skip to main content
Explore Scholarly Publications and Datasets in the NSF-PAR

  • NSF Public Access
  • Search Results
  • Accepted Manuscript: Coastal sources, sinks and strong organic complexation of dissolved cobalt within the US North Atlantic GEOTRACES transect GA03
Title: Coastal sources, sinks and strong organic complexation of dissolved cobalt within the US North Atlantic GEOTRACES transect GA03

Abstract. 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 more » 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.

« less
Authors:
; ; ; ;
Award ID(s):
1736599
Publication Date:
NSF-PAR ID:
10076508
Journal Name:
Biogeosciences
Volume:
14
Issue:
11
Page Range or eLocation-ID:
2715 to 2739
ISSN:
1726-4189
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ; ; ; ; ; ; ; ; et al ( , Biogeosciences)
    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 amore »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.« less
  2. ; ; ( , Scientific prospectus)
    The Iberian margin is a well-known source of rapidly accumulating sediment that contains a high-fidelity record of millennial climate variability (MCV) for the late Pleistocene. The late Sir Nicholas (Nick) Shackleton demonstrated that piston cores from the region can be correlated precisely to polar ice cores in both hemispheres. Moreover, the narrow continental shelf off Portugal results in the rapid delivery of terrestrial material to the deep-sea environment, thereby permitting correlation of marine and ice core records to European terrestrial sequences. Few places exist in the world where such detailed marine-ice-terrestrial linkages are possible. The continuity, high sedimentation rates, andmore »fidelity of climate signals preserved in Iberian margin sediments make this region a prime target for ocean drilling. During Integrated Ocean Drilling Program Expedition 339 (Mediterranean Outflow), one of the sites proposed here was drilled to a total depth of 155.9 meters below seafloor in multiple holes. At Site U1385 (the “Shackleton site”) a complete record of hemipelagic sedimentation was recovered for the last 1.45 My corresponding to Marine Isotope Stage 47 with sedimentation rates of 10–20 cm/ky. Preliminary results from Site U1385 demonstrate the great promise of the Iberian margin to yield long records of millennial-scale climate change and land–sea comparisons. International Ocean Discovery Program (IODP) Expedition 397 will extend this remarkable sediment archive through the Pliocene and expand the depth range of available sites by drilling additional sequences in water depths from 1304 to 4686 meters below sea level (mbsl). This depth transect is designed to complement those sites drilled during Expedition 339 (560–1073 mbsl) where sediment was recovered at intermediate water depth under the influence of Mediterranean Outflow Water (MOW). Together, the sites recovered during Expeditions 339 and 397 will constitute a complete depth transect with which to study past variability of all the major subsurface water masses of the eastern North Atlantic. Because most of the mass, thermal inertia, and carbon in the ocean-atmosphere system is contained in the deep ocean, well-placed depth transects in each of the major ocean basins are needed to understand the underlying mechanisms of glacial–interglacial cycles and MCV. We have identified four primary sites (SHACK-4C, SHACK-10B, SHACK-11B, and SHACK-14A) at which multiple holes will be drilled to ensure complete recovery of the stratigraphic sections at each site, ranging in age from the latest Miocene to Holocene. Building on the success of Site U1385 and given the seminal importance of the Iberian margin for paleoclimatology and marine-ice-terrestrial correlations, the cores recovered during Expedition 397 will provide present and future generations of paleoceanographers with the raw material needed to reconstruct the North Atlantic climate at high temporal resolution for the entire Quaternary and Pliocene.« less
  3. ; ; ; ; ; ; ( , Biogeosciences)

    Abstract. The patterns of the large-scale, meso- and submesoscale surface circulation on biogeochemical and biological distributions are examined in the western tropical South Pacific (WTSP) in the context of the OUTPACE cruise (February–April 2015). Multi-disciplinary original in situ observations were achieved along a zonal transect through the WTSP and their analysis was coupled with satellite data. The use of Lagrangian diagnostics allows for the identification of water mass pathways, mesoscale structures, and submesoscale features such as fronts. In particular, we confirmed the existence of a global wind-driven southward circulation of surface waters in the entire WTSP, using a new high-resolution altimetry-derivedmore »product, validated by in situ drifters, that includes cyclogeostrophy and Ekman components with geostrophy. The mesoscale activity is shown to be responsible for counter-intuitive water mass trajectories in two subregions: (i) the Coral Sea, with surface exchanges between the North Vanuatu Jet and the North Caledonian Jet, and (ii) around 170°W, with an eastward pathway, whereas a westward general direction dominates. Fronts and small-scale features, detected with finite-size Lyapunov exponents (FSLEs), are correlated with 25% of surface tracer gradients, which reveals the significance of such structures in the generation of submesoscale surface gradients. Additionally, two high-frequency sampling transects of biogeochemical parameters and microorganism abundances demonstrate the influence of fronts in controlling the spatial distribution of bacteria and phytoplankton, and as a consequence the microbial community structure. All circulation scales play an important role that has to be taken into account not only when analysing the data from OUTPACE but also, more generally, for understanding the global distribution of biogeochemical components.

    « less
  4. ; ; ; ; ; ; ; ; ; ; et al ( , Nature Microbiology)
    Marine microeukaryotes play a fundamental role in biogeochemical cycling through the transfer of energy to higher trophic levels and vertical carbon transport. Despite their global importance, microeukaryote physiology, nutrient metabolism and contributions to carbon cycling across offshore ecosystems are poorly characterized. Here, we observed the prevalence of dinoflagellates along a 4,600-km meridional transect extending across the central Pacific Ocean, where oligotrophic gyres meet equatorial upwelling waters rich in macronutrients yet low in dissolved iron. A combined multi-omics and geochemical analysis provided a window into dinoflagellate metabolism across the transect, indicating a continuous taxonomic dinoflagellate community that shifted its functional transcriptomemore »and proteome as it extended from the euphotic to the mesopelagic zone. In euphotic waters, multi-omics data suggested that a combination of trophic modes were utilized, while mesopelagic metabolism was marked by cytoskeletal investments and nutrient recycling. Rearrangement in nutrient metabolism was evident in response to variable nitrogen and iron regimes across the gradient, with no associated change in community assemblage. Total dinoflagellate proteins scaled with particulate carbon export, with both elevated in equatorial waters, suggesting a link between dinoflagellate abundance and total carbon flux. Dinoflagellates employ numerous metabolic strategies that enable broad occupation of central Pacific ecosystems and play a dual role in carbon transformation through both photosynthetic fixation in the euphotic zone and remineralization in the mesopelagic zone.« less
  5. ; ; ; ( , Preliminary report)
    International Ocean Discovery Program (IODP) Expedition 357 successfully cored an east–west transect across the southern wall of Atlantis Massif on the western flank of the Mid-Atlantic Ridge to study the links between serpentinization processes and microbial activity in the shallow subsurface of highly altered ultramafic and mafic sequences that have been uplifted to the seafloor along a major detachment fault zone. The primary goals of this expedition were to (1) examine the role of serpentinization in driving hydrothermal systems, sustaining microbial communities, and sequestering carbon; (2) characterize the tectonomagmatic processes that lead to lithospheric heterogeneities and detachment faulting; and (3)more »assess how abiotic and biotic processes change with variations in rock type and progressive exposure on the seafloor. To accomplish these objectives, we developed a coring and sampling strategy based around the use of seabed rock drills—the first time that such systems have been used in the scientific ocean drilling programs. This technology was chosen in hopes of achieving high recovery of the carbonate cap sequences and intact contact and deformation relationships. The expedition plans also included several engineering developments to assess geochemical parameters during drilling; sample bottom water before and after drilling; supply synthetic tracers during drilling for contamination assessment; gather downhole electrical resistivity and magnetic susceptibility logs for assessing fractures, fluid flow, and extent of serpentinization; and seal boreholes to provide opportunities for future experiments. Seventeen holes were drilled at nine sites across Atlantis Massif, with two sites on the eastern end of the southern wall (Sites M0068 and M0075), three sites in the central section of the southern wall north of the Lost City hydrothermal field (Sites M0069, M0072, and M0076), two sites on the western end (Sites M0071 and M0073), and two sites north of the southern wall in the direction of the central dome of the massif and Integrated Ocean Drilling Program Site U1309 (Sites M0070 and M0074). Use of seabed rock drills enabled collection of more than 57 m of core, with borehole penetration ranging from 1.3 to 16.44 meters below seafloor and core recoveries as high as 75% of total penetration. This high level of recovery of shallow mantle sequences is unprecedented in the history of ocean drilling. The cores recovered along the southern wall of Atlantis Massif have highly heterogeneous lithologies, types of alteration, and degrees of deformation. The ultramafic rocks are dominated by harzburgites with intervals of dunite and minor pyroxenite veins, as well as gabbroic rocks occurring as melt impregnations and veins, all of which provide information about early magmatic processes and the magmatic evolution in the southernmost portion of Atlantis Massif. Dolerite dikes and basaltic rocks represent the latest stage of magmatic activity. Overall, the ultramafic rocks recovered during Expedition 357 revealed a high degree of serpentinization, as well as metasomatic talc-amphibole-chlorite overprinting and local rodingitization. Metasomatism postdates an early phase of serpentinization but predates late-stage intrusion and alteration of dolerite dikes and the extrusion of basalt. The intensity of alteration is generally lower in the gabbroic and doleritic rocks. Chilled margins in dolerite intruded into talc-amphibole-chlorite schists are observed at the most eastern Site M0075. Deformation in Expedition 357 cores is variable and dominated by brecciation and formation of localized shear zones; the degree of carbonate veining was lower than anticipated. All types of variably altered and deformed ultramafic and mafic rocks occur as components in sedimentary breccias and as fault scarp rubble. The sedimentary cap rocks include basaltic breccias with a carbonate sand matrix and/or fossiliferous carbonate. Fresh glass on basaltic components was observed in some of the breccias. The expedition also successfully applied new technologies, namely (1) extensively using an in situ sensor package and water sampling system on the seabed drills for evaluating real-time dissolved oxygen and methane, pH, oxidation-reduction potential, temperature, and conductivity during drilling; (2) deploying a borehole plug system for sealing seabed drill boreholes at four sites to allow access for future sampling; and (3) proving that tracers can be delivered into drilling fluids when using seabed drills. The rock drill sensor packages and water sampling enabled detection of elevated dissolved methane and hydrogen concentrations during and/or after drilling, with “hot spots” of hydrogen observed over Sites M0068–M0072 and methane over Sites M0070–M0072. Shipboard determination of contamination tracer delivery confirmed appropriate sample handling procedures for microbiological and geochemical analyses, which will aid all subsequent microbiological investigations that are part of the science party sampling plans, as well as verify this new tracer delivery technology for seabed drill rigs. Shipboard investigation of biomass density in select samples revealed relatively low and variable cell densities, and enrichment experiments set up shipboard reveal growth. Thus, we anticipate achieving many of the deep biosphere–related objectives of the expedition through continued scientific investigation in the coming years. Finally, although not an objective of the expedition, we were serendipitously able to generate a high-resolution (20 m per pixel) multibeam bathymetry map across the entire Atlantis Massif and the nearby fracture zone, Mid-Atlantic Ridge, and eastern conjugate, taking advantage of weather and operational downtime. This will assist science party members in evaluating and interpreting tectonic and mass-wasting processes at Atlantis Massif.« less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email