Grain boundary widening controls siderite (FeCO3) replacement of limestone (CaCO3)

Weber, Juliane; Starchenko, Vitalii; Ilavsky, Jan; Allard, Lawrence F.; Mata, Jitendra; Debeer-Schmitt, Lisa; Cooke, Carolyn Grace; Littrell, Ken; He, Lilin; Zhang, Rui; Stack, Andrew G.; Anovitz, Lawrence M.

doi:10.1038/s41598-023-30757-y

Title: Grain boundary widening controls siderite (FeCO3) replacement of limestone (CaCO3)

Journal Article · 19 March 2023 · Scientific Reports

DOI: https://doi.org/10.1038/s41598-023-30757-y · OSTI ID:1963362

Weber, Juliane; Starchenko, Vitalii; Ilavsky, Jan; Allard, Lawrence F.; Mata, Jitendra; Debeer-Schmitt, Lisa; Cooke, Carolyn Grace; Littrell, Ken; He, Lilin; Zhang, Rui; Stack, Andrew G.; Anovitz, Lawrence M.

Abstract The microstructure of minerals and rocks can significantly alter reaction rates. This study focuses on identifying transport paths in low porosity rocks based on the hypothesis that grain boundary widening accelerates reactions in which one mineral is replaced by another (replacement reaction). We conducted a time series of replacement experiments of three limestones (CaCO ₃ ) of different microstructures and solid impurity contents using FeCl ₂ . Reacted solids were analyzed using chemical imaging, small angle X-ray and neutron scattering and Raman spectroscopy. In high porosity limestones replacement is reaction controlled and complete replacement was observed within 2 days. In low porosity limestones that contain 1–2% dolomite impurities and are dominated by grain boundaries, a reaction rim was observed whose width did not change with reaction time. Siderite (FeCO ₃ ) nucleation was observed in all parts of the rock cores indicating the percolation of the solution throughout the complete core. Dolomite impurities were identified to act as nucleation sites leading to growth of crystals that exert force on the CaCO ₃ grains. Widening of grain boundaries beyond what is expected based on dissolution and thermal grain expansion was observed in the low porosity marble containing dolomite impurities. This leads to a self-perpetuating cycle of grain boundary widening and reaction acceleration instead of reaction front propagation.

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Sponsoring Organization:: USDOE

OSTI ID:: 1963362

Alternate ID(s):: OSTI ID: 1965240; OSTI ID: 2216918

Journal Information:: Scientific Reports, Journal Name: Scientific Reports Journal Issue: 1 Vol. 13; ISSN 2045-2322

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United Kingdom

Language:: English

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