Tracing the deep geological water cycle requires knowledge of the hydrogen isotope systematics between and within hydrous materials. For quenched hydrous alkali-silicate melts, hydrogen NMR reveals a distinct heterogeneity in the distribution of stable hydrogen isotopes (D, H) within the silicate tetrahedral network, where deuterons concentrate strongly in network regions that are associated with alkali cations. Previous hydrogen NMR studies performed in the sodium tetrasilicate system (Na2O x 4SiO2, NS4) with a 1:1 D2O/H2O ratio showed on average 1300 %o deuterium enrichment in the alkali-associated network, but the effect on varying bulk D2O/ H2O ratios on this intramolecular isotope effect remained unconstrained. Experiments in the hydrous sodium tetrasilicate system with 8 wt% bulk water and varying bulk D2O/H2O ratios were performed at 1400 degrees C and 1.5 GPa. It is found that both hydrogen isotopes preferably partition into the silicate network that is associated with alkali ions. The partitioning is always stronger for the deuterated than for the protonated hydrous species. The relative enrichment of deuterium over protium in the alkali-associated network, i.e., the intramolecular isotope effect, correlates positively with the D2O/H2O bulk ratio of the hydrous NS4 system. Modeled for natural deuterium abundance (D/H near 1.56 x 10-4), a 1.4-fold (c. 340 %o) deuterium enrichment in the alkaliassociated silicate network is predicted. The partitioning model further predicts a positive correlation between the bulk water content of the silicate melt and the intramolecular deuterium partitioning into the alkaliassociated silicate network. Such heterogeneities may explain the magnitude and direction of hydrogen isotope fractionation in hydrous silicate melts coexisting with silicate-saturated fluids. As such, this intramolecular isotope effect appears to be an effective mechanism for deuterium separation, particularly in hydrous magmatic settings, such as subduction zones.