An immediate EM science need is a reliable kinetic model that predicts long-term waste glass performance. A framework for which the kinetics of mineral-solution reactions can be used to interpret complex silicate glass properties is required to accurately describe the current and future behavior of glasses as synthetic monoliths or natural analogs. Reaction rates and mechanisms are essential elements in deciphering mineral/material reactivity trends within a compositional series or across a matrix of complex solution compositions. An essential place to start, and the goal of this research, 2 is to quantify the reactivity of crystalline and amorphous SiO 2 phases in the complex fluids of natural systems.Perhaps the most important motivation for quantifying SiO 2 reactivity in subsurface environments is that an understanding of fundamental controls on the reactivity of simple Si-O bonded phases establishes baseline behavior for silica phases widely found in waste storage environments. Host rock silicate minerals dominate virtually every repository rock-water system. Further, complex silicate glasses will be the frontline of defense in containing radioactive wastes in both interim and long-term storage strategies. However, we have little quantitative understanding of pure SiO 2 reactivity in the solutes of natural and perturbed groundwaters even though current EM strategy calls for dispersal of waste into silica-based glass materials. Findings will establish quantitative relationships between silica reactivity and complex solution chemistries never investigated which are presently speculative at best. Further, we will be able to uncover underlying principles that govern how solutes affect silica reactivity in a systematic and predictable way.
FINAL REPORT OF FINDINGS:The new research project was initiated on February 1, 2001 and has now been completed. We focused the funding on the costly experimental work rather than extensive travel. In the end, our efforts paid off with findings in all aspects of the research activities that have been described by others as "transformational".A particularly exciting outcome is the paper recently published in Dove et al. We show that seemingly disparate data sets and dissolution regimes can be unified within a single model by analyzing mineral dissolution using the same physical 3 picture used for crystal growth. In fact, our work found that the entire spectrum of growth and dissolution can be viewed within a single continuum, in which transitions from one dominant mechanism to another are determined by a single, simple consideration, namely which one produces the greatest step density. This tour de force was recently highlighted by both Science and Elements, in their Editor's Choice articles for its significance.Owing to the breakthrough in the PNAS paper, we realized a new mechanismbased way of understanding glasses. This was part of our original goal for the EMSP project and has taken some time, but is still forthcoming. Again, thanks to the support of this project, we are abo...