Beschreibung: © The Author(s), 2018. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Biogeosciences 15 (2018): 6451-6460, doi:10.5194/bg-15-6451-2018.

Beschreibung: 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 24h 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 8h 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.

Beschreibung: This work was funded by the National Science Foundation in a Chemical Oceanography Program Grant (OCE-1031271) awarded to Carl H. Lamborg and Mak A. Saito and a graduate student fellowship to Kathleen M. Munson.

Beschreibung: © The Author(s), 2016. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Biogeosciences 13 (2016): 5697-5717, doi:10.5194/bg-13-5697-2016.

Beschreibung: Cobalt is a nutrient to phytoplankton, but knowledge about its biogeochemical cycling is limited, especially in the Pacific Ocean. Here, we report sections of dissolved cobalt and labile dissolved cobalt from the US GEOTRACES GP16 transect in the South Pacific. The cobalt distribution is closely tied to the extent and intensity of the oxygen minimum zone in the eastern South Pacific with highest concentrations measured at the oxycline near the Peru margin. Below 200 m, remineralization and circulation produce an inverse relationship between cobalt and dissolved oxygen that extends throughout the basin. Within the oxygen minimum zone, elevated concentrations of labile cobalt are generated by input from coastal sources and reduced scavenging at low O2. As these high cobalt waters are upwelled and advected offshore, phytoplankton export returns cobalt to low-oxygen water masses underneath. West of the Peru upwelling region, dissolved cobalt is less than 10 pM in the euphotic zone and strongly bound by organic ligands. Because the cobalt nutricline within the South Pacific gyre is deeper than in oligotrophic regions in the North and South Atlantic, cobalt involved in sustaining phytoplankton productivity in the gyre is heavily recycled and ultimately arrives from lateral transport of upwelled waters from the eastern margin. In contrast to large coastal inputs, atmospheric deposition and hydrothermal vents along the East Pacific Rise appear to be minor sources of cobalt. Overall, these results demonstrate that oxygen biogeochemistry exerts a strong influence on cobalt cycling.

Beschreibung: This work was funded by NSF awards OCE-1233733 to MAS, OCE-1232814 to BST, and OCE-1237011 to JAR.

Beschreibung: © The Author(s), 2018. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Biogeosciences 15 (2018): 4923-4942, doi:10.5194/bg-15-4923-2018.

Beschreibung: Phaeocystis antarctica is an important phytoplankter of the Ross Sea where it dominates the early season bloom after sea ice retreat and is a major contributor to carbon export. The factors that influence Phaeocystis colony formation and the resultant Ross Sea bloom initiation have been of great scientific interest, yet there is little known about the underlying mechanisms responsible for these phenomena. Here, we present laboratory and field studies on Phaeocystis antarctica grown under multiple iron conditions using a coupled proteomic and transcriptomic approach. P. antarctica had a lower iron limitation threshold than a Ross Sea diatom Chaetoceros sp., and at increased iron nutrition (〉120pM Fe') a shift from flagellate cells to a majority of colonial cells in P. antarctica was observed, implying a role for iron as a trigger for colony formation. Proteome analysis revealed an extensive and coordinated shift in proteome structure linked to iron availability and life cycle transitions with 327 and 436 proteins measured as significantly different between low and high iron in strains 1871 and 1374, respectively. The enzymes flavodoxin and plastocyanin that can functionally replace iron metalloenzymes were observed at low iron treatments consistent with cellular iron-sparing strategies, with plastocyanin having a larger dynamic range. The numerous isoforms of the putative iron-starvation-induced protein (ISIP) group (ISIP2A and ISIP3) had abundance patterns coinciding with that of either low or high iron (and coincident flagellate or the colonial cell types in strain 1871), implying that there may be specific iron acquisition systems for each life cycle type. The proteome analysis also revealed numerous structural proteins associated with each cell type: within flagellate cells actin and tubulin from flagella and haptonema structures as well as a suite of calcium-binding proteins with EF domains were observed. In the colony-dominated samples a variety of structural proteins were observed that are also often found in multicellular organisms including spondins, lectins, fibrillins, and glycoproteins with von Willebrand domains. A large number of proteins of unknown function were identified that became abundant at either high or low iron availability. These results were compared to the first metaproteomic analysis of a Ross Sea Phaeocystis bloom to connect the mechanistic information to the in situ ecology and biogeochemistry. Proteins associated with both flagellate and colonial cells were observed in the bloom sample consistent with the need for both cell types within a growing bloom. Bacterial iron storage and B12 biosynthesis proteins were also observed consistent with chemical synergies within the colony microbiome to cope with the biogeochemical conditions. Together these responses reveal a complex, highly coordinated effort by P. antarctica to regulate its phenotype at the molecular level in response to iron and provide a window into the biology, ecology, and biogeochemistry of this group.

Beschreibung: Support for this study was provided by an Investigator grant to Mak A. Saito from the Gordon and Betty Moore Foundation (GBMF3782), National Science Foundation grants NSF-PLR 0732665, OCE-1435056, OCE-1220484, and ANT-1643684, the WHOI Coastal Ocean Institute, and a CINAR Postdoctoral Scholar Fellowship provided to Sara J. Bender through the Woods Hole Oceanographic Institution. Support was provided to Andrew E. Allen through NSF awards ANT-0732822, ANT-1043671, and OCE-1136477 and Gordon and Betty Moore Foundation grant GBMF3828. Additional support was provided to GRD through NSF award OPP-0338097.

Beschreibung: © The Author(s), 2017. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Biogeosciences 14 (2017): 2715-2739, doi:10.5194/bg-14-2715-2017.

Beschreibung: Cobalt is the scarcest of metallic micronutrients and displays a complex biogeochemical cycle. This study examines the distribution, chemical speciation, and biogeochemistry of dissolved cobalt during the US North Atlantic GEOTRACES transect expeditions (GA03/3_e), which took place in the fall of 2010 and 2011. Two major subsurface sources of cobalt to the North Atlantic were identified. The more prominent of the two was a large plume of cobalt emanating from the African coast off the eastern tropical North Atlantic coincident with the oxygen minimum zone (OMZ) likely due to reductive dissolution, biouptake and remineralization, and aeolian dust deposition. The occurrence of this plume in an OMZ with oxygen above suboxic levels implies a high threshold for persistence of dissolved cobalt plumes. The other major subsurface source came from Upper Labrador Seawater, which may carry high cobalt concentrations due to the interaction of this water mass with resuspended sediment at the western margin or from transport further upstream. Minor sources of cobalt came from dust, coastal surface waters and hydrothermal systems along the Mid-Atlantic Ridge. The full depth section of cobalt chemical speciation revealed near-complete complexation in surface waters, even within regions of high dust deposition. However, labile cobalt observed below the euphotic zone demonstrated that strong cobalt-binding ligands were not present in excess of the total cobalt concentration there, implying that mesopelagic labile cobalt was sourced from the remineralization of sinking organic matter. In the upper water column, correlations were observed between total cobalt and phosphate, and between labile cobalt and phosphate, demonstrating a strong biological influence on cobalt cycling. Along the western margin off the North American coast, this correlation with phosphate was no longer observed and instead a relationship between cobalt and salinity was observed, reflecting the importance of coastal input processes on cobalt distributions. In deep waters, both total and labile cobalt concentrations were lower than in intermediate depth waters, demonstrating that scavenging may remove labile cobalt from the water column. Total and labile cobalt distributions were also compared to a previously published South Atlantic GEOTRACES-compliant zonal transect (CoFeMUG, GAc01) to discern regional biogeochemical differences. Together, these Atlantic sectional studies highlight the dynamic ecological stoichiometry of total and labile cobalt. As increasing anthropogenic use and subsequent release of cobalt poses the potential to overpower natural cobalt signals in the oceans, it is more important than ever to establish a baseline understanding of cobalt distributions in the ocean.

Beschreibung: We also gratefully acknowledge support of funding agencies on the following grants: the US National Science Foundation (NSF-OCE 0928414, 1233261, 1435056) and the Gordon and Betty Moore Foundation (grant 3738).

Beschreibung: © The Authors, 2010. This article is distributed under the terms of the Creative Commons Attribution 3.0 License. The definitive version was published in Biogeosciences 7 (2010): 4059-4082, doi:10.5194/bg-7-4059-2010.

Beschreibung: We report the distribution of cobalt (Co) in the Ross Sea polynya during austral summer 2005–2006 and the following austral spring 2006. The vertical distribution of total dissolved Co (dCo) was similar to soluble reactive phosphate (PO43−), with dCo and PO43− showing a significant correlation throughout the water column (r2 = 0.87, 164 samples). A strong seasonal signal for dCo was observed, with most spring samples having concentrations ranging from ~45–85 pM, whereas summer dCo values were depleted below these levels by biological activity. Surface transect data from the summer cruise revealed concentrations at the low range of this seasonal variability (~30 pM dCo), with concentrations as low as 20 pM observed in some regions where PO43− was depleted to ~0.1 μM. Both complexed Co, defined as the fraction of dCo bound by strong organic ligands, and labile Co, defined as the fraction of dCo not bound by these ligands, were typically observed in significant concentrations throughout the water column. This contrasts the depletion of labile Co observed in the euphotic zone of other ocean regions, suggesting a much higher bioavailability for Co in the Ross Sea. An ecological stoichiometry of 37.6 μmol Co:mol−1 PO43− calculated from dissolved concentrations was similar to values observed in the subarctic Pacific, but approximately tenfold lower than values in the Eastern Tropical Pacific and Equatorial Atlantic. The ecological stoichiometries for dissolved Co and Zn suggest a greater overall use of Zn relative to Co in the shallow waters of the Ross Sea, with a Co:PO43−/Zn:PO43− ratio of 1:17. Comparison of these observed stoichiometries with values estimated in culture studies suggests that Zn is a key micronutrient that likely influences phytoplankton diversity in the Ross Sea. In contrast, the observed ecological stoichiometries for Co were below values necessary for the growth of eukaryotic phytoplankton in laboratory culture experiments conducted in the absence of added zinc, implying the need for significant Zn nutrition in the Zn-Co cambialistic enzymes. The lack of an obvious kink in the dissolved Co:PO43− relationship was in contrast to Zn:PO43− and Cd:PO43− kinks previously observed in the Ross Sea. An excess uptake mechanism for kink formation is proposed as a major driver of Cd:PO43− kinks, where Zn and Cd uptake in excess of that needed for optimal growth occurs at the base of the euphotic zone, and no clear Co kink occurs because its abundances are too low for excess uptake. An unusual characteristic of Co geochemistry in the Ross Sea is an apparent lack of Co scavenging processes, as inferred from the absence of dCo removal below the euphotic zone. We hypothesize that this vertical distribution reflects a low rate of Co scavenging by Mn oxidizing bacteria, perhaps due to Mn scarcity, relative to the timescale of the annual deep winter mixing in the Ross Sea. Thus Co exhibits nutrient-like behavior in the Ross Sea, in contrast to its hybrid-type behavior in other ocean regions, with implications for the possibility of increased marine Co inventories and utility as a paleooceanographic proxy.

Beschreibung: This research was supported by the US National Science Foundation through research grants (OPP-0440840, OPP-0338097, OPP-0732665, OCE-0452883, OCE-0752991, OCE-0928414).

Beschreibung: © The Author(s), 2017. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Biogeosciences 14 (2017): 4637-4662, doi:10.5194/bg-14-4637-2017.

Beschreibung: The stoichiometry of biological components and their influence on dissolved distributions have long been of interest in the study of the oceans. Cobalt has the smallest oceanic inventory of inorganic micronutrients and hence is particularly vulnerable to influence by internal oceanic processes including euphotic zone uptake, remineralization, and scavenging. Here we observe not only large variations in dCo : P stoichiometry but also the acceleration of those dCo : P ratios in the upper water column in response to several environmental processes. The ecological stoichiometry of total dissolved cobalt (dCo) was examined using data from a US North Atlantic GEOTRACES transect and from a zonal South Atlantic GEOTRACES-compliant transect (GA03/3_e and GAc01) by Redfieldian analysis of its statistical relationships with the macronutrient phosphate. Trends in the dissolved cobalt to phosphate (dCo : P) stoichiometric relationships were evident in the basin-scale vertical structure of cobalt, with positive dCo : P slopes in the euphotic zone and negative slopes found in the ocean interior and in coastal environments. The euphotic positive slopes were often found to accelerate towards the surface and this was interpreted as being due to the combined influence of depleted phosphate, phosphorus-sparing (conserving) mechanisms, increased alkaline phosphatase metalloenzyme production (a zinc or perhaps cobalt enzyme), and biochemical substitution of Co for depleted Zn. Consistent with this, dissolved Zn (dZn) was found to be drawn down to only 2-fold more than dCo, despite being more than 18-fold more abundant in the ocean interior. Particulate cobalt concentrations increased in abundance from the base of the euphotic zone to become  ∼  10 % of the overall cobalt inventory in the upper euphotic zone with high stoichiometric values of  ∼  400 µmol Co mol−1 P. Metaproteomic results from the Bermuda Atlantic Time-series Study (BATS) station found cyanobacterial isoforms of the alkaline phosphatase enzyme to be prevalent in the upper water column, as well as a sulfolipid biosynthesis protein indicative of P sparing. The negative dCo : P relationships in the ocean interior became increasingly vertical with depth, and were consistent with the sum of scavenging and remineralization processes (as shown by their dCo : P vector sums). Attenuation of the remineralization with depth resulted in the increasingly vertical dCo : P relationships. Analysis of particulate Co with particulate Mn and particulate phosphate also showed positive linear relationships below the euphotic zone, consistent with the presence and increased relative influence of Mn oxide particles involved in scavenging. Visualization of dCo : P slopes across an ocean section revealed hotspots of scavenging and remineralization, such as at the hydrothermal vents and below the oxygen minimum zone (OMZ) region, respectively, while that of an estimate of Co* illustrated stoichiometrically depleted values in the mesopelagic and deep ocean due to scavenging. This study provides insights into the coupling between the dissolved and particulate phase that ultimately creates Redfield stoichiometric ratios, demonstrating that the coupling is not an instantaneous process and is influenced by the element inventory and rate of exchange between phases. Cobalt's small water column inventory and the influence of external factors on its biotic stoichiometry can erode its limited inertia and result in an acceleration of the dissolved stoichiometry towards that of the particulate phase in the upper euphotic zone. As human use of cobalt grows exponentially with widespread adoption of lithium ion batteries, there is a potential to affect the limited biogeochemical inertia of cobalt and its resultant ecology in the oceanic euphotic zone.

Beschreibung: This work was funded by the National Science Foundation as part of the US GEOTRACES North Atlantic Zonal Transect program under grants OCE-0928414 and OCE-1435056 (to Mak A. Saito), OCE-0928289 (to Benjamin S. Twining), OCE-0963026 (to Phoebe Lam) and support from the Gordon and Betty Moore Foundation (3782 to Mak A. Saito).