Hydrogen–Rock Interactions in Carbonate and Siliceous Reservoirs: A Petrophysical Perspective

Underground hydrogen storage (UHS) in carbonate and siliceous formations presents a promising solution for managing intermittent renewable energy. However, experimental data on hydrogen–rock interactions under representative subsurface conditions remain limited. This study systematically investigates mineralogical and petrophysical alterations in dolomite, calcite-rich limestone, and quartz-dominant siliceous cores subjected to high-pressure hydrogen (100 bar, 70 °C, 100 days). Distinct from prior research focused on diffraction peak shifts, our analysis prioritizes quantitative changes in mineral concentration (%) as a direct metric of reactivity and structural integrity, offering more robust insights into long-term storage viability. Hydrogen exposure induced significant dolomite dissolution, evidenced by reduced crystalline content (from 12.20% to 10.53%) and accessory phase loss, indicative of partial decarbonation and ankerite-like formation via cation exchange. Conversely, limestone exhibited more pronounced carbonate reduction (vaterite from 6.05% to 4.82% and calcite from 2.35% to 0%), signaling high reactivity, mineral instability, and potential pore clogging from secondary precipitation. In contrast, quartz-rich cores demonstrated exceptional chemical inertness, maintaining consistent mineral concentrations. Furthermore, Brunauer–Emmett–Teller (BET) surface area and Barrett–Joyner–Halenda (BJH) pore distribution analyses revealed enhanced porosity and permeability in dolomite (pore volume increased >10×), while calcite showed declining properties and quartz showed negligible changes. SEM-EDS supported these trends, detailing Fe migration and textural evolution in dolomite, microfissuring in calcite, and structural preservation in quartz. This research establishes a unique experimental framework for understanding hydrogen–rock interactions under reservoir-relevant conditions. It provides crucial insights into mineralogical compatibility and structural resilience for UHS, identifying dolomite as a highly promising host and highlighting calcitic rocks’ limitations for long-term hydrogen containment.