Micha J. A. Rijkenberg

The oceanic budgets of nickel and zinc isotopes: the importance of sulfidic environments as illustrated by the Black Sea

Isotopic data collected to date as part of the GEOTRACES and other programmes show that the oceanic dissolved pool is isotopically heavy relative to the inputs for zinc (Zn) and nickel (Ni). All Zn sinks measured until recently, and the only output yet measured for Ni, are isotopically heavier than the dissolved pool. This would require either a non-steady-state ocean or other unidentified sinks. Recently, isotopically light Zn has been measured in organic carbon-rich sediments from productive upwelling margins, providing a potential resolution of this issue, at least for Zn. However, the origin of the isotopically light sedimentary Zn signal is uncertain. Cellular uptake of isotopically light Zn followed by transfer to sediment does not appear to be a quantitatively important process. Here, we present Zn and Ni isotope data for the water column and sediments of the Black Sea. These data demonstrate that isotopically light Zn and Ni are extracted from the water column, probably through an equilibrium fractionation between different dissolved species followed by sequestration of light Zn and Ni in sulfide species to particulates and the sediment. We suggest that a similar, non-quantitative, process, operating in porewaters, explains the Zn data from organic carbon-rich sediments. This article is part of the themed issue ‘Biological and climatic impacts of ocean trace element chemistry’.

An Intercomparison of Dissolved Iron Speciation at the Bermuda Atlantic Time-series Study (BATS) Site: Results from GEOTRACES Crossover Station A

The organic complexation of dissolved iron (Fe) was determined in depth profile samples collected from GEOTRACES Crossover Station A, the Bermuda Atlantic Time-series Study (BATS) site, as part of the Dutch and U.S. GEOTRACES North Atlantic programs in June 2010 and November 2011, respectively. The two groups employed distinct competitive ligand exchange-adsorptive cathodic stripping voltammetry (CLE-AdCSV) methods, and resulting ligand concentrations and conditional stability constants from each profile were compared. Excellent agreement was found between the total ligand concentrations determined in June 2010 and the strongest, L1-type, ligand concentrations determined in November 2011. Yet a primary distinction between the datasets was the number of ligand classes observed: a single ligand class was characterized in the June 2010 profile while two ligand classes were observed in the November 2011 profile. To assess the role of differing interpretation approaches in determining final results, analysts exchanged titration data and accompanying parameters from the profiles for reinterpretation. The reinterpretation exercises highlighted the considerable influence of the sensitivity (S) parameter applied on interpretation results, consistent with recent intercalibration work on interpretation of copper speciation titrations. The potential role of titration data structure, humic-type substances, differing dissolved Fe concentrations, and seasonality are also discussed as possible drivers of the one versus two ligand class determinations between the two profiles, leading to recommendations for future studies of Fe-binding ligand cycling in the oceans.

The biogeochemistry of cobalt in the Mediterranean Sea

The soluble (sCou2009 u20090.2u2009µm) fractions of cobalt were investigated along the GEOTRACES-A04 section. Our results show that sCo was the predominant form (90%) of the DCo in the MS and that cCo and pCo generally followed the same distribution suggesting a biogeochemical link between these two fractions. In the Mediterranean Sea, DCo displayed an overall scavenged-like profile in the different sub-basins, with high concentrations (up to 350 pM) in surface and quasi-uniformed low concentrations of DCo (~45 pM) in the deep sea. However, the decoupling between the surface and the deep reservoirs suggested that the transfer of Co from dissolved to particulate pools during the sink of particles may not be the only process governing DCo distribution. High surface Co inputs, stabilization of DCo in a soluble form and the extremely high regeneration rate of biogenic pCo, all lead to the accumulation of DCo in surface. Conversely, low pCo export from the surface waters, low remineralization of biogenic pCo and slow but efficient removal of DCo by scavenging including colloids aggregation into particles, prevented its accumulation in the intermediate and deep sea. Moreover, Mediterranean circulation prevented the exchanges between the DCo-rich surface and the DCo-poor deep layers enhancing the scavenged-like profile of DCo. Finally, tentative DCo budgets were balanced at basin scale and showed the strong imprint of the surface inputs at Gibraltar Strait on the Mediterranean cobalt biogeochemistry.

Dissolved Fe in the Deep and Upper Arctic Ocean With a Focus on Fe Limitation in the Nansen Basin

Global warming resulting from the release of anthropogenic carbon dioxide is rapidly changing the Arctic Ocean. Over the last decade sea ice declined in extent and thickness. As a result, improved light availability has increased Arctic net primary production, including in under-ice phytoplankton blooms. During the GEOTRACES cruise PS94 in the summer of 2015 we measured dissolved iron (DFe), nitrate and phosphate throughout the central part of the Eurasian Arctic. In the deeper waters concentrations of DFe were higher, which we relate to resuspension on the continental slope in the Nansen Basin and hydrothermal activity at the Gakkel Ridge. The main source of DFe in the surface was the Trans Polar Drift (TPD), resulting in concentrations up to 4.42 nM. Nevertheless, using nutrient ratios we show that a large under-ice bloom in the Nansen basin was limited by Fe. Fe limitation potentially prevented up to 54% of the available nitrate and nitrite from being used for primary production. In the Barents Sea, Fe is expected to be the first nutrient to be depleted as well. Changes in the Arctic biogeochemical cycle of Fe due to retreating ice may therefore have large consequences for primary production, the Arctic ecosystem and the subsequent drawdown of carbon dioxide.

The Biogeochemistry of Electroactive Humic Substances and Its Connection to Iron Chemistry in the North East Atlantic and the Western Mediterranean Sea

We present the zonal distribution of electroactive humic‐like substances (eHS) along a section from Offshore Portugal in the North East Atlantic to the Sicily Channel in the Mediterranean Sea. The concentrations were normalized to Suwannee River Fulvic Acid and ranged from 11 μg/L to 81 μg/L. The vertical distributions were typical of those previously reported for dissolved organic carbon in the Mediterranean Sea. High eHS concentrations were measured in surface water and concentrations decreased with depth before increasing again toward benthic maxima measured at some stations. We estimate that eHS represented a relatively small fraction of the natural organic matter in the Mediterranean Sea (2–5%) but considering their important role in the complexation and the solubility of key trace elements (e.g., iron and copper), the eHS cycle could influence the entire biogeochemistry of these marine systems. We identified key processes controlling the concentration of eHS. While biologically mediated production was the major source of eHS, riverine and rain inputs as well as sediment release were also likely external sources. Low eHS concentrations at subsurface depths pointed to photodegradation as a possible sink of eHS, but degradation by heterotrophic bacteria seemed to be the main sink in the deep sea. Finally, we found a positive correlation between dissolved iron and eHS concentrations. Estimation of eHS contribution to iron binding ligand concentrations indicates the complexation of iron by eHS in the Mediterranean Sea. These observations suggest links between the cycles of eHS and iron in the Mediterranean Sea.