LAUSR

Abstract Glauconite is an authigenic, iron-rich clay mineral that is abundant in greensands formations worldwide. Evidence from these formations suggests that glauconite is commonly diagenetically converted to carbonate minerals such as siderite, ankerite, and ferroan dolomite. This process represents a natural CO2 sink that may provide an effective mechanism for the engineered mineralization of anthropogenic CO2. To evaluate glauconite carbonation reactions and improve our understanding of glauconite diagenesis, we performed a detailed evaluation of the mechanisms through which carbonate minerals naturally replace glauconite during diagenesis of glauconitic sandstones from the Lower Cretaceous Upper Mannville Group in western Alberta, Canada. Using a combination of optical microscopy and scanning electron imaging, electron microprobe and bulk geochemical analyses, and X-ray fluorescence mapping, we show glauconite carbonation in the Mannville group is an reduction-facilitated, coupled glauconite recrystallization and siderite precipitation reaction. X-ray absorption near-edge spectroscopic mapping and spot analyses demonstrate that this reaction is accompanied by a significant shift in the oxidation state of Fe, from dominantly oxidized in glauconite to reduced in carbonate reaction products. Together, these results suggest that geochemical conditions - most importantly, temperature, partial pressure of CO2, and fluid redox state - were thermodynamically favorable for glauconite carbonation during burial diagenesis of Mannville Group sandstones. Results of thermodynamic models illustrate that, although K-feldspar is favored to precipitate during reductive glauconite dissolution and accompanying Fe-carbonate precipitation, its precipitation is likely kinetically limited, and that an Fe-impoverished glauconite is expected to recrystallize instead. Our findings show that glauconite carbonation is likely a common phenomenon in the subsurface, and thus that glauconite is potentially a significant cation source for mineralizing anthropogenic CO2.