Dissolved sulfide-catalyzed precipitation of disordered dolomite: Implications for the formation mechanism of sedimentary dolomite

Dolomite is a common mineral in the rock record. However, the rarity of modern dolomite and the notorious difficulty in synthesizing dolomite abiotically under normal Earth-surface conditions result in the long-standing “dolomite problem” in sedimentary geology. Some modern dolomites are associated...

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Published in:Geochimica et cosmochimica acta 2012-11, Vol.97, p.148-165
Main Authors: Zhang, Fangfu, Xu, Huifang, Konishi, Hiromi, Kemp, Joshua M., Roden, Eric E., Shen, Zhizhang
Format: Article
Language:eng
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Summary:Dolomite is a common mineral in the rock record. However, the rarity of modern dolomite and the notorious difficulty in synthesizing dolomite abiotically under normal Earth-surface conditions result in the long-standing “dolomite problem” in sedimentary geology. Some modern dolomites are associated with sediments where microbial sulfate reduction is active; however, the role of sulfate-reducing bacteria in dolomite formation is still under debate. In this study, we tested the effect of dissolved sulfide on the precipitation of Ca–Mg carbonates, which has been never explored before although dissolved sulfide is one of the major products of microbial sulfate reduction. Our results demonstrated that dissolved sulfide with a concentration of as low as several millimoles can enhance the Mg2+ incorporation into the calcitic structure, and promote the crystallization of high magnesian calcite and disordered dolomite. We also conducted seeded precipitation in experimental solutions containing dissolved sulfide, which showed that calcite seeds can inhibit the precipitation of aragonite and monohydrocalcite (CaCO3·H2O), and induce more Mg2+ incorporation. We propose that accumulated dissolved sulfide in pore waters in organic-rich sediments may trigger the precipitation of disordered dolomite which can be considered as a precursor of some sedimentary dolomite. Our adsorption experiments revealed a strong adsorption of dissolved sulfide onto calcite faces. We suggest that adsorbed dissolved sulfide can lower the energy barrier to the dehydration of Mg2+–water complexes on the growing carbonate surfaces. This study sheds new light on understanding the role of sulfate-reducing bacteria in dolomite formation and the formation mechanism of sedimentary dolomite.
ISSN:0016-7037
1872-9533