Alteration layers developed on SRL-165 simulated waste glasses in dilute sodium silicate/bicarbonate leaching solutions have been examined by Secondary Ionization Mass Spectrometry (SIMS) using fine-scale, multiple-element depth profiling. Selected samples were examined with an imaging detector system, which demonstrated the horizontal homogeneity of the layer development at all depths within the layer. After 1 day of reaction at 90°C the reaction layer shows depletion of glass elements to a depth of 0.2 μm. The surface of the layer in contact with the solution shows enrichment of Si, Al, and alkali elements even at this short reaction time, suggesting the early stages of development of secondary aluminosilicate phases. With increased reaction time, the layer thickens to about 1.3 μm at 91 days, while the evidence for aluminosilicate development at the surface of the layer becomes more prominent. Penetration of hydrogen into the “unreacted” glass proceeds to a depth of about 0.5 μm deeper than the alkali depletion zone. This suggests the mechanism of initial reaction of the glass is by attack of the silicate structure by molecular water or hydroxide ion rather than by alkali-hydrogen ion exchange. The simple structure of the layers developed in the silicate solution is in contrast to the complexity of layer structure found when glasses are reacted in deionized water. Since the conditions for geologic disposal will be closer to those used in the silicate leaching experiments, these results hold promise for the ability to model the system to predict long-term performance after disposal in a repository.