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Garnet is a common and important mineral in metamorphic systems, but the mechanisms by which it incorporates Ti-one of the major elements in the crust-are not well constrained. This study draws upon garnets synthesized at a range of temperatures and pressures to understand Ti solubility and the substitution mechanisms that govern its incorporation into garnet at eclogite and granulite facies conditions. Garnets from these synthesis experiments can incorporate up to several wt% TiO2. Comparison of Ti content with deficits in Al and Si in garnet indicates that Ti is incorporated by at least two substitution mechanisms (VITi4+ + VIM2+ ↔ 2VIAl3+, and VITi4+ + IVAl3+ ↔ VIAl3+ + IVSi4+). Increasing Ti solubility is correlated with increasing Ca and Fe/Mg ratios in garnet, clinopyroxene and melt. The complexity of the substitution mechanisms involved in Ti solubility in garnet makes practical Ti-in- garnet thermobarometry infeasible at present. However, a model fit to Ti partitioning between garnet and melt can be used to predict melt compositions in high-grade metamorphic systems. Additionally, the solubility and substitution mechanisms described here can help explain the presence of crystallographically aligned rutile needles in high-grade metamorphic systems. [ABSTRACT FROM AUTHOR]

Titanium can be incorporated either tetrahedrally (IVTi) or octahedrally (VITi) in most silicate minerals. Ti K-edge X-ray absorption fine structure (XAFS) spectroscopy enables observation of Ti coordination in minerals and melts. In this study, XAFS is used to determine the coordination of Ti in synthetic and natural garnets. Garnets grown synthetically at eclogite- and granulite-facies conditions can contain several wt% TiO2, most of which is incorporated as VITi. This observation aligns with major element trends in these garnets. In natural garnets grown at lower temperatures and pressures, on the other hand, Ti is observed to occupy both the octahedral and tetrahedral sites in garnet-in some cases Ti is almost entirely fourfold coordinated. Combined with previous research (see Ackerson et al. 2017, this issue) on substitution mechanisms for VITi, the results of this study demonstrate that Ti is incorporated on two crystallographic sites in garnet by at least three primary substitution mechanisms. In both natural and synthetic garnets, there is a discernible increase in VITi content in garnet with increasing temperature and pressure, suggesting a significant role for these two parameters in determining Ti solubility. However, a continuous increase in VITi with increasing grossular content also suggests that the Ca content of the garnet plays a critical role. [ABSTRACT FROM AUTHOR]