113 research outputs found

    Dynamic mercury methylation and demethylation in oligotrophic marine water

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    Mercury bioaccumulation in open-ocean food webs depends on the net rate of inorganic mercury conversion to monomethylmercury in the water column. We measured significant methylation rates across large gradients in oxygen utilization in the oligotrophic central Pacific Ocean. Overall, methylation rates over 24&thinsp;h incubation periods were comparable to those previously published from Arctic and Mediterranean waters despite differences in productivity between these marine environments. In contrast to previous studies that have attributed Hg methylation to heterotrophic bacteria, we measured higher methylation rates in filtered water compared to unfiltered water. Furthermore, we observed enhanced demethylation of newly produced methylated mercury in incubations of unfiltered water relative to filtered water. The addition of station-specific bulk filtered particulate matter, a source of inorganic mercury substrate and other possibly influential compounds, did not stimulate sustained methylation, although transient enhancement of methylation occurred within 8&thinsp;h of addition. The addition of dissolved inorganic cobalt also produced dramatic, if transient, increases in mercury methylation. Our results suggest important roles for noncellular or extracellular methylation mechanisms and demethylation in determining methylated mercury concentrations in marine oligotrophic waters. Methylation and demethylation occur dynamically in the open-ocean water column, even in regions with low accumulation of methylated mercury.</p

    Increased accumulation of sulfur in lake sediments of the high Arctic

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    Author Posting. © The Author(s), 2010. This is the author's version of the work. It is posted here by permission of American Chemical Society for personal use, not for redistribution. The definitive version was published in Environmental Science & Technology 44 (2010): 8415-8421, doi:10.1021/es101991p.We report a synchronous increase in accumulation of reduced inorganic sulfur since c. 1980 in sediment cores from eight of nine lakes studied in the Canadian Arctic and Svalbard (Norway). Sediment incubations and detailed analyses of sediment profiles from two of the lakes indicate that increases in sulfur accumulation may be due ultimately to a changing climate. Warming-induced lengthening of the ice-free season is resulting in well-documented increases in algal production and sedimentation of the resulting detrital matter. Algal detritus is a rich source of labile carbon, which in these sediments stimulates dissimilatory sulfate reduction. The sulfide produced is stored in sediment (as acid volatile sulfide), converted to other forms of sulfur, or reoxidized to sulfate and lost to the water column. An acceleration of the sulfur cycle in Arctic lakes could have profound effects on important biogeochemical processes, such as carbon burial and mercury methylation.Funding was provided by the WHOI Ocean and Climate Change Institute, the USGS WHOI Postdoctoral Scholar Program, Environment Canada, the Danmarks Grundforskningsfond, and the Norges forskningsråd (grant number 107745/730)

    Basin-scale inputs of cobalt, iron, and manganese from the Benguela-Angola front to the South Atlantic Ocean

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    Author Posting. © Association for the Sciences of Limnology and Oceanography, 2012. This article is posted here by permission of Association for the Sciences of Limnology and Oceanography for personal use, not for redistribution. The definitive version was published in Limnology and Oceanography 57 (2012): 989-1010, doi:10.4319/lo.2012.57.4.0989.We present full-depth zonal sections of total dissolved cobalt, iron, manganese, and labile cobalt from the South Atlantic Ocean. A basin-scale plume from the African coast appeared to be a major source of dissolved metals to this region, with high cobalt concentrations in the oxygen minimum zone of the Angola Dome and extending 2500 km into the subtropical gyre. Metal concentrations were elevated along the coastal shelf, likely due to reductive dissolution and resuspension of particulate matter. Linear relationships between cobalt, N2O, and O2, as well as low surface aluminum supported a coastal rather than atmospheric cobalt source. Lateral advection coupled with upwelling, biological uptake, and remineralization delivered these metals to the basin, as evident in two zonal transects with distinct physical processes that exhibited different metal distributions. Scavenging rates within the coastal plume differed for the three metals; iron was removed fastest, manganese removal was 2.5 times slower, and cobalt scavenging could not be discerned from water mass mixing. Because scavenging, biological utilization, and export constantly deplete the oceanic inventories of these three hybrid-type metals, point sources of the scale observed here likely serve as vital drivers of their oceanic cycles. Manganese concentrations were elevated in surface waters across the basin, likely due to coupled redox processes acting to concentrate the dissolved species there. These observations of basin-scale hybrid metal plumes combined with the recent projections of expanding oxygen minimum zones suggest a potential mechanism for effects on ocean primary production and nitrogen fixation via increases in trace metal source inputs.This research was supported US National Science Foundation Chemical Oceanography (Division of Ocean Sciences OCE-0452883, OCE-0752291, OCE-0928414, OCE-1031271), the Center for Microbial Research and Education, the Gordon and Betty Moore Foundation, the WHOI Coastal Ocean Institute, and the WHOI Ocean Life Institute

    Spatial heterogeneity in particle-associated, light-independent superoxide production within productive coastal waters

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    © The Author(s), 2020. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Sutherland, K. M., Grabb, K. C., Karolewski, J. S., Plummer, S., Farfan, G. A., Wankel, S. D., Diaz, J. M., Lamborg, C. H., & Hansel, C. M. Spatial heterogeneity in particle-associated, light-independent superoxide production within productive coastal waters. Journal of Geophysical Research: Oceans, 125(10), (2020): e2020JC016747, https://doi.org/10.1029/2020JC016747.In the marine environment, the reactive oxygen species (ROS) superoxide is produced through a diverse array of light‐dependent and light‐independent reactions, the latter of which is thought to be primarily controlled by microorganisms. Marine superoxide production influences organic matter remineralization, metal redox cycling, and dissolved oxygen concentrations, yet the relative contributions of different sources to total superoxide production remain poorly constrained. Here we investigate the production, steady‐state concentration, and particle‐associated nature of light‐independent superoxide in productive waters off the northeast coast of North America. We find exceptionally high levels of light‐independent superoxide in the marine water column, with concentrations ranging from 10 pM to in excess of 2,000 pM. The highest superoxide concentrations were particle associated in surface seawater and in aphotic seawater collected meters off the seafloor. Filtration of seawater overlying the continental shelf lowered the light‐independent, steady‐state superoxide concentration by an average of 84%. We identify eukaryotic phytoplankton as the dominant particle‐associated source of superoxide to these coastal waters. We contrast these measurements with those collected at an off‐shelf station, where superoxide concentrations did not exceed 100 pM, and particles account for an average of 40% of the steady‐state superoxide concentration. This study demonstrates the primary role of particles in the production of superoxide in seawater overlying the continental shelf and highlights the importance of light‐independent, dissolved‐phase reactions in marine ROS production.This work was funded by grants from the Chemical Oceanography program of the National Science Foundation (OCE‐1355720 to C. M. H. and C. H. L.), NASA Earth and Space Science Fellowship (Grant NNX15AR62H to K. M. S.), Agouron Institute Postdoctoral Fellowship (K. M. S.), NSF GRFPs (2016230268 to K. C. G. and 2017250547 to S. P.), and a Sloan Research Fellowship (J. M. D.). The Guava flow cytometer was purchased through an NSF equipment improvement grant (1624593)

    Mercury Cycling in the North Pacific Subtropical Gyre as Revealed by Mercury Stable Isotope Ratios

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    The oceans are an important global reservoir for mercury (Hg), and marine fish consumption is the dominant human exposure pathway for its toxic methylated form. A more thorough understanding of the global biogeochemical cycle of Hg requires additional information on the mechanisms that control Hg cycling in pelagic marine waters. In this study, Hg isotope ratios and total Hg concentrations are used to explore Hg biogeochemistry in oligotrophic marine environments north of Hawaii. We present the first measurements of the vertical water column distribution of Hg concentrations and the Hg isotopic composition in precipitation, marine particles, and zooplankton near Station ALOHA (22°45′N, 158°W). Our results reveal production and demethylation of methylmercury in both the euphotic (0–175 m) and mesopelagic zones (200–1,000 m). We document a strong relationship between Hg isotopic composition and depth in particles, zooplankton, and fish in the water column and diurnal variations in Δ199Hg values in zooplankton sampled near the surface (25 m). Based on these observations and stable Hg isotope relationships in the marine food web, we suggest that the Hg found in large pelagic fish at Station ALOHA was originally deposited largely by precipitation, transformed into methyl‐Hg, and bioaccumulated in situ in the water column. Our results highlight how Hg isotopic compositions reflect abiotic and biotic production and degradation of methyl‐Hg throughout the water column and the importance of particles and zooplankton in the vertical transport of Hg

    Mercury Cycling in the North Pacific Subtropical Gyre as Revealed by Mercury Stable Isotope Ratios

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    The oceans are an important global reservoir for mercury (Hg), and marine fish consumption is the dominant human exposure pathway for its toxic methylated form. A more thorough understanding of the global biogeochemical cycle of Hg requires additional information on the mechanisms that control Hg cycling in pelagic marine waters. In this study, Hg isotope ratios and total Hg concentrations are used to explore Hg biogeochemistry in oligotrophic marine environments north of Hawaii. We present the first measurements of the vertical water column distribution of Hg concentrations and the Hg isotopic composition in precipitation, marine particles, and zooplankton near Station ALOHA (22°45â ²N, 158°W). Our results reveal production and demethylation of methylmercury in both the euphotic (0â 175 m) and mesopelagic zones (200â 1,000 m). We document a strong relationship between Hg isotopic composition and depth in particles, zooplankton, and fish in the water column and diurnal variations in Î 199Hg values in zooplankton sampled near the surface (25 m). Based on these observations and stable Hg isotope relationships in the marine food web, we suggest that the Hg found in large pelagic fish at Station ALOHA was originally deposited largely by precipitation, transformed into methylâ Hg, and bioaccumulated in situ in the water column. Our results highlight how Hg isotopic compositions reflect abiotic and biotic production and degradation of methylâ Hg throughout the water column and the importance of particles and zooplankton in the vertical transport of Hg.Key PointsMMHg bioaccumulated in fish is derived primarily from Hg (II) deposited in atmospheric precipitationMarine particles host the majority of Hg available for production of MMHg in the open oceanMethylation and demethylation of Hg occurs throughout the euphotic and mesopelagic zones in the North Pacific Subtropical GyrePeer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/150543/1/gbc20883.pdfhttps://deepblue.lib.umich.edu/bitstream/2027.42/150543/2/gbc20883_am.pd

    Hydrothermal trace metal release and microbial metabolism in the northeastern Lau Basin of the South Pacific Ocean

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    © The Author(s), 2021. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Cohen, N. R., Noble, A. E., Moran, D. M., McIlvin, M. R., Goepfert, T. J., Hawco, N. J., German, C. R., Horner, T. J., Lamborg, C. H., McCrow, J. P., Allen, A. E., & Saito, M. A. Hydrothermal trace metal release and microbial metabolism in the northeastern Lau Basin of the South Pacific Ocean. Biogeosciences, 18(19), (2021): 5397–5422, https://doi.org/10.5194/bg-18-5397-2021.Bioactive trace metals are critical micronutrients for marine microorganisms due to their role in mediating biological redox reactions, and complex biogeochemical processes control their distributions. Hydrothermal vents may represent an important source of metals to microorganisms, especially those inhabiting low-iron waters, such as in the southwest Pacific Ocean. Previous measurements of primordial 3He indicate a significant hydrothermal source originating in the northeastern (NE) Lau Basin, with the plume advecting into the southwest Pacific Ocean at 1500–2000 m depth (Lupton et al., 2004). Studies investigating the long-range transport of trace metals associated with such dispersing plumes are rare, and the biogeochemical impacts on local microbial physiology have not yet been described. Here we quantified dissolved metals and assessed microbial metaproteomes across a transect spanning the tropical and equatorial Pacific with a focus on the hydrothermally active NE Lau Basin and report elevated iron and manganese concentrations across 441 km of the southwest Pacific. The most intense signal was detected near the Mangatolo Triple Junction (MTJ) and Northeast Lau Spreading Center (NELSC), in close proximity to the previously reported 3He signature. Protein content in distal-plume-influenced seawater, which was high in metals, was overall similar to background locations, though key prokaryotic proteins involved in metal and organic uptake, protein degradation, and chemoautotrophy were abundant compared to deep waters outside of the distal plume. Our results demonstrate that trace metals derived from the NE Lau Basin are transported over appreciable distances into the southwest Pacific Ocean and that bioactive chemical resources released from submarine vent systems are utilized by surrounding deep-sea microbes, influencing both their physiology and their contributions to ocean biogeochemical cycling.This research has been supported by the National Science Foundation (grant nos. 1031271, 1924554, 1850719, 1736599, and 1851007); the Gordon and Betty Moore Foundation (grant no. 3782); and the Simons Foundation (grant no. 544236)

    Lignin biomarkers as tracers of mercury sources in lakes water column

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    This study presents the role of specific terrigenous organic compounds as important vectors of mercury (Hg) transported from watersheds to lakes of the Canadian boreal forest. In order to differentiate the autochthonous from the allochthonous organic matter (OM), lignin derived biomarker signatures [Lambda, S/V, C/V, P/(V ? S), 3,5-Bd/V and (Ad/Al)v] were used. Since lignin is exclusively produced by terrigenous plants, this approach can give a non equivocal picture of the watershed inputs to the lakes. Moreover, it allows a characterization of the source of OM and its state of degradation. The water column of six lakes from the Canadian Shield was sampled monthly between June and September 2005. Lake total dissolved Hg concentrations and Lambda were positively correlated, meaning that Hg and ligneous inputs are linked (dissolved OM r2 = 0.62, p\0.0001; particulate OM r2 = 0.76, p\0.0001). Ratios of P/(V ? S) and 3,5-Bd/V from both dissolved OM and particulate OM of the water column suggest an inverse relationship between the progressive state of pedogenesis and maturation of the OM in soil before entering the lake, and the Hg concentrations in the water column. No relation was found between Hg levels in the lakes and the watershed flora composition—angiosperm versus gymnosperm or woody versus non-woody compounds. This study has significant implications for watershed management of ecosystems since limiting fresh terrestrial OM inputs should reduce Hg inputs to the aquatic systems. This is particularly the case for largescale land-use impacts, such as deforestation, agriculture and urbanization, associated to large quantities of soil OM being transferred to aquatic systems

    Nutrient Supply and Mercury Dynamics in Marine Ecosystems: A Conceptual Model

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    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
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