Biological Control of Chromium Redox and Stable Isotope Composition in the Surface Ocean

• Published in: Global biogeochemical cycles 2020-01, Vol.34 (1), p.e2019GB006397-n/a
• Main Authors: Janssen, David J., Rickli, Jörg, Quay, Paul D., White, Angelicque E., Nasemann, Philipp, Jaccard, Samuel L.
• Format: Article
• Language: English
• Subjects: Availability; Biogeochemical Cycles, Processes, and Modeling; Biogeochemical Kinetics and Reaction Modeling; Biogeochemistry; Biogeosciences; Biological control; biological productivity; Chromium; chromium redox; Cryosphere; Depletion; Fractionation; Geochemical Tracers; Geochemistry; GEOTRACES; Global Change; Isotope composition; Isotopes; Isotopic Composition and Chemistry; Isotopic enrichment; Marine sediments; Oceanography: Biological and Chemical; Oceans; Oxidation/Reduction Reactions; Oxidoreductions; Oxygen; Paleoceanography; paleoproxy; Particulates; Perturbation; Phytoplankton; Productivity; Quaternary; Ratios; Records; Sediments; Stable Isotope Geochemistry; Stable Isotopes; Surface water; Trace Element Cycling; Trace Elements; Tracers; Trivalent chromium
• ISSN: 0886-6236; 1944-9224
• DOI: 10.1029/2019GB006397

While chromium stable isotopes (δ53Cr) have received significant attention for their utility as a tracer of oxygen availability in the distant geological past, a mechanistic understanding of modern oceanic controls on Cr and δ53Cr is still lacking. Here we present total dissolved δ53Cr, concentrations of Cr (III) and total dissolved Cr, and net community productivity (NCP) from the North Pacific. Chromium concentrations show surface depletions in waters with elevated NCP, but not in lower productivity waters. Observed Cr deficits correspond well with calculated Cr export derived from NCP and Cr:C ratios of natural phytoplankton and marine particulates. Chromium (III) concentrations are stable over the diel cycle yet correlate with NCP, with maxima found in highly productive surface waters but not in lower productivity waters, indicating biological control on Cr (III). The relationship between Cr (III) and δ53Cr suggests that δ53Cr distributions may be controlled by the removal of isotopically light Cr (III) at an isotopic enrichment factor (∆53Cr) of −1.08‰ ± 0.25 relative to total dissolved δ53Cr, in agreement with the global δ53Cr‐Cr fractionation factor (−0.82‰ ± 0.05). No perturbation to δ53Cr, Cr, or Cr (III) is observed in oxygen‐depleted waters (~10 μmol/kg), suggesting no strong control by O2 availability, in agreement with other recent studies. Therefore, we propose that biological productivity is the primary control on Cr and δ53Cr in the modern ocean. Consequently, δ53Cr records in marine sediments may not faithfully record oxygen availability in the Late Quaternary. Instead, our data demonstrate that δ53Cr records may be a useful tracer for biological productivity. Key Points Chromium (III) correlates with biological productivity but not with irradiance, and no diel cycle is observed Biological export of Cr at previously observed Cr:C explains vertical [Cr] profiles locally and is similar to Cr sources globally Cr (III) export at Δ53Cr = −1.08‰ ± 0.25 relative to total dissolved δ53Cr matches our δ53Cr trends and the global δ53Cr‐[Cr] correlation