Mobilization and isotope fractionation of chromium during water-rock interaction in presence of siderophores

Abstract

Chromium mobilization and isotope fractionation during water-rock interaction in presence of the biogenic siderophore desferrioxamine B (DFOB) was studied with batch leaching experiments on chromitite and other igneous oxide and silicate rocks. Siderophores are a group of organic ligands synthesized and excreted by bacteria, fungi and plants to enhance the bioavailability of key nutrients like Fe. However, the DFOB siderophore also has a strong affinity for complexation with other metals such as Cr, U and rare earth elements. Here we show that leaching of rocks in the presence of the hydroxamate siderophore DFOB significantly increased the mobilization of Cr from all investigated rocks and caused an enrichment of the heavier 53Cr isotope in leachates from chromitite (δ53Crleach = +0.15 ± 0.087‰ to +2.14 ± 0.042‰) and from altered silicate rock (δ53Crleach = +0.48 ± 0.07‰). In contrast, stable isotope fractionation of Cr was not observed in DFOB leachates of pristine silicate and low-Cr oxide rocks. Leaching in the presence of citric acid significantly enhanced Cr mobility, but did not result in fractionation of Cr isotopes. Chromium isotope fractionation is used in geochemistry as a quantitative proxy for oxidative weathering, because Cr(III) is oxidized to Cr(VI) in presence of MnO2 and the associated Cr isotope fractionation is commonly linked to the presence of oxygen in the atmosphere. Our findings indicate that the presence of specific biogenic ligands with a high affinity for Cr may also cause Cr isotope fractionation. The presence of biomolecules like siderophores during weathering, hydrothermal alteration or during mineral precipitation, therefore, may put constraints on the applicability of certain trace metals and their isotopes as redox proxies in modern and past environments. The results of our study also suggest that siderophores may have a high potential for (bio)remediation of Cr-contaminated sites and detoxification of contaminated natural waters.