D/H fractionation in the system methane-hydrogen-water

We report measurements of the equilibrium D/H fractionation factor (alpha) between methane and hydrogen in the temperature range 200-500 degrees C, Isotopic equilibrium was achieved by recycling the gases over a Ni-Thoria catalyst, using an in-line sampling volume for sequestering aliquots of the gas mixture without contributions from adsorbed gases on the catalyst, Equilibrium values of cr were approached from both sides by use of (1) enriched CH3D in the initial mixture and (2) pre-equilibration of the gases at temperatures below that of the final equilibrium mixture. The measured values of alpha are linear vs. 1/T-2 and fit the equation alpha = 0.8994 + 183,540/T-2, with a standard deviation sigma = +/-12.5%. The D/H fractionation factors for water vapor-hydrogen exchange measured by Suess (1949) and by Cerrai et al. (1954) are also linear in alpha vs. 1/T-2 over the temperature range of the data: comparison with published D/H ratios in high-temperature (1127 degrees C) volcanic gases at Surtsey volcano shows that the Suess (1949) data are much closer to the observed ratios in H-2 and H2O. The Suess (1949) measurements (80-200 degrees C) are also much closer to the theoretical values calculated by Bardo and Wolfsberg (1976), which fit the observed Surtsey fractionations slightly better than the extrapolated Suess (1949) results. We conclude that (1) the Suess (1949) measurements are the better set of experimental data, (2) the Surtsey gases are close to isotopic equilibrium at the vent temperatures, and (3) the Bardo and Wolfsberg (1976) theoretical equation gives the best representation of the H2O-H-2 fractionation factors. This equation is combined with the Horita and Wesolowski (1994) equation for H2O liquid-vapor fractionation factors and can be used with the CH4-H-2 alpha values to determine whether concordant temperatures are observed in the system CH4H2-H2O. Application to the D/H ratios in the East Pacific Rise hydrothermal vents measured by Welhan and Craig (1979) shows that concordant temperatures are obtained for both CH4-H-2 and H2O-H-2 data, and are close to the approximate vent temperatures (similar to 350 degrees C). We note that fractionation equations in which alpha, rather than 1n alpha, is fit to powers of T are much more useful for geochemical studies because the precision estimate is uniform over the entire temperature range of the data..