TiO2 exsolution from garnet by open-system precipitation: evidence from crystallographic and shape preferred orientation of rutile inclusions

Abstract

We investigated rutile needles with a clear shape preferred orientation in garnet from (ultra) high-pressure metapelites from the Kimi Complex of the Greek Rhodope by electron microprobe, electron backscatter diffraction and TEM techniques. A definite though complex crystallographic orientation relationship between the garnet host and rutile was identified in that Rt[001] is either parallel to Grt or describes cones with opening angle 27.6° around Grt . Each Rt[001] small circle representing a cone on the pole figure displays six maxima in the density plots. This evidence together with microchemical observations in TEM, when compared to various possible mechanisms of formation, corroborates a precipitate origin. A review of exchange vectors for Ti substitution in garnet indicates that rutile formation from garnet cannot occur in a closed system. It requires that components are exchanged between the garnet interior and the rock matrix by solid-state diffusion, a process we refer to as “open-system precipitation” (OSP). The kinetically most feasible reaction of this type will dominate the overall process. The perhaps most efficient reaction involves internal oxidation of Fe2+ to Fe3+ and transfer from the dodecahedral to the octahedral site just vacated by $$ {\text{Ti}}^{ 4+ }: 6\,{\text{M}}^{ 2+ }_{ 3} {\text{TiAl}}\left[ {{\text{AlSi}}_{ 2} } \right]{\text{O}}_{ 1 2} + 6\,{\text{M}}^{ 2+ }_{ 2, 5} {\text{TiAlSi}}_{ 3} {\text{O}}_{ 1 2} = 10\,{\text{M}}^{ 2+ }_{ 3.0} {\text{Al}}_{ 1. 8} {\text{Fe}}_{0. 2} {\text{Si}}_{ 3} {\text{O}}_{ 1 2} + {\text{M}}^{2+} + 2 {\text{e}}^{-} + 1 2\,{\text{TiO}}_{ 2} . $$ OSP is likely to occur at conditions where the transition of natural systems to open-system behaviour becomes apparent, as in the granulite and high-temperature eclogite facies.