In-situ redox conditions in hydrothermal diamond-anvil cell experiments using various metal gaskets

Abstract

Hydrothermal diamond-anvil cells (HDACs) have been widely used in various research fields since they were introduced in 1993. Unlike temperature (T) and pressure (P), the redox states of the samples in HDAC experiments were poorly controlled or measured; they were usually estimated by observing the reduction/disappearance of redox-sensitive mineral(s) (e.g., Mo metal) and corresponding formation and growth of such mineral(s) (e.g., MoO2) without in-situ redox measurement. In this study, we demonstrated the generation of H2 during experiments using various metal gaskets, including inert (Re) and chemically more reactive metals (Ni, Co, Mo, and W), in the pure H2O system under various P-T conditions. A technique for quantitative Raman spectroscopic analysis of H2 in HDAC is designed. Based on this technique, the oxygen fugacity (fO2) values of Mo-MoO2 buffer at the experimental P-T conditions were then calculated from these measured H2 pressures. We demonstrated that steady-state redox control can be maintained at a fixed T between 400 and 500 °C in HDAC experiments using a Mo gasket for durations of up to two hours and for those using a Re gasket with an additional Mo rod in the sample between 400 and 800 °C for durations of up to 90 min, regardless of the considerable changes in sample pressure. This demonstration was established by the balance between the rates of H2 generation and H2 loss from the sample chamber. The loss of H2 enhanced the consumption of H2O and therefore reduced the sample pressures during the experiments.We believe that hydrogen contents in every HDAC experiment, which attempt to control the redox state, need in situ measurement, then estimate the real redox state and compare it to thermodynamic equilibrium prediction. To enhance in situ redox control and measurements, modifications of HDAC are required for improving the quantitative Raman spectroscopic analysis technique in both sensitivity and accuracy.