Chromium stable isotope distributions in the southwest Pacific Ocean and constraints on hydrothermal input from the Kermadec Arc

Special attention has been given to chromium (Cr) as a paleoproxy tracing redox cycling throughout Earth’s history, due to differences in the solubility of its primary redox species at Earth’s surface (Cr (III) and Cr(VI)) and isotope fractionation associated with their interconversion. In turn, chromium’s pale- oproxy potential has motivated studies of the modern ocean to better understand which processes drive its cycling and to constrain their impact on the Cr isotope composition (d53Cr) of seawater. Here, we pre- sent total dissolved seawater Cr concentrations and d53Cr along the GEOTRACES GP13 section. This sec- tion is a zonal transect extending from Australia in the subtropical southwest Pacific Ocean. Surface signals of local biological Cr cycling are minimal, in agreement with distributions of dissolved major nutrients as well as biologically-controlled trace metals in this low productivity, oligotrophic environ- ment. Depth profiles have Cr concentration minima in surface waters and maxima at depth, and are lar- gely shaped by the advection of nutrient- and Cr-rich subsurface waters rather than vertically-driven processes. Samples close to the sediment–water interface indicate important benthic Cr fluxes across the section. The GP13 transect crosses the hydrothermally-active Kermadec Arc. Hydrothermal fluids (consisting of <15% background seawater) were collected from three venting sites at the Brothers Volcano (along the Kermadec Arc). These fluids yielded near-crustal d53Cr values (!0.17 to +0.08‰) and elevated [Cr] (7.5–23 nmol kg!1, hydrothermal endmember [Cr] % 8–27 nmol kg!1), indicating that the Kermadec Arc may be an isotopically light Cr source. Dissolved [Fe] enrichments have been reported previously in deep waters ($1600–3000 m) along the GP13 transect, east of the Kermadec Arc. These same waters show ele- vated [Cr] compared to Circumpolar Deep Water ([Cr] = 3.88 ± 0.11, d53Cr = 0.89 ± 0.08, n = 32), with an aver- age [Cr] accumulation of 0.71 ± 0.11 nmol kg!1 (1 SD), and an estimated d53Cr of +0.46 ± 0.30‰ (2 SD, n = 9) for the accumulated Cr. Comparing high-temperature vent and neutrally buoyant plume data, hydrothermal-sourced Cr is likely negligable compared to Cr contributions from other processes (benthic fluxes, release from particles), and the advection of more Cr-rich Pacific Deep Water. It is unlikely that hydrothermal vents would be a major contributor within the regional or global biogeochemical Cr cycle, even if hydrothermal fluxes change by orders of magnitude, and therefore d53Cr trends in the paleorecord may be attributable, at least in part, to major changes in other controls on Cr (e.g. widespread anoxia)

Release from biogenic particles, benthic fluxes, and deep water circulation control Cr and δ53Cr distributions in the ocean interior

Chromium (Cr) has shown promise as a paleoceanographic proxy due to the redox-driven control of dissolved Cr concentrations ([Cr]) and stable isotope composition (δ53Cr). To improve the mechanistic understanding of Cr cycling in the modern ocean and strengthen its potential proxy applications, we present new data from regeneration incubations, bottom and sediment pore waters, and a compilation of intermediate and deep water data. While Cr removal and biological export from the surface ocean is associated with organic carbon export, the deep water release of dissolved Cr from sinking particles is not directly dependent on organic carbon respiration, as indicated by differing trends between Cr, oxygen utilization and the regeneration of organic-associated macronutrients (e.g. N, P). Pore water and bottom water data demonstrate that benthic Cr fluxes are locally important and may be significant globally. The pore water dissolved Cr flux at our CaCO3-rich site is likely driven by the re-release of Cr scavenged from the water column by sinking particles, with minor contributions from lithogenic phases. We argue this is consistent with the highest open ocean [Cr] to date being found in the water column below oxygen minimum zones, likely reflecting the release of scavenged Cr in deep waters or surface sediments. Chromium released from suspended particles and surface sediments follows the global δ53Cr–[Cr] array, supporting the proposed role of biological export and regeneration in shaping global Cr and δ53Cr distributions. Global intermediate and deep water [Cr], δ53Cr and Cr:macronutrient relationships are thus shaped by a synergy of circulation patterns, water mass mixing, a deep Cr regeneration cycle, and benthic Cr sources. A biogenic control on global Cr distributions indicates that sedimentary Cr records may reflect biogenic as well as O2-dependent processes, while more research is needed to assess sediment Cr record fidelity based on an active diagenetic cycle