HR: 1330h
AN: P22A-0060    [PDF]
TI: Mg-Sulfate Salts as Possible Water Reservoirs in Martian Regolith
AU: * Vaniman, D T
EM: vaniman@lanl.gov
AF: Los Alamos National Laboratory, MS D462, Los Alamos, NM 87545 United States
AU: Bish, D L
EM: bish@indiana.edu
AF: Indiana University, Dept. of Geological Sciences 1001 E. 10th St., Bloomington, IN 47405 United States
AU: Chipera, S J
EM: chipera@lanl.gov
AF: Los Alamos National Laboratory, MS D462, Los Alamos, NM 87545 United States
AU: Carey, J W
EM: bcarey@lanl.gov
AF: Los Alamos National Laboratory, MS D462, Los Alamos, NM 87545 United States
AU: Feldman, W C
EM: wfeldman@lanl.gov
AF: Los Alamos National Laboratory, MS D462, Los Alamos, NM 87545 United States
AB: Neutron spectrometer data from the Mars Odyssey orbiter provide evidence of high water-equivalent hydrogen abundance in some near-equatorial locations on Mars. In broad regions shallow ($<$1 m) regolith appears to have water abundances of up to $\sim$13 wt%. Water ice is predicted to be unstable at the present time at all depths below the surface in these equatorial regions. If present in hydrous silicate minerals such as clays or zeolites, which may contain water in abundances of $\sim$10-20% at Martian surface conditions, the Odyssey data require a regolith very enriched in hydrous silicates - an unlikely proposition. Viking X-ray fluorescence data and alteration assemblages in martian meteorites suggest the presence of sulfate salts in martian regolith. Viking data from excavated duricrust indicate that Mg and S are correlated and that $\sim$10% of an Mg-sulfate salt is a likely cementing agent. However, the range of possible Mg sulfates is large. Epsomite (7-hydrate, 51% water) and hexahydrite (6-hydrate, 47% water) are the most hydrated; both form structures of isolated SO$_{4}$ tetrahedra with isolated octahedral sites consisting of Mg coordinated by six H$_{2}$O molecules (epsomite has an extra H$_{2}$O in addition to the six required to coordinate with Mg). Pentahydrite (5-hydrate, 43% water) has infinite chains of alternating SO$_{4}$ tetrahedra and Mg octahedra, with 4/5 of the water forming apices in octahedral sites. Starkeyite (4-hydrate, 37% water) has clusters of two SO$_{4}$ tetrahedra and two Mg octahedra, linked only by hydrogen bonds. The Mg-sulfate sanderite (2-hydrate, 23% water) is rare and has poorly known structure. Kieserite (1-hydrate, 13% water) is relatively common in evaporite deposits and has a framework structure of infinite tetrahedral-octahedral chains cross-linked by hydrogen bonds. The stability of Mg-sulfate hydrates under martian near-surface conditions depends on their structures; those with excess water beyond that required to form the octahedral Mg site (e.g., epsomite, pentahydrite) lose that excess readily. Experiments with epsomite and hexahydrite indicate great sensitivity to environmental conditions; epsomite is not stable at 295 K at relative humidity (RH) values less than about 55%, below which hexahydrite is the observed phase. More importantly, hexahydrite - with all water coordinated to Mg in octahedral sites - is unstable at pressures less than $\sim$20 mtorr. X-ray diffraction analysis of hexahydrite held at 20 mtorr for six hours shows that structural degradation is slow at 100 K but becomes obvious in 1 hour at 273 K. Thermogravimetric analysis of this amorphous solid shows that it contains $\sim$26% H$_{2}$O (compared with 47% in crystalline hexahydrite), and its observed macroscopic expansion behavior suggests that it can reversibly hydrate and dehydrate. Although neither epsomite nor hexahydrite is likely to be stable near the surface of Mars, their amorphous derivatives or crystalline forms of the lower hydrates might be present (preliminary thermogravimetric data indicate that kieserite is likely to be stable). However, the limited rehydration of structurally degraded hexahydrite indicates that unrealistically large amounts ($\sim$50%) would be required in the upper meter of regolith to account for the higher water contents ($\sim$13%) suggested for some martian equatorial regions; even larger amounts of kieserite ($\sim$100%) would be required. A more important role for sulfates may be in the formation of a low-permeability salt crust that could restrict dewatering of underlying soil horizons.
DE: 3672 Planetary mineralogy and petrology (5410)
DE: 6225 Mars
SC: Planetary Sciences [P]
MN: 2003 Fall Meeting