Mercury species concentrations and fluxes in the Central Tropical Pacific Ocean

Author Posting. © American Geophysical Union, 2015. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Global Biogeochemical Cycles 29 (2015): 656–676, doi:10.1002/2015GB005120.The formation of the toxic and bioaccumulating monomethylmercury (MMHg) in marine systems is poorly understood, due in part to sparse data from many ocean regions. We present dissolved mercury (Hg) speciation data from 10 stations in the North and South Equatorial Pacific spanning large water mass differences and gradients in oxygen utilization. We also compare the mercury content in suspended particles from six stations and sinking particles from three stations to constrain local Hg sources and sinks. Concentrations of total Hg (THg) and methylated Hg in the surface and intermediate waters of the Equatorial and South Pacific suggest Hg cycling distinct from that of the North Pacific gyre. Maximum concentrations of 180 fM for both MMHg and dimethylmercury (DMHg) are observed in the Equatorial Pacific. South of the equator, concentrations of MMHg and DMHg are less than 100 fM. Sinking fluxes of particulate THg can reasonably explain the shape of dissolved THg profiles, but those of MMHg are too low to account for dissolved MMHg profiles. However, methylated Hg species are lower than predicted from remineralization rates based on North Pacific data, consistent with limitation of methylation in Equatorial and South Pacific waters. Full water column depth profiles were also measured for the first time in these regions. Concentrations of THg are elevated in deep waters of the North Pacific, compared to those in the intermediate and surface waters, and taper off in the South Pacific. Comparisons with previous measurements from nearby regions suggest little enrichment of THg or MMHg over the past 20 years.Financial support for this study was provided by the National Science Foundation in a grant from the Chemical Oceanography Program (OCE-1031271) to C.H. Lamborg and M.A. Saito and a Graduate Student Fellowship to K.M. Munson.2015-11-2

Metabolite diversity among representatives of divergent Prochlorococcus ecotypes.

Approximately half of the annual carbon fixation on Earth occurs in the surface ocean through the photosynthetic activities of phytoplankton such as the ubiquitous picocyanobacterium Prochlorococcus. Ecologically distinct subpopulations (or ecotypes) of Prochlorococcus are central conduits of organic substrates into the ocean microbiome, thus playing important roles in surface ocean production. We measured the chemical profile of three cultured ecotype strains, observing striking differences among them that have implications for the likely chemical impact of Prochlorococcus subpopulations on their surroundings in the wild. Subpopulations differ in abundance along gradients of temperature, light, and nutrient concentrations, suggesting that these chemical differences could affect carbon cycling in different ocean strata and should be considered in models of Prochlorococcus physiology and marine carbon dynamics

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)

Seasonal and daily patterns in known dissolved metabolites in the northwestern Sargasso Sea

Abstract: Organic carbon in seawater plays a significant role in the global carbon cycle. The concentration and composition of dissolved organic carbon reflect the activity of the biological community and chemical reactions that occur in seawater. From 2016 to 2019, we repeatedly sampled the oligotrophic northwest Sargasso Sea in the vicinity of the Bermuda Atlantic Time‐series Study site (BATS) to quantitatively follow known compounds within the pool of dissolved organic matter in the upper 1000 m of the water column. Most metabolites showed surface enrichment, and 83% of the metabolites had significantly lower concentrations with increasing depth. Dissolved metabolite concentrations most notably revealed temporal variability. Fourteen metabolites displayed seasonality that was repeated in each of the 4 yr sampled. Concentrations of vitamins, including pantothenic acid (vitamin B5) and riboflavin (vitamin B2), increased annually during winter periods when mixed layer depths were deepest. During diel sampling, light‐sensitive riboflavin decreased significantly during daylight hours. The temporal variability in metabolites at BATS was less than the spatial variability in metabolites from a previous sample set collected over a broad latitudinal range in the western Atlantic Ocean. The metabolites examined in this study are all components of central carbon metabolism. By examining these metabolites at finer resolution and in a time‐series, we begin to provide insights into the chemical compounds that may be exchanged by microorganisms in marine systems, data which are fundamental to understanding the chemical response of marine systems to future changes in climate

Mercury Speciation and Mobilization in a Wastewater-Contaminated Groundwater Plume

We measured the concentration and speciation of mercury (Hg) in groundwater down-gradient from the site of wastewater infiltration beds operated by the Massachusetts Military Reservation, western Cape Cod, Massachusetts. Total mercury concentrations in oxic, mildly acidic, uncontaminated groundwater are 0.5–1 pM, and aquifer sediments have 0.5–1 ppb mercury. The plume of impacted groundwater created by the wastewater disposal is still evident, although inputs ceased in 1995, as indicated by anoxia extending at least 3 km down-gradient from the disposal site. Solutes indicative of a progression of anaerobic metabolisms are observed vertically and horizontally within the plume, with elevated nitrate concentrations and nitrate reduction surrounding a region with elevated iron concentrations indicating iron reduction. Mercury concentrations up to 800 pM were observed in shallow groundwater directly under the former infiltration beds, but concentrations decreased with depth and with distance down-gradient. Mercury speciation showed significant connections to the redox and metabolic state of the groundwater, with relatively little methylated Hg within the iron reducing sector of the plume, and dominance of this form within the higher nitrate/ammonium zone. Furthermore, substantial reduction of Hg­(II) to Hg⁰ within the core of the anoxic zone was observed when iron reduction was evident. These trends not only provide insight into the biogeochemical factors controlling the interplay of Hg species in natural waters, but also support hypotheses that anoxia and eutrophication in groundwater facilitate the mobilization of natural and anthropogenic Hg from watersheds/aquifers, which can be transported down-gradient to freshwaters and the coastal zone

Chitin utilization by marine picocyanobacteria and the evolution of a planktonic lifestyle

Marine picocyanobacteria (Prochlorococcus and Synechococcus), the most abundant photosynthetic cells in the oceans, are generally thought to have a primarily single-celled and free-living lifestyle. However, we find that genes for breaking down chitin - an abundant source of organic carbon that primarily exists as particles - are widespread in this group. We further show that cells with a chitin degradation pathway display chitin degradation activity, attach to chitin particles and show enhanced growth under low light conditions when exposed to chitosan, a partially deacetylated form of chitin. Marine chitin is largely derived from arthropods, whose roots lie in the early Phanerozoic, 520-535 million years ago, close to when marine picocyanobacteria began colonizing the ocean. We postulate that attachment to chitin particles allowed benthic cyanobacteria to emulate their mat-based lifestyle in the water column, initiating their expansion into the open ocean, seeding the rise of modern marine ecosystems. Transitioning to a constitutive planktonic life without chitin associations along a major early branch within the Prochlorococcus tree led to cellular and genomic streamlining. Our work highlights how coevolution across trophic levels creates metabolic opportunities and drives biospheric expansions

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