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

Mercury Distributions and Cycling in the North Atlantic and Eastern Tropical Pacific Oceans

The distribution of mercury (Hg) in the ocean is complex as a result of in situ chemical transformations and inputs from natural and anthropogenic sources. Within the ocean, inorganic Hg is methylated to monomethylmercury (MMHg), which bioaccumulates and biomagnifies in marine food webs and poses a health risk to humans who eat fish. The biogeochemistry of Hg in the ocean has been studied for decades, however, recently improved sampling and analytical techniques have allowed for an enhanced understanding of global distributions of different Hg species. This dissertation uses a newly developed method for the analysis of MMHg that improves detection limits 10-fold over previous methods and allows for separation and analysis of dissolved gaseous dimethylmercury (DMHg) in the same sample. Filtered total Hg (HgT), MMHg, DMHg, and elemental Hg (Hg(0)) were measured in high vertical and horizontal resolution in the water column of the North Atlantic (GA03) and eastern tropical South Pacific (GP16) Oceans, using vetted methods for the trace-metal clean sampling and analysis of Hg through the U.S. GEOTRACES program. Total Hg and MMHg were also measured in suspended particles across both sections. A wide range of oceanographic features important to Hg chemistry were sampled including oligotrophic waters in the Atlantic, productive upwelling waters in the Pacific, hydrothermal vent plumes, and deep and intermediate water masses of varying ages and source regions. The subsurface distribution of Hg(0) was connected to the nitrogen cycle, with nutrient-like vertical distributions, similar to nitrate, in the Atlantic basin and increasing Hg(0) concentrations with denitrification in the Pacific. Filtered total Hg exhibited both scavenged- and nutrient-type vertical distributions in the Atlantic and nutrient-type distributions in the Pacific. Elevated concentrations of HgT were observed in a hydrothermal vent plume stemming from the Mid-Atlantic Ridge; however, Hg was not increased in a plume extending from the East Pacific Rise. Total Hg concentrations increased from younger to older Pacific deep waters but were anomalously high in Atlantic deep waters subducted within the past 200 y due to anthropogenic inputs. Young deep water impacted by anthropogenic Hg in the Atlantic contained 1.4x more methylated Hg (MMHg + DMHg) on average compared to unimpacted deep water in the Pacific. Dimethylmercury was often the dominant form of methylated Hg in deep water and concentrations of both MMHg and DMHg increased in aging Pacific deep water. Vertically stratified maxima of MMHg and DMHg were observed often near the subsurface chlorophyll maximum and frequently in low-oxygen thermocline waters where MMHg concentrations were 2x greater than DMHg. Methylated Hg was weakly positively correlated with apparent oxygen utilization, however, methylated Hg concentrations decreased with greater oxygen consumption. Concentrations of MMHg and DMHg were similar between Atlantic thermocline waters affected by anthropogenic Hg inputs and thermocline waters underlying the highly productive upwelling region in the eastern Pacific, despite substantial differences in oxygen concentrations. Analytical separation of methylated Hg species revealed unique and independent distributions of MMHg and DMHg. Data from both cruise sections suggests that MMHg and DMHg are produced throughout the water column in oxygenated subsurface waters, low-oxygen thermocline waters, and likely in deep water masses. Comparison of oceanic sections following thermohaline circulation revealed the impact of anthropogenic Hg inputs with increased concentrations of HgT, MMHg, and DMHg in young (\u3c 200 y) deep and subsurface Atlantic waters

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 (K(d)) 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’

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

Dark reduction drives evasion of mercury from the ocean

© The Author(s), 2021. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Lamborg, C. H., Hansel, C. M., Bowman, K. L., Voelker, B. M., Marsico, R. M., Oldham, V. E., Swarr, G. J., Zhang, T., & Ganguli, P. M. Dark reduction drives evasion of mercury from the ocean. Frontiers in Environmental Chemistry, 2, (2021): 659085, https://doi.org/10.3389/fenvc.2021.659085.Much of the surface water of the ocean is supersaturated in elemental mercury (Hg0) with respect to the atmosphere, leading to sea-to-air transfer or evasion. This flux is large, and nearly balances inputs from the atmosphere, rivers and hydrothermal vents. While the photochemical production of Hg0 from ionic and methylated mercury is reasonably well-studied and can produce Hg0 at fairly high rates, there is also abundant Hg0 in aphotic waters, indicating that other important formation pathways exist. Here, we present results of gross reduction rate measurements, depth profiles and diel cycling studies to argue that dark reduction of Hg2+ is also capable of sustaining Hg0 concentrations in the open ocean mixed layer. In locations where vertical mixing is deep enough relative to the vertical penetration of UV-B and photosynthetically active radiation (the principal forms of light involved in abiotic and biotic Hg photoreduction), dark reduction will contribute the majority of Hg0 produced in the surface ocean mixed layer. Our measurements and modeling suggest that these conditions are met nearly everywhere except at high latitudes during local summer. Furthermore, the residence time of Hg0 in the mixed layer with respect to evasion is longer than that of redox, a situation that allows dark reduction-oxidation to effectively set the steady-state ratio of Hg0 to Hg2+ in surface waters. The nature of these dark redox reactions in the ocean was not resolved by this study, but our experiments suggest a likely mechanism or mechanisms involving enzymes and/or important redox agents such as reactive oxygen species and manganese (III).This work was supported by NSF Grant OCE-1355720 (to CH, CL, and BV)

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

Starlikeness of Libera transformation (II) (Applications of Complex Function Theory to Differential Equations)

The GEOTRACES Intermediate Data Product 2017 (IDP2017) is the second publicly available data product of the international GEOTRACES programme, and contains data measured and quality controlled before the end of 2016. The IDP2017 includes data from the Atlantic, Pacific, Arctic, Southern and Indian oceans, with about twice the data volume of the previous IDP2014. For the first time, the IDP2017 contains data for a large suite of biogeochemical parameters as well as aerosol and rain data characterising atmospheric trace element and isotope (TEI) sources. The TEI data in the IDP2017 are quality controlled by careful assessment of intercalibration results and multi-laboratory data comparisons at crossover stations. The IDP2017 consists of two parts: (1) a compilation of digital data for more than 450 TEIs as well as standard hydrographic parameters, and (2) the eGEOTRACES Electronic Atlas providing an on-line atlas that includes more than 590 section plots and 130 animated 3D scenes. The digital data are provided in several formats, including ASCII, Excel spreadsheet, netCDF, and Ocean Data View collection. Users can download the full data packages or make their own custom selections with a new on-line data extraction service. In addition to the actual data values, the IDP2017 also contains data quality flags and 1-σ data error values where available. Quality flags and error values are useful for data filtering and for statistical analysis. Metadata about data originators, analytical methods and original publications related to the data are linked in an easily accessible way. The eGEOTRACES Electronic Atlas is the visual representation of the IDP2017 as section plots and rotating 3D scenes. The basin-wide 3D scenes combine data from many cruises and provide quick overviews of large-scale tracer distributions. These 3D scenes provide geographical and bathymetric context that is crucial for the interpretation and assessment of tracer plumes near ocean margins or along ridges. The IDP2017 is the result of a truly international effort involving 326 researchers from 25 countries. This publication provides the critical reference for unpublished data, as well as for studies that make use of a large cross-section of data from the IDP2017. This article is part of a special issue entitled: Conway GEOTRACES - edited by Tim M. Conway, Tristan Horner, Yves Plancherel, and Aridane G. González