Reaction pathways and textural aspects of the replacement of anhydrite by calcite at 25 ºC

Roncal-Herrero, Teresa and Astilleros, Jose Manuel and Bots, Pieter and Rodriguez-Blanco, Juan Diego and Prieto, Manuel and Benning, Liane G. and Fernández-Díaz, Lurdes (2017) Reaction pathways and textural aspects of the replacement of anhydrite by calcite at 25 ºC. American Mineralogist, 102 (6). pp. 1270-1278. ISSN 0003-004X (https://doi.org/10.2138/am-2017-5963CCBY)

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Abstract

The replacement of sulfate minerals by calcium carbonate polymorphs (carbonation) has important implications in a variety of geological processes occurring in Earth surface environments. In this paper we report the results of an experimental study of the interaction between anhydrite (100), (010) and (001) surfaces and Na2CO3 aqueous solutions under ambient conditions. Carbonation progress was monitored by glancing incidence X-ray diffraction (GIXRD) and scanning electron microscopy (SEM). We show that the reaction progresses through the dissolution of anhydrite and the simultaneous growth of calcite. The growth of calcite occurs oriented on the three anhydrite cleavage surfaces and its formation is accompanied by minor vaterite. The progress of the carbonation always occurs from the outer-ward to the inner-ward surfaces and its rate depends on the anhydrite surface considered, with the (001) surface being much more reactive than the (010) and (100) surfaces. The thickness of the formed carbonate layer grows linearly with time. The original external shape of the anhydrite crystals and their surface details (e.g., cleavage steps) are preserved during the carbonation reaction. Textural characteristics of the transformed regions, such as the gradation in the size of calcite crystals, from ~2 µm in the outer region to ~17 µm at the calcite-anhydrite interface, the local preservation of calcite crystalographic orientation with respect to anhydrite and the distribution of the microporosity mainly within the carbonate layer without development of any significant gap between at the calcite-anhydrite interface. Finally, we compare these results on anhydrite carbonation with those on gypsum carbonation and can explain the differences on the basis of four parameters: (i) the molar volume change involved in the replacement process in each case, (ii) the lack/existence of epitactic growth between parent and product phases, (iii) the kinetics of dissolution of the different surfaces, and (iv) the chemical composition (amount of structural water) of the parent phases.

ORCID iDs

Roncal-Herrero, Teresa, Astilleros, Jose Manuel, Bots, Pieter ORCID logoORCID: https://orcid.org/0000-0001-6863-0648, Rodriguez-Blanco, Juan Diego, Prieto, Manuel, Benning, Liane G. and Fernández-Díaz, Lurdes;
CORE (COnnecting REpositories)