Thermodynamic and structural aspects of the dehydration of smectites in sedimentary rocks

Abstract

AbstractThe diagenetic conversion of smectite to illite in shales has been proposed as a mechanism for generating overpressure (fluid pressure above hydrostatic) in sedimentary basins. However, the mechanism and rate-controlling factors of the reaction and the magnitude of the resulting volume change are not known. In this paper the thermodynamics of the reversible hydration/dehydration of smectite are analysed in the pressure/temperature regime of sedimentary rocks. If the interlamellar water is more dense than bulk water, and the pressures on the solid and fluid phases are equal, the dehydration temperature should increase with increasing confining pressureviathe Clapeyron-Clausius equation. However, either fluid pressures below the pressure on the solid matrix or high pore-fluid salinities can reduce the dehydration temperature. Experiments on Ca2+-montmorillonite compacted in the presence of distilled water in a steel autoclave fitted with a sensitive pressure transducer failed to detect any overall volume change due to dehydration up to 185°C and 1400 bar. This finding, which is consistent with recent high-pressure DTA and XRD studies on Na+-montmorillonite, suggests that reversible loss of the last two water layers does not occur in sedimentary basins except as part of the more complex diagenetic conversion of smectite to illite. Some recent evidence from high-resolution TEM and microprobe analyses regarding the mechanism of the reaction is also discussed.