The Role and Implications of Bassanite as a Stable Precursor Phase to Gypsum Precipitation
Roundabout Gypsum
Calcium sulfates are a common but perhaps underappreciated group of minerals used in a number of natural and industrial processes. In many ways, these crystals precipitate from solution in the same way that most other aqueous minerals form; however, mounting evidence suggests that different, unexplored mechanisms may be at work. Van Driessche et al. (p. 69; see the cover) performed high-resolution microscopy of the most common calcium sulfate mineral, gypsum, at various points along time-resolved, fast-quenching growth experiments. The images reveal that gypsum particles actually start out as crystalline nanoparticles of another mineral, bassanite, which then self-assemble into well-ordered nanorods. Finally, the nanorods transform into gypsum following a hydration reaction. The observation that the reaction pathway occurs below the solubility limit of the intermediate phase has wide-ranging implications for biomineralization processes and may provide ways to prevent fouling on the surfaces of desalination membranes.
Abstract
Calcium sulfate minerals such as gypsum play important roles in natural and industrial processes, but their precipitation mechanisms remain largely unexplored. We used time-resolved sample quenching and high-resolution microscopy to demonstrate that gypsum forms via a three-stage process: (i) homogeneous precipitation of nanocrystalline hemihydrate bassanite below its predicted solubility, (ii) self-assembly of bassanite into elongated aggregates co-oriented along their c axis, and (iii) transformation into dihydrate gypsum. These findings indicate that a stable nanocrystalline precursor phase can form below its bulk solubility and that in the CaSO4 system, the self-assembly of nanoparticles plays a crucial role. Understanding why bassanite forms prior to gypsum can lead to more efficient anti-scaling strategies for water desalination and may help to explain the persistence of CaSO4 phases in regions of low water activity on Mars.
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Science
Volume 336 | Issue 6077
6 April 2012
6 April 2012
Copyright
Copyright © 2012, American Association for the Advancement of Science.
Submission history
Received: 24 October 2011
Accepted: 24 February 2012
Published in print: 6 April 2012
Acknowledgments
Supported by the Marie Curie EU-FP6 Mineral Nucleation and Growth Kinetics (MIN-GRO) Research and Training Network (contract MRTNCT-2006-035488), the School of Earth and Environment at the University of Leeds, the Consolíder-Ingenio 2010 project “Factoría Española de Cristalización,” and project CGL2010-16882 of the Ministerio de Ciencia e Innovación (MICINN). We thank M. Ward, A. Brown, and S. Allshorn for help with sample preparation and characterization and three anonymous reviewers for their helpful comments.
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