Iodine Incorporation in Calcite: Insights from Computational and Experimental Study
Abstract
The incorporation of iodine into calcite is important both in the context of radioactive waste disposal (carbonates seem to be the principal host for iodine at the Hnaford site) as well as in paleoproxy methods applied in paleo-oceanography, where iodine content has been proposed as a proxy for fO2. Here, we report on studies of iodine incorporation into calcite carried out by a combination of earlier X-Ray absorption spectroscopy, Raman spectroscopy, X-Ray diffraction and new ab initio DFT calculations (using VASP). Our results show that iodine is principally incorporated into the calcite lattice as IO3, replacing carbon in the carbonate group. The much larger size of iodine, and different outer shell electronic configuration, leads to a distortion of the calcite structure locally. Our DFT results show that the adjacent layers of CO3 groups are significantly distorted, over a length scale of around 0.5 nm, and that this distortion leads to a slight increase in enthalpy associated with the iodine point defect. The relationship to the distorted structure of calcite II is considered, and the role of iodine as an agent of "internal pressure" will be discussed.
- Publication:
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AGU Fall Meeting Abstracts
- Pub Date:
- December 2016
- Bibcode:
- 2016AGUFMMR13A2383F
- Keywords:
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- 3909 Elasticity and anelasticity;
- MINERAL PHYSICSDE: 3954 X-ray;
- neutron;
- and electron spectroscopy and diffraction;
- MINERAL PHYSICSDE: 3620 Mineral and crystal chemistry;
- MINERALOGY AND PETROLOGYDE: 3694 Instruments and techniques;
- MINERALOGY AND PETROLOGY