Magic Angle Spinning Nuclear Magnetic Resonance (MAS-NMR) spectroscopy has been used to characterize the structural and chemical environments of B, Al, and Si in model Hanford low-activity waste glasses. The average 29Si NMR peak position was found to systematically change with changing glass composition and structure. From an understanding of the structural roles of Al and B obtained from MAS-NMR experiments, we first developed a model that reliably predicts the distribution of structural units and the average 29Si chemical shift value, δ, based purely on glass composition. A product consistency test (PCT) was used to determine the normalized elemental release (NL) from the prepared glasses. Comparison of the NMR and PCT data obtained from sodium boro-aluminosilicate glasses indicates that a rudimentary exponential relationship exists between the 29Si chemical shift value, and the boron NL value.