Stable hydrogen and oxygen isotope geochemistry of Fe3+-rich, interstratified clay minerals from seafloor hydrothermal sites

Abstract

Chemical and structural complexities in interstratified clay minerals arising from mineral transformations and evolving formation conditions should be recorded in their stable isotope signatures. This paper examines the controls on the stable hydrogen and oxygen isotope compositions of Fe3+-rich, glauconite-nontronite, talc-nontronite and talc-saponite from submarine hydrothermal sites, with a focus on the Red Sea Atlantis II Deep. Values of δ18O became less positive in the order nontronite > glauconite-nontronite > talc-nontronite > talc-saponite, yielding oxygen isotope temperatures ranging from ∼40 °C for nontronite to ∼135–300 °C for talc-saponite. These clay minerals have low δ2H, ranging from −145 to −127‰ for talc-nontronite, −135‰ for nontronite, −129 to −85‰ for glauconite-nontronite, and −95 to −59‰ for talc-saponite. The clay mineral-water hydrogen isotope fractionation is strongly affected by Fe3+ content, with increasing structural Fe3+ causing progressive weakening of O-H bonds. The large ionic radius and high charge of Fe3+ cause it to be more poorly shielded by surrounding oxygen from hydroxyl hydrogen relative to other octahedral or tetrahedral cations. The resulting lengthening of O-H bonds favours 1H over 2H. Our results confirm that Fe-rich phases, such as nontronite-glauconite, are produced at the lowest temperatures and Mg-rich phases, such as talc-saponite, are formed at the highest temperatures in seafloor hydrothermal environments. Evolving fluid chemistry and fluid pathways during clay mineral formation are also important. Glauconite layer formation from precursor nontronite likely occurred during diagenesis; redox changes causing Fe-reduction and an increase in layer charge facilitated interlayer K-fixation. Talc-saponite compositions vary with temperature and fluid chemistry, forming at variable sediment depths depending on access to the hottest hydrothermal fluids.