Experimental determination of hydrogen isotopic equilibrium in the system H2O(l)-H2(g) from 3 to 90 °C

Abstract

Molecular hydrogen (H2) is found in a variety of settings on and in the Earth from low-temperature sediments to hydrothermal vents, and is actively being considered as an energy resource for the transition to a green energy future. The hydrogen isotopic composition of H2, given as D/H ratios or δD, varies in nature by hundreds of per mil from ∼−800 ‰ in hydrothermal and sedimentary systems to ∼+450 ‰ in the stratosphere. This range reflects a variety of processes, including kinetic isotope effects associated with formation and destruction and equilibration with water, the latter proceeding at fast (order year) timescales at low temperatures (<100 °C). At isotopic equilibrium, the D/H fractionation factor between liquid water and hydrogen (DαH2O(l)-H2(g)) is a function of temperature and can thus be used as a geothermometer for H2 formation or re-equilibration temperatures. Multiple studies have produced theoretical calculations for hydrogen isotopic equilibrium between H2 and water vapor. However, only three published experimental calibrations used in geochemistry exist for the H2O-H2 system: two between 51 and 742 °C for H2O(g)-H2(g) (Suess, 1949; Cerrai et al., 1954), and one in the H2O(l)-H2(g) system for temperatures <100 °C (Rolston et al., 1976). Despite these calibrations existing, there is uncertainty on their accuracy at low temperatures (<100 °C; e.g., Horibe and Craig, 1995).