effects of suspended solids and dissolved organic carbon on nickel toxicity.

Nickel (Ni) is a common and potentially toxic heavy metal in many fluvial ecosystems. We examined the potentially competitive and complementary roles of suspended sediment and a dissolved organic ligand, humate, in affecting the partitioning and toxicity of Ni to a model organism, Daphnia magna, in both batch and stream-recirculating flume (SRF) tests. Sediments included a fine-grained deposit, montmorillonite, and kaolinite. Survival of D. magna was unaffected by the range of suspended solids used in the present study (8-249 mg/L). However, exposure to suspended solids that were amended with Ni had a deleterious effect on test organism survival, which is attributed to partitioning of Ni into the aqueous phase. At comparable levels of dissolved Ni, survival of D. magna was reduced in tests with Ni-amended suspended solids compared to Ni-only aqueous exposures, suggesting potentiation between these two aquatic contaminants. Addition of humate attenuated toxicity to D. magna in both Ni-only and Ni-amended suspended sediment exposures. These results indicate that organic ligands and suspended solids have important functions in affecting the bioavailability and toxicity of Ni to aquatic organisms and should be incorporated into predictive models to protect ecosystem quality.