skip to main content


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 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.

 
more » « less
Award ID(s):
1736599
NSF-PAR ID:
10076508
Author(s) / Creator(s):
; ; ; ;
Date Published:
Journal Name:
Biogeosciences
Volume:
14
Issue:
11
ISSN:
1726-4189
Page Range / eLocation ID:
2715 to 2739
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. 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. 
    more » « less
  2. Abstract. Over the past decade, the GEOTRACES and wider trace metalgeochemical community has made substantial contributions towardsconstraining the marine cobalt (Co) cycle and its major biogeochemicalprocesses. However, few Co speciation studies have been conducted in theNorth and equatorial Pacific Ocean, a vast portion of the world's oceans byvolume and an important end-member of deep thermohaline circulation.Dissolved Co (dCo) samples, including total dissolved and labile Co, weremeasured at-sea during the GEOTRACES Pacific Meridional Transect (GP15) expedition along the 152∘ W longitudinal from 56∘ N to20∘ S. Along this transect, upper-ocean dCo (σ0<26) was linearly correlated with dissolved phosphate (slope = 82±3, µmol : mol) due to phytoplankton uptake and remineralization.As depth increased, dCo concentrations became increasingly decoupled fromphosphate concentrations due to co-scavenging with manganese oxide particlesin the mesopelagic. The transect revealed an organically bound coastalsource of dCo to the Alaskan Stream associated with low-salinity waters. Anintermediate-depth hydrothermal flux of dCo was observed off the Hawaiiancoast at the Loihi Seamount, and the elevated dCo was correlated withpotential xs3He at and above the vent site; however, the Loihi Seamountlikely did not represent a major source of Co to the Pacific basin. Elevatedconcentrations of dCo within oxygen minimum zones (OMZs) in the equatorialNorth and South Pacific were consistent with the suppression of oxidativescavenging, and we estimate that future deoxygenation could increase the OMZdCo inventory by 18 % to 36 % over the next century. In Pacific Deep Water(PDW), a fraction of elevated ligand-bound dCo appeared protected fromscavenging by the high biogenic particle flux in the North Pacific basin.This finding is counter to previous expectations of low dCo concentrationsin the deep Pacific due to scavenging over thermohaline circulation.Compared to a Co global biogeochemical model, the observed transectdisplayed more extreme inventories and fluxes of dCo than predicted by themodel, suggesting a highly dynamic Pacific Co cycle. 
    more » « less
  3. Abstract

    The biogeochemical cycling of dissolved zinc (dZn) was investigated in the Western Arctic along the U.S. GEOTRACES GN01 section. Vertical profiles of dZn in the Arctic are strikingly different than the classic “nutrient‐type” profile commonly seen in the Atlantic and Pacific Oceans, instead exhibiting higher surface concentrations (~1.1 nmol/kg), a shallow subsurface absolute maximum (~4–6 nmol/kg) at 200 m coincident with a macronutrient maximum, and low deep water concentrations (~1.3 nmol/kg) that are homogeneous (sp.) with depth. In contrast to other ocean basins, typical inputs such as rivers, atmospheric inputs, and especially deep remineralization are insignificant in the Arctic. Instead, we demonstrate that dZn distributions in the Arctic are controlled primarily by (1) shelf fluxes following the sediment remineralization of high Zn:C and Zn:Si cells and the seaward advection of those fluxes and (2) mixing of dZn from source waters such as the Atlantic and Pacific Oceans rather than vertical biological regeneration of dZn. This results in both the unique profile shapes and the largely decoupled relationship between dZn and Si found in the Arctic. We found a weak dZn:Si regression in the full water column (0.077 nmol/μmol,r2 = 0.58) that is higher than the global slope (0.059 nmol/μmol,r2 = 0.94) because of the shelf‐derived halocline dZn enrichments. We hypothesize that the decoupling of Zn:Si in Western Arctic deep waters results primarily from a past ventilation event with unique preformed Zn:Si stoichiometries.

     
    more » « less
  4. Abstract

    Copper (Cu) is an important micronutrient for marine organisms, which can also be toxic at elevated concentrations. Here, we present a new model of global ocean Cu biogeochemical cycling, constrained by GEOTRACES observations, with key processes including sources from rivers, dust, and sediments, biological uptake and remineralization of Cu, reversible scavenging of Cu onto sinking particles, conversion of Cu between labile and inert species, and ocean circulation. In order for the model to match observations, in particular the relatively small increase in Cu concentrations along the global “conveyor belt,” we find it is necessary to include significant external sources of Cu with a magnitude of roughly 1.3 Gmol yr−1, having a relatively stronger impact on the Atlantic Ocean, though the relative contributions of river, dust, and sediment sources are poorly constrained. The observed nearly linear increase in Cu concentrations with depth requires a strong benthic source of Cu, which includes the sedimentary release of Cu that was reversibly scavenged from the water column. The processes controlling Cu cycling in the Arctic Ocean appear to be unique, requiring both relatively high Cu concentrations in Arctic rivers and reduced scavenging in the Arctic. Observed partitioning of Cu between labile and inert phases is reproduced in the model by the slow conversion of labile Cu to inert in the whole water column with a half‐life of ∼250 years, and the photodegradation of inert Cu to labile in the surface ocean with a minimum half‐life of ∼2 years at the equator.

     
    more » « less
  5. Abstract

    Processes controlling dissolved barium (dBa) were investigated along the GEOTRACES GA03 North Atlantic and GP16 Eastern Tropical Pacific transects, which traversed similar physical and biogeochemical provinces. Dissolved Ba concentrations are lowest in surface waters (∼35–50 nmol kg−1) and increase to 70–80 and 140–150 nmol kg−1in deep waters of the Atlantic and Pacific transects, respectively. Using water mass mixing models, we estimate conservative mixing that accounts for most of dBa variability in both transects. To examine nonconservative processes, particulate excess Ba (pBaxs) formation and dissolution rates were tracked by normalizing particulate excess230Th activities. Th‐normalized pBaxsfluxes, with barite as the likely phase, have subsurface maxima in the top 1,000 m (∼100–200 μmol m−2 year−1average) in both basins. Barite precipitation depletes dBa within oxygen minimum zones from concentrations predicted by water mass mixing, whereas inputs from continental margins, particle dissolution in the water column, and benthic diffusive flux raise dBa above predications. Average pBaxsburial efficiencies along GA03 and GP16 are ∼37% and 17%–100%, respectively, and do not seem to be predicated on barite saturation indices in the overlying water column. Using published values, we reevaluate the global freshwater dBa river input as 6.6 ± 3.9 Gmol year−1. Estuarine mixing processes may add another 3–13 Gmol year−1. Dissolved Ba inputs from broad shallow continental margins, previously unaccounted for in global marine summaries, are substantial (∼17 Gmol year−1), exceeding terrestrial freshwater inputs. Revising river and shelf dBa inputs may help bring the marine Ba isotope budget more into balance.

     
    more » « less