Redox induced sulfur-selenium isotope decoupling recorded in pyrite

Abstract

This study presents the first combined S and Se isotope investigation of sulfide suited to explore differences in fractionation between these two redox sensitive isotope systematics as recorded in the same mineral. A case study of Cretaceous Navajún pyrite from the Mesozoic Cameros Basin, Spain, with known petrogenesis and geological context shows systematic decoupling at the microscale: Variable S isotope values within the analyzed pyrite coincide with rather constant Se isotope values and vice versa. These signatures were not generated during pyrite growth but record previous redox induced fractionations in fluids that each contributed both elements from two sources. It is likely that both S and Se isotope fractionation occurred during strong reduction from one fully oxidized source whereas only S but no Se isotope fractionation occurred during minor reduction following sulfide dissolution via H2O from another source. Subsequent mixing of these two H2S-H2Se fluids at different elemental S-Se ratios during incorporation into the pyrite can then explain the S-Se isotope variations in the investigated specimen. These inferences are in accordance with a larger range in the redox potential Eh of Se relative to S, resulting in coupled or decoupled Se and S isotope fractionation depending on the oxygen fugacity during the reduction process. If extended to other sulfides of diverse origin, for a given pH, combined Se and S isotope studies may allow to investigate the magnitude of redox variations and place more robust constraints on minimum and maximum oxygen concentrations in the source. We therefore suggest combined S-Se isotope analyses in sulfide as a new powerful proxy for studying Earth’s redox evolution beyond the bulk rock scale.