Effect of fO2 on the incorporation and diffusivity of Li in olivine
Abstract
Over the last decade the geochemical behaviour of Li has become of special interest since it was speculated that Li stable isotopes could be a promising tracer for subduction zone processes. However, there have been many studies of natural samples but our experimental and theoretical basis for interpreting these data is still lacking. Two diffusion mechanisms were identified for Li in olivine [1]. Their contribution to the net flux of Li in olivine depends on the vacancy concentration on the metal sites, which is sensitive to the fO2. Therefore we have studied the effect of fO2 on Li solubility and diffusion in olivine. Experimental approach: thin plates of crushed, natural olivine single crystals were embedded into two different kind of powders, ground plagioclase with about 2.5 ppm Li or a pre-annealed powder mixture of San Carlos olivine and isotopically enriched Li. All runs were performed in a gas-mixing furnace with fO2 controlled by flowing CO/CO2 mixture. In each run we simultaneously annealed about 100 micrometer-sized samples of Pakistan olivine and San Carlos olivine. In addition we have added to each run a mm sized crystallographically oriented parallelepiped of San Carlos olivine. For each powder reservoir we have performed a set of three anneals at 1200 C and different fO2. Cross sections of the run products were polished and analyzed with LA-ICP-MS. Results: In all cases the Li isotopes and concentrations were homogeneous in the 100 micrometer sized grains with one exception, the experiment at 1.e-10 bar with the highly enriched Li reservoir. The final Li concentration was slightly lower in the Pakistan than San Carlos olivine and was much lower in general if buffered by the plagioclase powder. Most importantly, the Li concentration increased systematically with increasing oxygen fugacity, indicating that the incorporation of Li in olivine is fO2 dependent. The mm-sized, oriented crystal was in most cases zoned and the extent of zoning depends on the diffusion direction. In addition the profiles became systematically longer with decreasing fugacity and at the most reducing conditions the crystal was almost homogenous. However, the isotopes were in all cases completely homogenized and equilibrated with the isotopically enriched reservoir. Thermodynamic model: We extended the quantitative point defect model for olivine [2] and reproduced the effect of fO2 on the solubility of Li when we assume it is mainly on the metal site and charge balanced by the formation of Fe3+ on the metal site. Conclusions: Our results strongly indicate that incorporation of Li is dependent on the fO2, less dependent on the trace element content. Diffusion of Li in olivine is anisotropic and dependent on fO2. Our quantitative point defect model for olivine underpins the experimental results. This will allow us to develop a multi-component diffusion model considering relevant point defects, e.g. Fe3+ and metal vacancies. Such a model will hopefully help us to simulate diffusion of Li at various natural circumstances including fO2 as a critical parameter. References: [1] Dohmen et al. (2010) Geochim Cosmochim Acta 74, 274-292; [2] Dohmen and Chakraborty (2007), Phys Chem Minerals 34, 597- 598.
- Publication:
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AGU Fall Meeting Abstracts
- Pub Date:
- December 2012
- Bibcode:
- 2012AGUFMMR11A2469D
- Keywords:
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- 1038 GEOCHEMISTRY / Mantle processes;
- 3621 MINERALOGY AND PETROLOGY / Mantle processes