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Fujii, T, Pringle EA, Chaussidon M, Moynier F.  2015.  Isotope fractionation of Si in protonation/deprotonation reaction of silicic acid: A new pH proxy. Geochimica et Cosmochimica Acta. 168:193-205.   10.1016/j.gca.2015.07.003   Abstract

Isotopic fractionation of Si in protonation/deprotonation reactions of monomeric silicic acids was theoretically and experimentally studied. The reduced partition function ratio for Si (as 1000 ln b) complexes was theoretically estimated by ab initio methods. Three permil of isotope fractionation was estimated to be possible for the 28Si-30Si isotope pair. This prediction was experimentally demonstrated by multi-collector inductively coupled plasma mass spectrometer measurements of Si-bearing aqueous solutions, for which equilibrated Si(OH)4 and SiO(OH)3 were separated using an anionic exchange column. The results create a new possibility for the application of Si isotopes as proxies for paleo-pH in the 9 < pH < 12 range.