previously he was at Sandia National Laboratories. His research concerns the energetics and kinetics of the reactions between minerals and aqueous solutions, and in recent work, he has determined rate coefficients for dissociation of Al−O bonds in various dissolved aluminum complexes.

No abstract

Shale formations play fundamental roles in large-scale geologic carbon sequestration (GCS) aimed primarily to mitigate climate change and in smaller-scale GCS targeted mainly for CO2-enhanced gas recovery operations. Reactive components of shales include expandable clays, such as montmorillonites and mixed-layer illite/smectite clays. In this study, in situ X-ray diffraction (XRD) and in situ infrared (IR) spectroscopy were used to investigate the swelling/shrinkage and H2O/CO2 sorption of Na(+)-exchanged montmorillonite, Na-SWy-2, as the clay is exposed to variably hydrated supercritical CO2 (scCO2) at 50 °C and 90 bar. Measured d001 values increased in stepwise fashion and sorbed H2O concentrations increased continuously with increasing percent H2O saturation in scCO2, closely following previously reported values measured in air at ambient pressure over a range of relative humidities. IR spectra show H2O and CO2 intercalation, and variations in peak shapes and positions suggest multiple sorbed types of H2O and CO2 with distinct chemical environments. Based on the absorbance of the asymmetric CO stretching band of the CO2 associated with the Na-SWy-2, the sorbed CO2 concentration increases dramatically at sorbed H2O concentrations from 0 to 4 mmol/g. Sorbed CO2 then sharply decreases as sorbed H2O increases from 4 to 10 mmol/g. With even higher sorbed H2O concentrations as saturation of H2O in scCO2 was approached, the concentration of sorbed CO2 decreased asymptotically. Two models, one involving space filling and the other a heterogeneous distribution of integral hydration states, are discussed as possible mechanisms for H2O and CO2 intercalations in montmorillonite. The swelling/shrinkage of montmorillonite could affect solid volume, porosity, and permeability of shales. Consequently, the results may aid predictions of shale caprock integrity in large-scale GCS as well as methane transmissivity in enhanced gas recovery operations.

Expandable clays such as montmorillonite have interlayer exchange sites whose hydration state can be systematically varied from near anhydrous to almost bulk-like water conditions. This phenomenon has new significance with the simultaneous implementation of geological sequestration and secondary utilization of CO 2 to both mitigate climate warming and enhance extraction of methane from hydrated clay-rich formations. In this study, the partitioning of CO 2 a n d H 2 O between Na-, Ca-, and Mg-exchanged montmorillonite and variably hydrated supercritical CO 2 (scCO 2 ) was investigated using in situ X-ray diffraction (HXRD), infrared (IR) spectroscopic titrations, and quartz crystal microbalance (QCM) measurements. Density functional theory calculations provided mechanistic insights. Structural volumetric changes were correlated to quantified changes in sorbed H 2 O and CO 2 concentrations as a function of percent H 2 O saturation in scCO 2 . Intercalation of CO 2 is inhibited when the clay is fully collapsed (dehydrated interlayer), peaks sharply with the introduction of some H 2 O and partial expansion of the interlayer region, and then decreases systematically with further hydration of the clay. This behavior is discussed in the context of recent theoretical calculations of the montmorillonite H 2 O-CO 2 system.