Chromium (Cr) is a redox-sensitive element and because Cr isotopes are fractionated by redox and/or biological processes, the Cr isotopic composition of ancient marine sediments may be used to infer changes in past seawater oxygenation or biological productivity. While there appears to be a ‘global correlation’ between the dissolved Cr concentration and Cr isotopic composition of seawater, there is ongoing debate about the relative importance of external sources and internal cycling on shaping the distribution of dissolved Cr that needs to be resolved to validate the efficacy of using Cr isotopes as a paleo proxy. Here, we present full water column depth profiles of total dissolved Cr (Cr(VI)+Cr(III)) and dissolved Cr isotopes (δ53Cr), together with ancillary data, for three stations along a transect (GEOTRACES GApr08) across the sub-tropical North Atlantic. Concentrations of dissolved Cr ranged between 1.84 and 2.63 nmol kg-1, and δ53Cr values varied from 1.06 to 1.42‰. Although atmospheric dust, hydrothermal vents and seabed sediments have the potential to modify the distribution of Cr in the oceans, based on our observations, there is no clear evidence for substantial input of Cr from these sources in our study region although benthic inputs of Cr may be locally important in the vicinity of hydrothermal vents. Subsurface waters (below the surface mixed layer to 700 m water depth) were very slightly depleted in Cr (by up to ~0.4 nmol kg-1), and very slightly enriched in heavy Cr isotopes (by up to ~0.14‰), relative to deeper waters and the lowest Cr concentrations and highest δ53Cr values coincided with lowest concentrations of colloidal (0.02 to 0.2 μm size fraction) Fe. We found no direct evidence for biological uptake of dissolved Cr in the oligotrophic euphotic zone or removal of Cr in modestly oxygen depleted waters (O2 concentrations ~130 μmol kg-1). Rather, we suggest removal of Cr (probably in the form of Cr(III)) in subsurface waters is associated with the formation of colloid aggregates of Fe-(oxyhydr)oxides. This process is likely enhanced by the high lithogenic particle load in this region, and represents a previously unrecognized export flux of Cr. Regeneration of Cr in deeper waters leads to subtly increased levels of Cr alongside decreased δ53Cr values at individual sites, but this trend is more obvious at the global scale, with δ53Cr values decreasing with increasing radiocarbon age of deep waters, from 1.16 ± 0.10‰ (1SD, n=11) in deep Atlantic waters to 0.77 ± 0.10‰ (1SD, n=25) in deep Pacific waters. Removal of relatively isotopically light Cr from subsurface waters onto particulate material and regeneration of this Cr back into the dissolved phase in deep waters partly accounts for the systematic relationship between δ53Cr and Cr concentrations in seawater discussed by other studies.
<p>Rhenium (Re) is a redox-sensitive element. Recent advances in the precision of measurement of the stable isotopic composition of Re (&#948;<sup>187</sup>Re) allow exploration of its potential as a proxy for paleoredox and/or chemical weathering <sup>[1]</sup>. However, as yet, there have been few studies reporting the geochemical cycling of Re and stable Re isotopes in the modern environments <sup>[2] [3]</sup>, and processes that regulate the Re isotope behavior in hydrothermal systems remain unexplored.</p><p>Here we present results of the analysis of Re concentration and &#948;<sup>187</sup>Re (relative to NIST3143) for water samples collected from hydrothermal and groundwater systems in Iceland. We show that Re in basalt-hosted boiled hydrothermal fluids from Hellisheidi, Nesjavellir, Reykjanes and Svartsengi sites is isotopically heavier (&#948;<sup>187</sup>Re = &#8211;0.01 to +0.32&#8240;) than Re in Icelandic basalts (&#948;<sup>187</sup>Re = ~&#8211;0.32&#8240;). The direction of fractionation holds regardless of types of fluid reservoir (meteoric vs. seawater), and is consistent with precipitation of isotopically light sulfides in the hydrothermal system and/or kinetic fractionation of Re during degassing. By contrast, Re in cold (< 10&#176;C) groundwaters collected from the M&#253;vatn area is isotopically indistinguishable from host basalt. Natural hot spring waters exhibit variable &#948;<sup>187</sup>Re values (&#8211;0.28 to +0.26&#8240;), likely reflecting mixing between hydrothermal and groundwater endmembers. The relatively isotopically heavy &#948;<sup>187</sup>Re from hydrothermal sources has the potential to modify the oceanic budget, which has implications for the isotope mass balance of Re.</p><p>[1] Dellinger et al. (2020) JAAS, 35, 377. [2] Dickson et al. (2020) GCA, 287, 221-228. [3] Dellinger et al. (2021) EPSL, 573, 117131.</p>
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.