Effect of Silica Activity on OH- IR Spectra of Olivine: Implications for Low-aSiO2 Mantle Metasomatism

Hydrogen solubility and hydroxyl substitution mechanism in olivineat upper-mantle conditions are not only a function of pressure,temperature, water fugacity and hydrogen fugacity, but are alsoinfluenced by silica activity. Olivine synthesized in equilibriumwith magnesiowüstite displays hydroxyl stretching bandsin the wavenumber range from 3640 to 3430 cm^–1. In contrast,olivine in equilibrium with orthopyroxene shows absorption bandsin a narrower wavenumber range from 3380 to 3285 cm^–1.The two fundamentally different spectra are assigned to hydroxylin tetrahedral and octahedral sublattices, respectively. Olivinein equilibrium with orthopyroxene is also less capable of incorporatinghydroxyl, relative to olivines in equilibrium with magnesiowüstite,by about a factor of ten. A comparison of spectra obtained aspart of this study with hydroxyl spectra of natural mantle olivinesshows that the latter display hydroxyl stretching patterns reminiscentof equilibrium with magnesiowüstite, although undoubtedlyolivine in the Earth’s mantle coexists with orthopyroxene.This may be attributed to a metasomatic overprint by a low-silicafluid and/or melt that was in reaction relationship with orthopyroxene.A likely metasomatic agent is a carbonatitic melt. When carbonatiticmelts decompose to oxides and CO₂, they may temporarily imposea low-aSiO₂ environment inherited by the olivine structure.If this suggestion proves true, Fourier transform IR spectroscopymay be used to fingerprint metasomatic episodes in the lithosphericmantle. KEY WORDS: FTIR spectrometry; olivine; mantle; metasomatism; water