Pure CO₂ and impure CO₂-SO₂-NO-O₂ reactions with carbon storage site underlying seals: Coaly mudstones and carbonate cemented sandstones

Abstract

The transition to net zero emissions requires the capture of carbon dioxide from industrial point sources, and direct air capture (DAC) from the atmosphere for geological storage. Dissolved CO2 has reactivity to rock core, and while the majority of previous studies have concentrated on reservoir rock or cap-rock reactivity, the underlying seal formation may also react with CO2. Drill core from the underlying seal of a target CO2 storage site was reacted at in situ conditions with pure CO2, and compared with an impure CO2 stream with SO2, NO and O2 that could be expected from hard to abate industries. Argillaceous sandstones, mudstones, coaly mudstones, and carbonate cemented sandstones of the Moolayember Formation, Bowen Basin, had significant natural alteration of feldspar to kaolinite creating porosity, with clays, siderite and textured ankerite filling and rimming porosities of 3.5 to 15.8 %. Synchrotron XFM quantified Mn mainly hosted in siderite veins and cements, Sr and Rb in feldspar, and Pb, Th and Sr in monazite. Pb was also in siderite; with As mainly in pyrite and associated with ankerite. On pure CO2 or impure CO2 reaction, ankerite and siderite dissolution, Fe-chlorite leaching, and apatite or sulphide alteration occurred. With the impure CO2 stream Fe-oxides precipitated on rock surfaces especially in argillaceous sandstone. Ferroan carbonates, calcite, and Fe oxides containing Cr were also precipitated. Ankerite and siderite dissolution released increasing concentrations of dissolved Ca, Mg and Mn from carbonate cemented core that were higher with mixed gas injection. Argillaceous sandstone however released higher concentrations Si, Rb, Co and Zn. Dissolved Fe initially increased then decreased in impure gas experiments via Fe oxide precipitation, and Pb, Ni, Cr, REE also increased and subsequently decreased. Geochemical modelling predicted that Fe was mobilised mainly from reaction of siderite and Fe chlorite. Mainly carbonates (siderite, ankerite) and chlorite dissolution released trace metals, with several metals also initially mobilised by desorption and exchange. Precipitated Fe oxides provided adsorption sites to adsorb a portion of metals from solution. These reactions are also relevant to CO2 streams from DAC that could be expected to contain O2 and to potential reactions in overlying aquifers.