Abstract

To investigate the influence of chemical composition on the behavior of H2O in Fe-rich nominally anhydrous minerals, and to determine the difference between H2O behavior in the martian and terrestrial mantles, we conducted high-pressure H2O storage capacity experiments employing a wide range of olivine compositions. Experiments were conducted with bulk compositions in the system FeO-MgO-SiO2-H2O with Mg no. [Mg no. = 100 × molar Mg/(Mg+Fe)] ranging between 50 and 100 at 3 GPa in a piston-cylinder and at 6 GPa in a multi-anvil apparatus. Experiments at 3 GPa were conducted at 1200 °C, with fO2 buffered by the coexistence of Fe and FeO, and at 1300–1500 °C in unbuffered assemblies. Experiments at 6 GPa were conducted at 1200 °C without buffers. Experiments at 1200 °C produced olivine+orthopyroxene+hydrous liquid (liq), and higher T experiments produced olivine+liq. Additionally, we synthesized a suite of 7 olivine standards (Mg no. = 90) for low blank secondary ion mass spectrometry (SIMS) analysis of H in multi-anvil experiments at 3–10 GPa and 1250 °C, resulting in large (200–400 μm) homogeneous crystals with 0.037 to 0.30 wt% H2O. Polarized Fourier transform infrared (FTIR) measurements on randomly oriented grains from the synthesis experiments were used to determine principal axis spectra through least-squares regression, and H contents were calculated from the total absorbance in the OH stretching region. Using these olivines as calibrants for SIMS analyses, the H contents of olivines and pyroxenes from the variable Mg no. experiments were measured by counting 16OH ions. Ignoring any matrix effects owing to variation in Mg no., H contents of olivine and pyroxene increase linearly with decreasing Mg no. At 6 GPa and 1200 °C, olivine H contents increase from 0.05 to 0.13 wt% H2O (8360 to 23 900 H/106 Si) as olivine Mg no. decreases from 100 to 68, and at 3 GPa and 1200 °C olivine H contents increase from 0.017 to 0.054 wt% (278 to 10 000 H/106 Si) as Mg no. decreases from 100 to 55. The partition coefficient for H between pyroxene and olivine, DHopx/ol, decreases from 1.05 at 3 GPa and 1200 °C to 0.61 at 6 GPa and 1200 °C. The storage capacity of Fe-rich olivines with compositions expected in the martian mantle is ~1.5 times greater than those in the terrestrial mantle, suggesting that the geochemical behavior of H2O in the mantles of the two planets are quite similar. If 50% of the K2O on Mars remains in its mantle (Taylor et al. 2006), then a similar or greater proportion of the H2O is also in the mantle. Given accretionary models of the total martian H2O budget (Lunine et al. 2003), this suggests concentrations of 100–500 ppm H2O in the martian mantle and 0.1–1.9 wt% H2O in primary martian basalts.

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