Zn isotope signatures in soil Fe[sbnd]Mn nodules with karst high geochemical background

Abstract

Zn isotope has the potential to be used as an environmental tracer, due to its role in fingerprinting specific sources and processes. However, few studies have focused on Zn isotope system in terrestrial ferromanganese (FeMn) nodules, which is important on understanding the behaviors of Zn in soils. In this study, we analyse the isotopic composition in soil FeMn nodules and surrounding materials from a typical karst region in Guangxi Province, southwestern China and use advanced synchrotron-based methods to characterize Zn speciation. The Zn isotope compositions of the FeMn nodules range from 0.09 to 0.66 ‰, with an average value of 0.24 ‰. Pb isotope fingerprinting reveals that the major material sources contributing to the FeMn nodules are the surrounding soil (δ66Zn: ~0.36 ‰) and partly weathered carbonate bedrock (δ66Zn: ~0.58 ‰), which contain heavier Zn isotopes than the nodules. Synchrotron-based X-ray fluorescence (μ-SXRF) shows that Zn is well correlated with both Fe and Mn. X-ray absorption near edge spectroscopy (XANES) measurements reveal that Zn is associated with both goethite and birnessite phases, with goethite-sorbed Zn accounting for ~76 % of the total Zn and birnessite-sorbed Zn accounting for ~24 %. By combining these new results, the isotopically light Zn in the FeMn nodules compared to their sources can be explained by equilibrium sorption of Zn on goethite and birnessite, during which light Zn is preferentially sorbed. Our study provides important new data on Zn isotope compositions in terrestrial soil FeMn nodules and constrains associated mechanisms, and have implications for using Zn isotopes as environmental tracers.