Equilibrium oxygen isotope fractionations have been extensively studied between H2O and minerals (like brucite-type hydroxides) in isotope geochemistry. In this study, pure 18O-enriched hydroxides were synthesized through reactions between M3N2 (M = Mg and Ca) powders and H218O water. In situ high-temperature (T) and high-pressure (P) Raman and Fourier transform infrared (FTIR) spectra were systematically collected for these phases. The observed 18O-16O effect on the frequency shifts aligns with the theoretical model, and has little impact on the anharmonic O-H potential well. The calculated intrinsic anharmonic parameters (ai) for both lattice and OH-stretching modes are essentially identical between M(16OH)2 and M(18OH)2, satisfying the classical limit for the Helmholtz free energy at extremely high temperature. Based on the measured vibrational data, the equilibrium oxygen isotope fractionation β(T,P) factors were modeled for both hydroxides. Both the intrinsic and external anharmonic contributions are smaller than the experimental uncertainties, and this model is also validated by ab initio calculation. Next, the 103·lnα(T) profiles were computed between brucite/portlandite and H2O, which are consistent with the reported oxygen isotope exchange measurements above 200 °C. Additionally, the discrepancy between this equilibrium model and the precipitation experiment below 120 °C also provides useful information for investigating the mechanism of kinetic isotope fractionation. The predicted 103·lnαbrucite-portlandite(T) curve also agrees well with points inferred from the 18O-16O exchange measurements, while the pressure effect can be ignored for 18O-16O fractionations. Therefore, vibrational spectroscopic measurements, including both Raman and infrared spectroscopies, have valuable applications in studying equilibrium non-metallic isotope fractionations in minerals.

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