In situ Ta L 3 -edge XAS measurements have been made from a Ta (~1400ppm)-bearing peraluminous silicate glass+H 2 O system to 960 o C and ~0.6GPa. A white-line doublet separated by ~4eV occurs in the Ta L 3 -edge XANES and results from octahedral crystal field splitting of the Ta 5d levels due to the local structure surrounding Ta coordinated by Q n -species (n=number of bridging oxygen atoms shared between SiO 4 and AlO 4 units) in the silicate glass/melt+H 2 O system. The XANES spectra measured from the hydrous silicate glass/melt and from the silicate-rich aqueous fluid have been analyzed using multi-peak fitting techniques. The white-line doublet intensity varies with increasing P-T conditions of the silicate glass/melt+water system, indicating a shift in the electronic density of states in the vicinity of quasi bound Ta 5d states probed by the 2p 3 / 2 core photoelectron. Ab initio modeling of the XANES indicates that water dissolution causes distortion of local structure surrounding the 6-fold coordinated Ta-Q n clusters in the hydrous silicate glass/melt and in the silicate-rich aqueous fluid. Calculation of the angular-momentum projected density of states (l-DOS) shows that the upper doublet level quasi-bound d-DOS is steadily reduced with increasing distortion of the local structure surrounding Ta-Q n clusters.