Major element and oxygen isotope geochemistry of vapour-phase garnet from the Topopah Spring Tuff at Yucca Mountain, Nevada, USA

Twenty vapour-phase garnets were studied in two samples of the Topopah Spring Tuff of the Paintbrush Group from Yucca Mountain, in southern Nevada. The Miocene-age Topopah Spring Tuff is a 350 m thick, devitrified, moderately to densely welded ash-flow tuff that is zoned compositionally from high-silica rhyolite to latite. During cooling of the tuff, escaping vapour produced lithophysae (former gas cavities) lined with an assemblage of tridymite (commonly inverted to cristobalite or quartz), sanidine and locally, hematite and/or garnet. Vapour-phase topaz and economic deposits associated commonly with topaz-bearing rhyolites (characteristically enriched in F) were not found in the Topopah Spring Tuff at Yucca Mountain. Based on their occurrence only in lithophysae, the garnets are not primary igneous phenocrysts, but rather crystals that grew from a F-poor magmaderived vapour trapped during and after emplacement of the tuff. The garnets are euhedral, vitreous, reddish brown, trapezohedral, as large as 2 mm in diameter and fractured. The garnets also contain inclusions of tridymite. Electron microprobe analyses of the garnets reveal that they are almandinespessartine (48.0 and 47.9 mol.%, respectively), have an average composition of (Fe1.46Mn1.45Mg0.03Ca0.10)(Al1.93Ti0.02)Si3.01O12and are comparatively homogeneous in Fe and Mn concentrations from core to rim. Composited garnets from each sample site have δ18O values of 7.2 and 7.4%. The associated quartz (after tridymite) has δ18O values of 17.4 and 17.6%, values indicative of reaction with later, low-temperature water. Unaltered tridymite from higher in the stratigraphic section has a δ18O of 11.1% which, when coupled with the garnet δ18O values in a quartz-garnet fractionation equation, indicates isotopic equilibration (vapour-phase crystallization) at temperatures of ∼600°C. This high-temperature mineralization, formed during cooling of the tuffs, is distinct from the later and commonly recognized low-temperature stage (generally 50−70°C) of calcite, quartz and opal secondary mineralization, formed from downward-percolating meteoric water, that locally coats fracture footwalls and lithophysal floors.

Evaporative Evolution of Carbonate-Rich Brines from Synthetic Topopah Spring Tuff Pore Water, YuccaMountain, NV

The evaporation of a range of synthetic pore water solutions representative of the potential high-level-nuclear-waste repository at Yucca Mountain, NV is being investigated. The motivation of this work is to understand and predict the range of brine compositions that may contact the wastecontainers from evaporation of pore waters, because these brines could form corrosive thin films on the containers and impact their long-term integrity. A relatively complex synthetic Topopah Spring Tuff pore water was progressively concentrated by evaporation in a closed vessel, heated to 95°C in a series of sequential experiments. Periodic samples of the evaporating solution were taken to determine the evolving water chemistry. According to chemical divide theory at 25°C and 95°C our starting solution should evolve towards a high pH carbonate brine. Results at 95°C show that this solution evolves towardsa complex brinethat contains about 99 mol% Na+for the cations, and 71 mol% Cl-, 18 mol% ΣCO2(aq), 9 mol% SO42- for the anions. Initial modeling ofthe evaporating solution indicates precipitation of aragonite, halite, silica, sulfate and fluoride phases. The experiments have been used to benchmark the use of the EQ3/6 geochemical code in predicting the evolution of carbonate-rich brines during evaporation.