Late diagenetic calcitization of anhydrite from the Mississippian of Saskatchewan, western Canada

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Abstract

Mississippian nodular anhydrites beneath an unconformity in the subsurface of southern Saskatchewan are locally replaced by calcite, pyrite and celestite. Triassic clastics above the unconformity are green, rather than red, and a usually developed subunconformity alteration zone (where carbonates are dolomitized, and porosity is filled with anhydrite) is absent. The unconformity lacks karstic features (unlike in the USA), and probably formed in a hyperarid climate. Mississippian anhydrites near the unconformity are not preferentially dissolved, nor were they extensively hydrated. Anhydrite calcitization occurred only after the unconformity was shallowly buried by redbeds, and it probably involved sulphate-reducing bacteria. Hydrogen sulphide, generated by bacteria, reduced redbed pigments. The replacement calcite contains pseudomorphs and relicts of anhydrite, and pseudomorphs of secondary gypsum. These indicate calcitization occurred only after original Mississippian gypsum was altered to anhydrite and this, in turn, was partially converted back to secondary gypsum beneath the unconformity. Replacement occurred concurrently with the formation elsewhere of the dolomitized zone beneath the unconformity. Sulphur isotopic ratios of replacement pyrite are depleted relative to Mississippian sulphate values, consistent with the activities of sulphate-reducing bacteria. Carbon isotopic ratios of replacive calcites, however, do not support this interpretation, and are identical to those of Mississippian limestones. Simple replacement of sulphate by pore-water bicarbonate (in equilibrium with host limestones) is unlikely because protons generated during the reaction should have created acidic conditions in which calcite would have dissolved. A full explanation of the calcitization remains elusive, but may involve replacement occurring in an active groundwater system and/or bacterial sulphate reduction occurring upstream of the site of calcitization.

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