Hydrogen isotope fractionation inside silicate melts and glasses studied by 1H and 2H MAS NMR spectroscopy – Molecular insights into deuterium exchange at the melt-fluid interface

Abstract Hydrogen isotope ratios (D/H) measured on geological samples are used to trace the pathways of water in magmatic and hydrothermal systems. Interpreting respective isotope data relies thereby on the theoretical and empirical constraints on hydrogen isotope fractionation. This study revisits a recently discovered hydrogen isotope fractionation effect between alkali-rich and alkali-poor regions within hydrous alkali silicate melts (Wang et al., 2015). In a series of experiments conducted at variable P-T-XH2O, D2O conditions, we studied this intramolecular isotope effect by 1H and 2H solid-state nuclear magnetic resonance (NMR) spectroscopy on quenched hydrous sodium tetrasilicate melts (Na2O⋅4SiO2 with 1:1 H2O and D2O). The results indicate a marked difference in the reactivity of the protonated and deuterated hydrous species. It is observed that c. 70% of deuterium concentrates as deuterated silanols (Si-OD) in proximity to the sodium cations in the silicate melt structure, while the remaining 30% occupy the Na-poor regions in the silicate melt in the form of Si-OD and presumably molecular water (HDOm). This distribution remains nearly constant under all experimental conditions. In contrast, the concentration of protonated hydrous species (Si-OH, H2Om) in the Na-rich and -poor regions of the silicate melt varies as a response to changing experimental P-T-XH2O and cooling rate, which is linked to common water speciation reactions taking place within the melt (Si-O-Si + H2Om = 2Si-OH). Previously considered insignificant, 1H NMR indicates that the speciation equilibrium is sensitive to pressure and correlates positively with Si-OH concentration. The significantly different reactivity of the isotope substituted hydrous species results in large molecular variations in the D/H ratio inside the sodium silicate melt. Measured intramolecular hydrogen isotope fractionation yields a 2- to 9-fold (in average 3-fold) enrichment of deuterium in Na-rich depolymerized regions in the silicate network, which translates to intramolecular fractionations of 1000ln(α) = 400 to 2200. Generally, intramolecular fractionation tends to increase when the melt evolves towards fluid-saturated conditions. The pre-concentration of deuterium in the depolymerized Na-rich regions of the silicate melt results in a higher local D/H ratio that may carry over when these regions disintegrate into a silicate saturated aqueous fluid. In this way, intramolecular isotope fractionation poses a potent way of enriching silicate saturated aqueous fluids in deuterium, potentially explaining previous experimental in-situ observations of large hydrogen isotope fractionations in the hydrous-melt – silicate-saturated fluid system. The observed affinity of deuterium to combine with alkali-associated silanols could comprise an important molecular sieving mechanism for deuterium that enhances the D/H fractionation between silicate-rich fluids (and hydrous melts) and the surrounding host rock. Consequently, intramolecular hydrogen isotope fractionation in hydrous silicate melts and silicate-rich aqueous fluids may be a very effective deuterium filter acting in the deep geological water cycle.