Constraints on Titanite Acitvity in the System CaTiSiO4O-CaAlSiO4F: Implications for Thermobarometry in Metamorphic Rocks

Titanite is a common accessory mineral that could be used reliably in phase equilibrium calculations, if activity-composition relations in Al-F titanites were known. Troitzsch and Ellis (2001, CMP, 142, 543) and Tropper et al. (2002, JPet., 43, 1787) gave non-ideal mixing models along the join CaTiSiO4O- CaAlSiO4F. Tropper et al. (2002) derived a negative interaction parameter W, whereas Troitzsch and Ellis (2001) derived a regular model with both positive and negative W, but favored positive values. These differences strongly influence calculated CaTiSiO4O activity (attn). Although more experiments are needed, our result that γttn<1 at high T indicates a large degree of non-ideal behavior, even at >900°C, which in turn will affect thermobarometry. Comparing available activity models shows that at these T, attn is substantially underestimated by the fully ionic model used by Manning and Bohlen (1991, CMP, 109, 1), in which attn = XCaXTiXSi(XO)5. This model assumes independent mixing of Al for Ti and random mixing of F and O on all O sites. However, F substitutes only in one O site (O1; Oberti et al., 1991, EJM, 3, 777). A fully ionic model should therefore be recast as attn = XCaXTiXSiXO, where XO indicates the mole fraction of O on the (O1) site. The substitution of F on the O1 site is coupled with Al, so it is called the ideal coupled model. Unlike the regular model, the prefered ionic model departs strongly from ideality at ≤600°C, consistent with independent constraints. However, experimentally determined attn is approximated by an ideal molecular model (XTi) at ≥900°C, so this model is recommended for thermobarometry in high- T metamorphic rocks until more data are available. Recalculation of the P recorded by the three eclogites from Manning and Bohlen (1991) using the different activity models discussed here yields differences that may be as high as 2.0 GPa.