An understanding of the mechanisms responsible for controlling the long-term corrosion rate of nuclear waste glass is paramount if reliable glass dissolution models are to be used to calculate the controlled release of radionuclides from nuclear waste glass under geologic disposal conditions. Understanding the mechanism that controls silicate glass dissolution rates is also important for natural glasses to understand the role from the dissolution of these glasses has on the composition of natural aquatic systems. Two general mechanisms appear to be responsible for the elemental release from glass to the surrounding biosphere – ion exchange (release principally of alkalis) and matrix dissolution (release of the structural components of the glass). Key unknowns related to these mechanisms are the impact of surface layers on the altered glass and how these layers participate in corrosion. To better understand the impact of these layers on the long-term glass corrosion rate, we made two glasses of the same elemental composition, but with selected elements enriched in specific isotopes for B (11B), Li (6Li), and Si (29Si). We reacted these glasses for 1 y then the solutions from each were exchanged and the chemistry of the solutions and the solids were followed for another 2 y (a total of 3 y). This allowed us to follow changes in the glasses with respect to these elements and how these elements were transported through the alteration layers with time and, for at least one element, into the glass and to deconvolute some competing kinetic steps, such as matrix dissolution and ion exchange. Results from these experiments demonstrate that the release behavior of different elements is strongly dependent on their structural role in the glass (e.g. network formers and modifiers), but, more importantly, the role of water transport and subsequent ion exchange has in the long-term dissolution of the glass studied here. In this article, we highlight the behavior of four elements: lithium, sodium, silicon, and boron. Lithium and sodium, network modifying elements, have similar chemistries. The behavior of Li could be tracked in more detail by following both 6Li and 7Li; Li penetrates through the gel layer in both directions without hinderance and is released from the glass deeper than Na. Silicon, a network forming element, reacts with the silica-rich alteration layer. Boron, a network forming element, does not accumulate in the gel or the pristine glass and has a very sharp elemental profile between the pristine glass and alteration layer. Boron, lithium, and sodium elemental profiles suggest that there is little if any transport control within the alteration layer. These results are similar to those found for basalt glass. However, the correlation between the Li and Na profiles and that of a water species suggest that the limiting release is not controlled by the formation of the gel but rather is a steady state between the diffusion of a water species and matrix dissolution that results in a low release rate for alkali and this provides a steady driving force for the long-term dissolution of glass.