Challenges to rutile-based geoscientific tools: low-temperature polymorphic TiO(2) transformations and corresponding reactive pathways

Rutile, a common accessory mineral in a wide variety of rocks, is the most stable naturally occurring TiO(2) polymorph. The relationship between its trace element composition and formation conditions has provided geoscientists with discriminant tools for fingerprinting geological processes, such as magmatic evolution and subduction zone metamorphism, alongside applications to the study of sediment provenance. In the present work, volcaniclastic rock samples belonging to Fara and Saiq Formations, outcropping in Jebel Akhdar mountains, Oman, are studied with Raman spectroscopy and Electron Microprobe (EMP) aiming: of (i) the identification of different naturally-occurring TiO(2) polymorphs, (ii) the evaluation of their trace element contents in relation with hydrothermal alteration features, and (iii) the analysis of the mineral reactive pathways behind the observed textural relationships. Raman investigations demonstrated that interstitial, fine-grained TiO(2) corresponds to anatase, whereas rutile occurs as isolated single grains. EMP determinations further revealed that an identified Nb-enrichment in anatase is coupled with a corresponding Nb-depletion in rutile. The combination of the obtained results with petrographic observations enabled unravelling the TiO(2) reactive pathways affecting the studied samples. Thus, a coupled polymorphic dissolution-precipitation reaction assisting rutile-to-anatase conversion has been defined, together with the role of Nb in further stabilizing the structure of the lower temperature polymorph. Semi-quantitative thermometric considerations suggest that rutile substrates are likely of magmatic origin, whereas anatase formation is clearly associated with a lower temperature aqueous environment. The gathered results raise fundamental questions concerning the application of commonly used rutile-based geochemical and thermometric tools.