From hydrothermal experiments three pressure-temperature-time curves have been refined for the system Al2O3−SiO2−H2O and reversal temperatures established for two of the principal reactions involving kaolinite. The temperatures of three isobaric invariant points enable the Gibbs free energy of formation of diaspore and pyrophyllite to be refined and the stability field of kaolinite to be calculated. The maximal temperature of stable kaolinite decreases from 296°C at 2 kb water pressure to 284°C at water's liquid/vapor pressure, and decreases rapidly at lower pressures. On an isobaric plot of [H4SiO4] vs. °K-1, kaolinite has a wedge-shaped stability field which broadens toward lower temperature to include much of the [H4SiO4] range of near-surface environments. If [H4SiO4] is above kaolinite's stability field and the temperature is < 100°C, halloysite forms rather than pyrophyllite, an uncommon pedogenic mineral. Pyrophyllite forms readily instead of kaolinite above 150°C if [H4SiO4] is controlled by cristobalite or noncrystalline silica.

Kaolinite and a common precursor, halloysite, are characteristic products of weathering and hydro-thermal alteration. In sediments, relatively little halloysite has survived due to its low dehydration temperature and instability at low water pressure, but kaolinite commonly has survived since the Devonian Period. In buried sediments, the water pressure and [H4SiO4] requisite for stable kaolinite generally are maintained. In oxidized sediments and in pyritic reduced sediments, kaolinite commonly has survived, but where alkalies, alkaline earths, or aqueous iron has concentrated in the pore fluid, kaolinite has tended to transform to illite, zeolites, berthierine, or other minerals.

Gibbs free energies for phases in the system Al2O3-SiO2-H2O have been calculated from reversed experiments in order to correct earlier values and to calculate a phase diagram consistent with more recent experiments. An internally consistent diagram could not be calculated that agreed with all published experiments, and choices of preferred data were made. The following Gibbs free energies, relative to the elements at STP (298.15 K, 1 bar), have been derived

The above values were calculated assuming literature values for corundum, quartz, and H2O (v).

Examination of available thermodynamic, experimental, and observational data on the aluminum hydroxides gibbsite, boehmite, bayerite, and nordstrandite suggests that these minerals are metastable with respect to diaspore + water at STP and at higher temperatures. Similarly, halloysite and dickite are metastable with respect to kaolinite at these conditions. The occurrence of these minerals in soils must therefore be ascribed to nonequilibrium processes, and the use of equilibrium phase diagrams to explain their occurrence is inappropriate.

Pressures of 10 GPa and above can bring about phase transformations in many oxides, an effect of great interest to geochemists and geophysicists. We can interpret such behaviour as due to the differential compressibility of 'anion' and 'cation' leading to a progressive rise in radius ratio with pressure, and hence, on the classic crystallochemical picture, eventually to an increase in co-ordination number (though with complications which make prediction difficult). More generally, pressure affects Gibbs free energy G directly; for oxides a pressure of 5 GPa gives, very roughly, the same contribution to G as 100°C in temperature (though with opposite sign). Thus high pressure significantly affects the shape and structure of phase diagrams, showing increasingly important effects above, say, 10 GPa—but again prediction can be difficult. However these two complementary approaches to the effects of pressure, helpful though they can be conceptually, are 'crystal-based' and totally neglect another rather littleknown but potentially important effect--the formation of amorphous solids; 'polymers' and glasses. Since amorphous materials are 'non-equilibrium' they are not readily dealt with theoretically; also, since they are difficult to detect by standard crystallographic techniques, they can be overlooked experimentally. The pressure-induced formation of amorphous solids could have significant implications for both geochemistry and geophysics.

We have explored chemical weathering of probable martian materials at low temperatures based on the increasing evidence for non-hydrothermal water at or near the martian surface. Chemical weathering of minerals at low temperatures (as low as 0 °C) in aqueous environments on Mars can provide geochemical energy to support construction of potential martian organisms. Here, we examine the geochemical energy available from the interaction of the martian surface or near-surface materials with low-temperature water. We calculate the Gibbs free energy for 13 different weathering reactions that are likely to be important on Mars. The aqueous weathering of 1 kg of an ultramafic rock such as the Chassigny meteorite under present martian conditions can support the construction of ~30 g of microbes. The aqueous weathering of 1 kg of a basaltic rock on Mars can support the construction of ~26 g of biomass under present martian conditions and ~32 grams for conditions probable in the past. This means that ~1.3×1019 g of potential biomass could have been supported from weathering a global layer of rock 1 m thick. Thus, low-temperature water–rock reactions on Mars can produce abundant geochemical energy for potential martian microbes.