Crystallization of ikaite and its pseudomorphic transformation into calcite: Raman spectroscopy evidence

Ikaite (CaCO3 center dot 6H(2)O) is a metastable phase that crystallizes in nature from alkaline waters with high phosphate concentrations at temperatures close to 0 degrees C. This mineral transforms into anhydrous calcium carbonate polymorphs when temperatures rise or when exposed to atmospheric conditions. During the transformation in some cases the shape of the original ikaite crystal is preserved as a pseudomorph. Pseudomorphs after ikaite are considered as a valuable paleoclimatic indicator. In this work we conducted ikaite crystal growth experiments at near-freezing temperatures using the single diffusion silica gel technique, prepared with a natural aqueous solution from the polymictic lake Laguna Potrok Aike (51 degrees 57'S, 70 degrees 23'W) in Patagonia, Argentina. The ikaite crystals were recovered from the gels and the transformation reactions were monitored by in situ Raman spectroscopy at two different temperatures. The first spectra collected showed the characteristic features of ikaite. In successive spectra new bands at 1072, 1081 and 1086 cm(-1) and changes in the intensity of bands corresponding to the OH modes were observed. These changes in the Raman spectra were interpreted as corresponding to intermediate stages of the transformation of ikaite into calcite and/or vaterite. After a few hours, the characteristics of the Raman spectrum were consistent with those of calcite. While ikaite directly transforms into calcite at 10 degrees C in contact with air, at 20 degrees C this transformation involves the formation of intermediate, metastable vaterite. During the whole process the external shape of ikaite crystals was preserved. Therefore, this transformation showed the typical characteristics of a pseudomorphic mineral replacement, involving the generation of a large amount of porosity to account for the large difference in molar volumes between ikaite and calcite. A mechanism involving the coupled dissolution of ikaite and crystallization of calcite/vaterite is proposed for this replacement. (C) 2015 Elsevier Ltd. All rights reserved.