Coupled Evolution of Clay Minerals and Organic Matter During Diagenesis: Mechanisms of Smectite Illitization in Organic-Rich Shale

The transformation of smectite to illite documents multi-scale water–rock–hydrocarbon interaction dynamics. Current studies predominantly emphasize the influence of inorganic systems on this process, while overlooking the dynamic regulation by organic matter and the synergistic effects of multiple controlling factors under actual geological conditions. In this study, we conducted integrated semi-open pyrolysis experiments on natural samples from the Chang-7 Member and hydrothermal experiments using synthetic analogs. The illitization process of smectite was characterized through XRD analysis and SEM observations, while organic geochemical testing was employed to track the corresponding thermal evolution of organic matter. The semi-open pyrolysis results reveal that significant changes in illite–smectite (I/S) mixed layer minerals and illite content/morphology occur above 320 °C, which coincides with the critical threshold for extensive organic matter evolution. Thermal degradation of organic matter generates pore space, thereby enhancing water–rock interactions involving clay minerals. This demonstrates the co-evolution of organic matter and smectite, and indicates that temperature indirectly influences illitization by regulating organic matter thermal evolution. The hydrothermal simulation experiments demonstrate the early-stage characteristics of illitization. Unlike long-term geological evolution, K+ under experimental conditions primarily originates from the aqueous medium due to kinetic constraints on feldspar dissolution. Notably, organic matter regulates K+ partitioning dynamics—increased organic matter content hinders K+ incorporation into smectite interlayers, thereby suppressing the illitization process. Cross-system experimental analysis reveals that organic matter exhibits temporally dependent dual functionality, serving both mediating and modulating roles within inorganic diagenetic systems. This study delineates diagnostic-stage-dependent mechanisms governing smectite illitization through multifactorial synergistic interplay, establishing a predictive framework applicable to organic-rich systems exemplified by the Chang-7 Shale.