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.

Global and Local Sources of Mercury Deposition in Coastal New England Reconstructed from a Multiproxy, High-Resolution, Estuarine Sediment Record.

Historical reconstruction of mercury (Hg) accumulation in natural archives, especially lake sediments, has been essential to understanding human perturbation of the global Hg cycle. Here we present a high-resolution chronology of Hg accumulation between 1727 and 1996 in a varved sediment core from the Pettaquamscutt River Estuary (PRE), Rhode Island. Mercury accumulation is examined relative to (1) historic deposition of polycyclic aromatic hydrocarbons (PAHs) and lead (Pb) and its isotopes (206Pb/207Pb) in the same core, and (2) other reconstructions of Hg deposition in urban and remote settings. Mercury deposition in PRE parallels the temporal patterns of PAHs, and both track industrialization and regional coal use between 1850 and 1950 as well as rising petroleum use after 1950. There is little indication of increased Hg deposition from late 19th-century silver and gold mining in the western U.S. A broad maximum of Hg deposition during 1930-1980, and not found in remote sites, is consistent with the predicted influence of additional industrial sources and commercial products. Our results imply that a significant portion of global anthropogenic Hg emissions during the 20th century was deposited locally, near urban and industrial centers of Hg use and release.

Nickel Partitioning and Toxicity in Sediment during Aging: Variation in Toxicity Related to Stability of Metal Partitioning.

Metals in sediment can be complexed by minerals, partition between solid and aqueous phases, and cause toxicity at high concentrations. We studied how the oxidation of surface sediment that occurs during aging alters the partitioning and toxicity of Ni. Two sediments (Burntwood and Raisin) were amended with Ni, equilibrated, incubated in a flow-through flume, and examined for sediment physicochemistry and toxicity to Hyalella azteca (7 day growth). Through time, the sediment surface (5 mm) was oxidized, acid-volatile sulfide concentrations declined in Raisin sediment, and amorphous Fe oxides increased. Porewater Ni concentrations declined through time but total Ni concentrations in sediment were unchanged, suggesting changes in Ni partitioning through time. Both sediments elicited a toxic dose-response by H. azteca early in the aging process; but only Burntwood, for which Ni was primarily partitioned to Fe oxide minerals, exhibited a consistent dose-response during aging. Low total Ni concentrations (20 mg kg-1) in Raisin sediment reduced H. azteca growth at initiation, but all Ni treatments (up to 3000 mg kg-1) exhibited similar growth after 12 days of aging. The dynamic toxicity observed in Raisin sediment was likely due to the instability of NiS in surface sediments early in the aging process. These data suggest that short-term toxicity assays with homogenized Ni-amended sediment (i.e., standard sediment toxicity tests) may be accurate for sediments where Ni speciation is dominated by oxidized ligands; however, under high-AVS and high-Fe conditions, calculated toxicity thresholds may be overly conservative (here by >100-fold) with respect to natural sediment conditions.

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'.

Copper Sediment Toxicity and Partitioning during Oxidation in a Flow-Through Flume.

The bioavailability of transition metals in sediments often depends on redox conditions in the sediment. We explored how the physicochemistry and toxicity of anoxic Cu-amended sediments changed as they aged (i.e., naturally oxidized) in a flow-through flume. We amended two sediments (Dow and Ocoee) with Cu, incubated the sediments in a flow-through flume, and measured sediment physicochemistry and toxicity over 213 days. As sediments aged, oxygen penetrated sediment to a greater depth, the relative abundance of Fe oxides increased in surface and deep sediments, and the concentration of acid volatile sulfide declined in Ocoee surface sediments. The total pool of Cu in sediments did not change during aging, but porewater Cu, and Cu bound to amorphous Fe oxides decreased while Cu associated with crystalline Fe oxides increased. The dose-response of the epibenthic amphipod Hyalella azteca to sediment total Cu changed over time, with older sediments being less toxic than freshly spiked sediments. We observed a strong dose-response relationship between porewater Cu and H. azteca growth across all sampling periods, and measurable declines in relative growth rates were observed at concentrations below interstitial water criteria established by the U.S. EPA. Further, solid-phase bioavailability models based on AVS and organic carbon were overprotective and poorly predicted toxicity in aged sediments. We suggest that sediment quality criteria for Cu is best established from measurement of Cu in pore water rather than estimating bioavailable Cu from the various solid-phase ligands, which vary temporally and spatially.

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.

Methylmercury Bioaccumulation in Stream Food Webs Declines with Increasing Primary Production.

Opposing hypotheses posit that increasing primary productivity should result in either greater or lesser contaminant accumulation in stream food webs. We conducted an experiment to evaluate primary productivity effects on MeHg accumulation in stream consumers. We varied light for 16 artificial streams creating a productivity gradient (oxygen production =0.048-0.71 mg O2 L(-1) d(-1)) among streams. Two-level food webs were established consisting of phytoplankton/filter feeding clam, periphyton/grazing snail, and leaves/shredding amphipod (Hyalella azteca). Phytoplankton and periphyton biomass, along with MeHg removal from the water column, increased significantly with productivity, but MeHg concentrations in these primary producers declined. Methylmercury concentrations in clams and snails also declined with productivity, and consumer concentrations were strongly correlated with MeHg concentrations in primary producers. Heterotroph biomass on leaves, MeHg in leaves, and MeHg in Hyalella were unrelated to stream productivity. Our results support the hypothesis that contaminant bioaccumulation declines with stream primary production via the mechanism of bloom dilution (MeHg burden per cell decreases in algal blooms), extending patterns of contaminant accumulation documented in lakes to lotic systems.

Methylmercury accumulation in plankton on the continental margin of the northwest Atlantic Ocean.

Accumulation of monomethylmercury (MMHg) by plankton is a key process influencing concentrations of this toxic mercury species in marine food webs and seafood. We examined bioaccumulation and biomagnification of MMHg in microseston and four size fractions of zooplankton on the continental shelf, slope, and rise of the northwest Atlantic Ocean. The bioaccumulation factor (BAF, L/kg) for MMHg in microseston averaged 10(4.3±0.3) among 21 locations, and concentrations were unrelated to those in colocated, filtered surface water. Instead, concentrations and the BAF of MMHg in microseston were related inversely with total suspended solids in surface water, a proxy for planktonic biomass at these remote locations. MMHg was biomagnified by a factor of 4 from microseston to zooplankton, and both concentrations of MMHg and the fraction of total mercury as MMHg increased with larger size fractions of zooplankton. These results suggest that the initial magnitude of MMHg uptake into pelagic marine food webs is influenced by the degree of primary production in surface waters and propagated up through large zooplankton. Accordingly, biological productivity, in addition to inputs of MMHg to surface waters, must be considered when predicting how MMHg bioaccumulation will vary spatially and temporally in the ocean.

Evaluating the performance of diffusive gradients in thin films for predicting Ni sediment toxicity.

Diffusive gradients in thin films (DGTs) rapidly measure labile fractions of metal and are promoted as an assessment tool for bioavailability. Using macroinvertebrate community composition as a response, this study compared the predictive ability of DGT-measured Ni with acid volatile sulfide (AVS) and organic carbon (OC) corrected Ni [(SEM(Ni)-AVS)/f(OC)] and total Ni concentrations. In two experiments, sediments were amended with Ni and placed within either a streamside mesocosm or deployed in situ. DGT-measured Ni concentrations (C(DGT)) increased with increasing total Ni, were greater at depth, and decreased over time. Relationships between Ni C(DGT) and sediment geochemistry indicated a shift in Ni partitioning from AVS-bound to Fe- and Mn-associated Ni. In both experiments, DGT-measured Ni poorly predicted the invertebrate response to metal, whereas models that included total Ni or (SEM(Ni)-AVS)/f(OC) effectively predicted the invertebrate response for the streamside mesocosm and in situ experiments, respectively. C(DGT) overestimated the available Ni fraction, possibly due to sampling either nonbioavailable solid-phase Ni or Ni irrespective of cations competing at the biotic ligand. We suggest that C(DGT) cannot replace (SEM(Ni)-AVS)/f(OC) for predicting invertebrate response to sediment Ni, and greater understanding of metal species lability to DGTs is needed before assuming equivalence between bioavailable and DGT-labile metals in sediments.

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.

Nutrient supply and mercury dynamics in marine ecosystems: a conceptual model.

There is increasing interest and concern over the impacts of mercury (Hg) inputs to marine ecosystems. One of the challenges in assessing these effects is that the cycling and trophic transfer of Hg are strongly linked to other contaminants and disturbances. In addition to Hg, a major problem facing coastal waters is the impacts of elevated nutrient, particularly nitrogen (N), inputs. Increases in nutrient loading alter coastal ecosystems in ways that should change the transport, transformations and fate of Hg, including increases in fixation of organic carbon and deposition to sediments, decreases in the redox status of sediments and changes in fish habitat. In this paper we present a conceptual model which suggests that increases in loading of reactive N to marine ecosystems might alter Hg dynamics, decreasing bioavailabilty and trophic transfer. This conceptual model is most applicable to coastal waters, but may also be relevant to the pelagic ocean. We present information from case studies that both support and challenge this conceptual model, including marine observations across a nutrient gradient; results of a nutrient-trophic transfer Hg model for pelagic and coastal ecosystems; observations of Hg species, and nutrients from coastal sediments in the northeastern U.S.; and an analysis of fish Hg concentrations in estuaries under different nutrient loadings. These case studies suggest that changes in nutrient loading can impact Hg dynamics in coastal and open ocean ecosystems. Unfortunately none of the case studies is comprehensive; each only addresses a portion of the conceptual model and has limitations. Nevertheless, our conceptual model has important management implications. Many estuaries near developed areas are impaired due to elevated nutrient inputs. Widespread efforts are underway to control N loading and restore coastal ecosystem function. An unintended consequence of nutrient control measures could be to exacerbate problems associated with Hg contamination. Additional focused research and monitoring are needed to critically examine the link between nutrient supply and Hg contamination of marine waters.

Nickel phase partitioning and toxicity in field-deployed sediments.

The pool of bioavailable metal in sediments can be much smaller than total metal concentration due to complexation and precipitation with ligands. Metal bioavailability and toxicity in sediment is often predicted from models of simultaneous extracted metal and acid volatile sulfide (SEM-AVS); however, studies of the applicability of these models for Ni-contaminated sediments have been conducted primarily in laboratory settings. We investigated the utility of the SEM-AVS models under field conditions: Five lotic sediments with a range of sulfide and organic carbon contents were amended with four concentrations of Ni, deployed in streams for eight weeks, and examined for colonizing macroinvertebrates. After four weeks, colonizing macroinvertebrates showed a strong negative response to the Ni-treated sediments and SEM-AVS models of bioavailability differentiated between toxic and nontoxic conditions. By Week 8, relationships deteriorated between colonizing macroinvertebrates and SEM-AVS model predictions. Total Ni in the sediment did not change through time; however, Ni partitioning shifted from being dominated by organic cabon at deployment to associations with Fe and Mn. Combined geochemical and toxicity results suggest that Fe and Mn oxides in surface sediments resulted in Ni being less available to biota. This implies that current SEM-AVS models may overestimate bioavailable Ni in sediments with oxic surface layers and sufficient Fe and Mn.

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.

Iron-mediated photochemical decomposition of methylmercury in an arctic Alaskan lake.

Sunlight-induced decomposition is the principal sink for methylmercury (CH(3)Hg(+)) in arctic Alaskan lakes and reduces its availability for accumulation in aquatic food webs. However, the mechanistic chemistry of this process in natural waters is unknown. We examined experimentally the mechanism of photochemical CH(3)Hg(+) decomposition in filter-sterilized epilimnetic waters of Toolik Lake in arctic Alaska (68 degrees 38'N, 149 degrees 36'W), a region illuminated by sunlight almost continuously during the summer. Results from in situ incubation tests indicate that CH(3)Hg(+) is not decomposed principally by either direct photolysis (i.e., no degradation in reagent-grade water) or primary photochemical reactions with dissolved organic material. The preeminent role of labile Fe and associated photochemically produced reactive oxygen species is implicated by tests that show 1) additions of Fe(III) to reagent-grade water enhance CH(3)Hg(+) photodecomposition, 2) strong complexation of ambient Fe(III) with desferrioxamine B inhibits the reaction in lake water, and 3) experimental additions of organic molecules that scavenge hydroxyl radicals specifically among reactive oxygen species (dimethylsulfoxide and formic acid) inhibit CH(3)Hg(+) degradation. Lake-water dilution and Fe(III) addition experiments indicate that Fe is not the limiting reactant for CH(3)Hg(+) photodecomposition in Toolik Lake, which is consistent with prior results indicating that photon flux is a major control. These results demonstrate that CH(3)Hg(+) is decomposed in natural surface water by oxidants, apparently hydroxyl radical, generated from the photo-Fenton reaction.

Temporal Variation of Mercury in Effluent from Two Municipal Wastewater-Treatment Plants in Southwest Ohio.

Wastewater-treatment plants (WWTPs) are an important source of mercury (Hg) to surface waters, but little is known about temporal variability of efflux to aquatic systems. We found that Hg concentrations in effluent varied by about a factor of 2 on monthly, weekly, and hourly timescale comparisons. These results suggest that limited sampling can yield a representative concentration with reasonable uncertainty for purposes of estimating the environmental significance of Hg from WWTPs. Environ Toxicol Chem 2020;39:1027-1031. © 2020 SETAC.

External Sources Inhibit Benthic Phosphorus Fluxes in the Lower Great Miami River, Southwest Ohio.

Human activities have increased nutrient loadings to aquatic ecosystems, especially during the past century. During low river flow in late summer and early fall, elevated concentrations of phosphorus (P) and nitrogen are present in the temperate Lower Great Miami River and contribute to its eutrophication. Although wastewater treatment plants are suspected of being major sources of P to the river, riverbed sediment has not been examined as an additional potential source of P. Benthic P fluxes were measured at 11 representative locations along the Lower Great Miami River during 3 sampling campaigns in late summer and early fall of 2015. Benthic fluxes of filtered total P (range, -1.6-12 mg m-2 d-1 ) were related inversely to filtered total P concentrations in river water (p = 0.002, r = -0.60). This relationship suggests that elevated P in river water inhibits mobilization from sediment, likely by minimizing the concentration gradient between porewater and overlying water. To effectively mitigate long-term effects of legacy P stored in Lower Great Miami River sediments, external sources must continue to be managed and discharges reduced to allow legacy P to be mobilized and flushed from the system. Reducing nutrient loading will help protect water quality in the Lower Great Miami River, in other comparable rivers, and in downstream aquatic habitats. Environ Toxicol Chem 2020;39:1517-1525. © 2020 SETAC.

Mercury biogeochemical cycling: A synthesis of recent scientific advances.

The focus of this paper is to briefly discuss the major advances in scientific thinking regarding: a) processes governing the fate and transport of mercury in the environment; b) advances in measurement methods; and c) how these advances in knowledge fit in within the context of the Minamata Convention on Mercury. Details regarding the information summarized here can be found in the papers associated with this Virtual Special Issue of STOTEN.

Hitting Reset on Sediment Toxicity: Sediment Homogenization Alters the Toxicity of Metal-Amended Sediments.

Laboratory testing of sediments frequently involves manipulation by amendment with contaminants and homogenization, which changes the physicochemical structure of sediments. These changes can influence the bioavailability of divalent metals, and field and mesocosm experiments have shown that laboratory-derived thresholds are often overly conservative. We assessed the mechanisms that lead to divergence between laboratory- and field-derived thresholds; specifically, we assessed the importance of slow equilibration to solid-phase ligands and vertical stratification. To mimic natural physicochemical conditions, we uniquely aged sediment with a flow-through exposure system. These sediments were then homogenized and compared, toxicologically, with freshly metal-amended sediments in a 28-d chronic toxicity bioassay with the amphipod Hyalella azteca. We assessed concentration-response relationships for 3 metals (copper, nickel, and zinc) and 5 geochemically distinct sediments. We observed minimal differences in growth and survival of H. azteca between aged and freshly spiked sediments across all sediments and metals. These trends suggest that a loss of toxicity observed during long-term sediment aging is reversed after sediment homogenization. By comparison with mesocosm experiments, we demonstrate that homogenizing sediment immediately before toxicity assays may produce artificially high toxicity thresholds. We suggest that toxicity assays with sediments that maintain vertical redox gradients are needed to generate field-relevant sediment metal toxicity thresholds. Environ Toxicol Chem 2019;38:1995-2007. © 2019 SETAC.

Bioaccumulation and biomagnification of mercury and methylmercury in four sympatric coastal sharks in a protected subtropical lagoon.

Mercury bioaccumulation is frequently observed in marine ecosystems, often with stronger effects at higher trophic levels. We compared total mercury (THg) and methylmercury (MeHg) from muscle with length, comparative isotopic niche, and diet (via δ13C and δ15N) among four sympatric coastal sharks in Florida Bay (USA): blacknose, blacktip, bull, and lemon. Mercury in blacknose and blacktip sharks increased significantly with size, whereas bull and lemon sharks had a high variance in mercury relative to size. Both δ13C and δ15N were consistent with general resource use and trophic position relationships across all species. A significant relationship was observed between δ13C and mercury in blacktip sharks, suggesting an ontogenetic shift isotopic niche, possibly a dietary change. Multiple regression showed that δ13C and δ15N were the strongest factors regarding mercury bioaccumulation in individuals across all species. Additional research is recommended to resolve the mechanisms that determine mercury biomagnification in individual shark species.