The diffusion of molecular water (H2Om) from the environment into volcanic glass can hydrate the glass up to several wt% at low temperature over long timescales. During this process, the water imprints its hydrogen isotope composition (δDH2O) to the glass (δDgl) offset by a glass-H2O fractionation factor (ΔDgl-H2O = δDgl – δDH2O) which is approximately -33‰ at Earth surface temperatures. Glasses hydrate much more rapidly at higher, sub-magmatic temperatures as they interact with H2O during eruption, transport, and emplacement. To aid in the interpretation of δDgl in natural samples, we present hydrogen isotope results from vapor hydration experiments conducted at 175–375 oC for durations of hours to months using natural volcanic glasses. The results can be divided into two thermal regimes: above 250 oC and below 250 oC. Lower temperature experiments yield raw ΔDgl-H2O values in the range of -33 ± 11‰. Experiments at 225 oC using both positive and negative initial ΔDgl-H2O values converge on this range of values, suggesting this range represents the approximate equilibrium fractionation for H isotopes between glass and H2O vapor (103lnαgl-H2O) below 250 oC. Variation in ΔDgl-H2O (-33 ± 11‰) between different experiments and glasses may arise from incomplete hydration, analytical uncertainty, differences in glass chemistry, and/or subordinate kinetic isotope effects. Experiments above 250 oC yield unexpectedly low δDgl values with ΔDgl-H2O values of ≤–85‰. While alteration alone is incapable of explaining the data, these run products have more extensive surface alteration and are not interpreted to reflect equilibrium fractionation between glass and H2O vapor. Fourier transform infrared spectroscopy (FTIR) shows that glass can hydrate with as much as 5.9 wt% H2Om and 1.0 wt% hydroxl (OH-) in the highest P-T experiment at 375 oC and 21.1 MPa. Therefore, we employ a 1D isotope diffusion– reaction model of glass hydration to evaluate the roles of equilibrium fractionation, isotope diffusion, water speciation reactions internal to the glass, and changing boundary conditions (e.g. alteration and dissolution). At lower temperatures, the best fitting model results to experimental data for low silica rhyolite (LSR) glasses require only an equilibrium fractionation factor and yield 103lnαgl-H2O values of -33‰± 5‰and -25‰± 5‰at 175 oC and 225 oC, respectively. At higher temperatures, ΔDgl-H2O is dominated by boundary layer effects during glass hydration and glass surface alteration. The modeled bulk δDgl value is highly responsive to changes in the δDgl boundary condition regardless of the magnitude of other kinetic effects. Observed glass dissolution and surficial secondary mineral formation are likely to impose a disequilibrium boundary layer that drives extreme δDgl fractionation with progressive glass hydration. These results indicate that the observed ΔDgl-H2O of ~-33 ± 11‰ can be cautiously applied as an equilibrium 103lnαgl-H2O value to natural silicic glasses hydrated below 250 oC to identify hydration sources. This approximate ΔDgl-H2O may be applicable to even higher temperature glasses hydrated on short timescales (of seconds to minutes) in phreatomagmatic or submarine eruptions before H2O in the glass is primarily affected by boundary layer effects associated with alteration on the glass surface
