Experimental constraints on Li isotope fractionation during clay formation

Hindshaw, Ruth S. and Tosca, Rebecca and Goût, Thomas L. and Farnan, Ian and Tosca, Nicholas J. and Tipper, Edward T. (2019) Experimental constraints on Li isotope fractionation during clay formation. Geochimica Et Cosmochimica Acta, 250. pp. 219-237. ISSN 0016-7037 DOI https://doi.org/10.1016/j.gca.2019.02.015

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Knowledge of the lithium (Li) isotope fractionation factor during clay mineral formation is a key parameter for Earth sys-tem models. This study refines our understanding of isotope fractionation during clay formation with essential implicationsfor the interpretation of field data and the global geochemical cycle of Li. We synthesised Mg-rich layer silicates (stevensiteand saponite) at temperatures relevant for Earth surface processes. The resultant solids were characterised by X-ray diffrac-tion (XRD) and Fourier-transform infrared spectroscopy (FT-IR) to confirm the mineralogy and crystallinity of the product.Bulk solid samples were treated with ammonium chloride to remove exchangeable Li in order to distinguish the Li isotopicfractionation between these sites and structural (octahedral) sites. Bulk solids, residual solids and exchangeable solutions wereall enriched in6Li compared to the initial solution. On average, the exchangeable solutions hadd7Li values 7‰lower than theinitial solution. The average difference between the residual solid and initial solutiond7Li values (D7Liresidue-solution) for the syn-thesised layer silicates was�16.6 ± 1.7‰at 20�C, in agreement with modelling studies, extrapolations from high tempera-ture experimental data and field observations. Three bonding environments were identified from7Li-NMR spectra which werepresent in both bulk and residual solid7Li-NMR spectra, implying that some exchangeable Li remains after treatment withammonium chloride. The7Li-NMR peaks were assigned to octahedral, outer-sphere (interlayer and adsorbed) and pseudo-hexagonal (ditrigonal cavity) Li. By combining the7Li-NMR data with mass balance constraints we calculated a fractionationfactor, based on a Monte Carlo minimum misfit method, for each bonding environment. The calculated values are�21.5± 1.1‰,�0.2 ± 1.9‰and 15.0 ± 12.3‰for octahedral, outer-sphere and pseudo-hexagonal sites respectively (errors 1r).The bulk fractionation factor (D7Libulk-solution) is dependent on the chemistry of the initial solution. The higher the Na concen-tration in the initial solution the lower the bulkd7Li value. We suggest this is due to Na outcompeting Li for interlayer sitesand as interlayer Li has a highd7Li value relative to octahedral Li, increased Na serves to lower the bulkd7Li value. Threeexperiments conducted at higher pH exhibited lowerd7Li values in the residual solid. This could either be a kinetic effect,resulting from the higher reaction rate at high pH, or an equilibrium effect resulting from reduced Li incorporation in theresidual solid and/or a change in Li speciation in solution.This study highlights the power of7Li-NMR in experimental studies of clay synthesis to target site specific Li isotope frac-tionation factors which can then be used to provide much needed constraints on field processes.

Item Type: Article
Uncontrolled Keywords: 2019AREP; IA75
Subjects: 03 - Mineral Sciences
Divisions: 01 - Climate Change and Earth-Ocean Atmosphere Systems
03 - Mineral Sciences
08 - Green Open Access
12 - PhD
Journal or Publication Title: Geochimica Et Cosmochimica Acta
Volume: 250
Page Range: pp. 219-237
Identification Number: https://doi.org/10.1016/j.gca.2019.02.015
Depositing User: Sarah Humbert
Date Deposited: 20 May 2019 10:33
Last Modified: 09 Jul 2020 17:34
URI: http://eprints.esc.cam.ac.uk/id/eprint/4490

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