Chromium isotope composition of reducing and anoxic sediments from the Peru Margin and Cariaco Basin

Abstract:

Chromium isotope systematics in marine sediments are now being used as a new redox proxy of the modern and ancient Earth’s surface. Chromium is primarily delivered to the oceans by riverine inputs through weathering of Cr(III)-rich minerals present in the continental crust and oxidation of insoluble Cr(III) to soluble Cr(VI) species. Since oxidation-reduction reactions fractionate Cr isotopes whereby oxidized Cr(VI) species are preferentially enriched in heavy Cr isotopes, the Cr isotope composition of marine sediments may be useful tracers of redox conditions at the Earth’s surface through geological time. Chromium is quantitatively removed in organic-rich sediments where reducing conditions prevail and promote reduction of Cr(VI) to Cr(III), and thus, these sediments should capture the ambient seawater Cr isotope composition. However, the isotopic composition of modern organic-rich sediments is poorly documented so far, and this step is essential for further modeling the global oceanic Cr isotope mass balance and assessing the effects of sedimentation and post-depositional processes on the marine Cr isotopes archive.

In this study, we have characterized modern marine organic-rich sediments for their Cr isotope composition (δ^53/52Cr) from two different settings, the Peru margin upwelling zone and the anoxic Cariaco Basin (Venezuela). Chromium isotopes were measured on a MC-ICP-MS (Nu Plasma) using a double-spike correction method. The authigenic fraction of shallow samples from the Peru margin sedimentary sequence with a high Total Organic Carbon (TOC) content (>10 wt%) yield an average δ^53/52Cr_authigenic value of +0.67 ±0.05 ‰ (2sd). However, although this value is close to the seawater value (Atlantic Ocean) and to Cariaco basin sediments (~ +0.6 ‰), reducing sediments from the Peru margin are on average isotopically slightly heavier, especially in samples having a low authigenic fraction and a low TOC content (δ^53/52Cr_authigenic values up to +1.30 ‰). Results suggest either a different Cr isotope composition for Pacific seawater or the effects of Cr removal processes in anoxic basins and reducing sediments from upwelling zones.