Mineralogical and Geochemical Evolution During Limestone Weathering and Pedogenesis in Shimen, Hunan Province, South China

Understanding mineralogical transformations and elemental mobility during limestone weathering is critical for deciphering carbon cycling and critical zone evolution in karst terrains. This study investigates an in situ limestone weathering profile (12.6 m depth) in Shimen, Hunan Province, using integrated mineralogical (XRD, EPMA-EDS), elemental (XRF, ICP-MS), and Sr isotopic (MC-ICP-MS) analyses. Results reveal a two-stage pedogenic model: (1) Rapid dissolution of primary calcite (>95 wt% in bedrock to 1.1–48.5 wt% in soil) creates an abrupt bedrock–soil interface via volumetric collapse (>90%), accumulating acid-insoluble residues (quartz-dominated); (2) Subsequent weathering drives illitization of K-feldspar, trace element enrichment (e.g., Ni, Tl, Th τ up to 180) via illite adsorption, and radiogenic 87Sr/86Sr evolution (0.7076 in bedrock to 0.7292 in soil). Depth-dependent increases in chemical index of alteration (CIA: 6.79–79.96) and mass transfer coefficients confirm progressive weathering intensity. The profile acts as a net carbon source (58.5% depletion in soil inorganic carbon), highlighting significant CO2 release during pedogenesis. These findings provide mechanistic insights into subtropical critical zone evolution and element cycling in carbonate-dominated systems.