Investigating the cycling of chromium in the oxygen deficient waters of the Eastern Tropical North Pacific Ocean and the Santa Barbara Basin using stable isotopes

Abstract

Cr isotope geochemistry is being explored in the context of a variety of geological problems as well as the environmental remediation of pollutant Cr(VI). There is a strong Cr isotope fractionation during reduction of oxidized Cr(VI) to reduced Cr(III). We present chromium concentration and Cr isotope data for samples from highly reducing environments ([O2] < 2 μmol/kg) in the Eastern Tropical North Pacific (ETNP) Oxygen Deficient Zone (ODZ) off of Mexico and the deep Santa Barbara Basin off of California. Total dissolvable Cr in the upper ETNP ODZ is slightly depleted (by up to 0.8 nmol/kg) and δ53Cr is up to 0.1–0.2‰ heavier compared to oxic waters of the same density seen at the SAFe station (30°N, 140°W), presumably both a result of reduction of Cr(VI) and removal of light Cr(III) by sinking particles. The Cr depletion and Cr isotope fractionation peak at the same depth as the highest δ15N of NO3− and decrease within the equally oxygen-deficient waters below, implying that microbial reduction dependent on the sinking organic matter flux may be the mechanism of Cr reduction. These data are consistent with a fractionation mechanism with a net isotope fractionation factor of ε ≈ −0.44‰. In the deepest anoxic waters of the Santa Barbara Basin in July 2014, dissolved (<0.2 μm) Cr is depleted by up to 1.8 nmol/kg and δ53Cr is up to 0.5‰ heavier compared to SAFe station waters of the same density. This is consistent with a net isotope fractionation factor of ε ≈ −0.65‰. At the Santa Barbara Basin site, it is possible that abiotic Fe(II) reduction (from Fe(II) diffusing out of reducing continental shelf sediments) also contributes to Cr reduction in addition to the microbial reduction mechanism.