Titanium- and water-rich metamorphic olivine in high-pressure serpentinites from the Voltri Massif (Ligurian Alps, Italy): evidence for deep subduction of high-field strength and fluid-mobile elements

Abstract

Titanium- and water-rich metamorphic olivine (Fo 86-88) is reported from partially dehydrated serpentinites from the Voltri complex, Ligurian Alps. The rocks are composed of mostly antigorite and olivine in addition to magnetite, chlorite, clinopyroxene and Ti-clinohumite. In situ secondary ion mass spectrometry (SIMS) data show that metamorphic olivine has very high and strongly correlated H2O (up to 0.7 wt%) and TiO2 contents (up to 0.85 wt%). Ti-rich olivine shows colourless to yellow pleochroism. Olivine associated with Ti-clinohumite contains low Ti, suggesting that Ti-rich olivine is not the breakdown product of Ti-clinohumite. Fourier transform infrared spectroscopy (FTIR) absorption spectra show peaks of serpentine, Ti-clinohumite and OH-related Si vacancies. Combining FTIR and SIMS data, we suggest the presence of clustered planar defects or nanoscale exsolutions of Ti-clinohumite in olivine. These defects or exsolutions contain more H2O (x similar to 0.1 in the formula 4Mg(2)SiO(4)center dot(1-x)Mg(OH, F)(2)center dot xTiO(2)) than Ti-clinohumite in the sample matrix (x = 0.34-0.46). In addition to TiO2 and H2O, secondary olivine contains significant Li (2-60 ppm), B (10-20 ppm), F (10-130 ppm) and Zr (0.9-2.1 ppm). It is enriched in B-11 (delta B-11 = +17 to +23 parts per thousand). Our data indicate that secondary olivine may play a significant role in transporting water, high-field strength and fluid-mobile elements into the deeper mantle as well as introduce significant B isotope anomalies. Release of hydrogen from H2O-rich olivine subducted into the deep mantle may result in strongly reduced mantle domains.