Fluid composition, mineralogy and morphological changes associated with the smectite-to-illite reaction: an experimental investigation of the effect of organic acid anions

Abstract The smectite-to-illite reaction (illitization) was examined in a dilute suspension of Wyoming bentonite in the presence of oxalate and acetate. Experiments were performed using fluidsampling apparatus at 200°C, 50 MPa, in which progressive changes in both clay mineralogy and fluid composition were monitored. The presence of K-oxalate and K-acetate under neutral-alkaline conditions produced significant reaction of smectite to either R1 or R2 ordered illite-smectite with 60–70% illite layers. Experiments at the same temperature with KCl, or oxalic acid plus KCl, produced no reaction. Fluid chemistry showed that K-oxalate and K-acetate resulted in the establishment of a K + / a H + conditions within the muscovite stability field, favouring the formation of illite. The extent of dissolution and precipitation indicated by fluid data is insufficient to account for the amount of illitization evident in the mineralogy. This implies that a localized dissolution-precipitation process occurs, perhaps on the scale of a single clay particle. These experiments highlight the importance of pH as a control over illitization and show that organic anions can buffer fluid composition into the optimum a K + / a H + condition for illitization. These findings are highly significant for the smectite-to-illite reaction occurring in organic bearing sediments where organic acid anions are generated during kerogen maturation.