Exploration of driving mechanisms of equilibrium boron isotope fractionation in tourmaline group minerals and fluid: A density functional theory study

The equilibrium boron isotope fractionations (alpha(3-4), Delta B-11((Tur-fluid))) between tourmaline mineral groups and fluids at 0.5 GPa, 600-1000 K are investigated using density functional theory calculations. The first solvent shell controls boron isotope fractionation in solution, where the beta values of both H3BO3 and B(OH)(4)(-) decrease with increasing numbers of hydrogen bonds. In supercritical fluids, the weakening of hydrogen bonds and the diversity in configurations of hydrated boron species both contribute to variations in the vibrational frequencies. The 1000ln alpha(Tur-fluid) value increases with increasing Mg/(Fe + Mg) ratios in the dravite-schorl solid solution series. This effect, together with the crystallization sequence predicted from the Gibbs free energies of tourmaline formation, accounts well for the association of boron isotope and chemical zonation observed in zoned tourmaline grains. The dependence of boron isotope fractionation on the B-O bond length in tourmaline group minerals reflects the changes in relevant molar volumes caused by differences in the mass and charge of the atoms occupying the X, Y, and Z sites of tourmalines. This study suggests that the chemical composition of the tourmaline plays an important role in controlling the boron isotope composition in tourmalines crystallized from hydrothermal systems.