Iron and manganese in oxide minerals and in glasses: preliminary consideration of Eh buffering potential at Yucca Mountain, Nevada

The tuffs of Yucca Mountain at the Nevada Test Site are currently under investigation as a possible deep burial site for high-level radioactive waste disposal. One of the main concerns is the effect of oxidizing groundwater on the transport of radionuclides. Rock components that may affect the oxygen content of groundwater include Fe-Ti oxides, Mn oxides, and glasses that contain ferrous iron. Some phenocryst Fe-Ti oxides at Yucca Mountain are in reduced states, whereas groundmass Fe-Ti oxides have been oxidized to hematite, rutile, and pseudobrookite (Fe{sup 3+}-bearing phases) exclusively. Estimates of Fe{sup 2+}-bearing oxides indicate that less than 0.33 vol% phenocrysts is available to act as solid buffering agents of Eh. Of this percentage, significant amounts of Fe-Ti oxides are isolated from effective interaction with groundwater because they occur in densely welded, devitrified tuffs that have low interstitial permeability. Manganese oxides occur primarily along fractures in the ash-flow tuffs. Because the Mn oxides are concentrated along the same pathways (fractures) where transport has occurred in the past, these small volume percentages could act as buffers. However, the oxidation states of actual Mn-oxide phases are high (Mn{sup 4+}), and these minerals have virtually no potential for reducing groundwater Eh. Manganese oxides may even act as oxidizing agents. However, regardless of their poor capabilities as reducing agents, the Mn oxides could be important as sorbents of heavy metals at Yucca Mountain. The lack of accessible, pristine Fe-Ti oxides and the generally high oxidation states of Mn oxides seem to rule out these oxides as Eh buffers of the Yucca Mountain groundwater system. Reduction of ferrous iron within glassy tuffs may have some effect on Eh, but further study is needed. At present it is prudent to assume that minerals and glasses have little or no capacity for reducing oxygen-rich groundwater at Yucca Mountain. 25 refs., 3 figs., 12 tab

Review of the thermal stability and cation exchange properties of the zeolite minerals clinoptilolite, mordenite, and analcime; applications to radioactive waste isolation in silicic tuff

Silicic tuffs of the southern Great Basin and basalts of the Columbia River Plateau are under investigation as potential host rocks for high- and intermediate-level radioactive wastes. Nonwelded and partially welded tuffs may contain major amounts (> 50%) of the zeolite minerals clinoptilolite, mordenite, and analcime. Densely welded tuffs and some basalt flows may contain clinoptilolite as fracture filling that limits the permeability of these rocks. The cation exchange properties of these zeolite minerals allow them to pose a formidable natural barrier to the migration of cationic species of various radionuclides in aqueous solutions. However, these minerals are unstable at elevated temperatures and at low water-vapor pressures and may break down either by reversible dehydration or by irreversible mineralogical reactions. All the breakdown reactions occurring at increased temperature involve a net volume reduction and evolution of fluids. Thus, they may provide a pathway (shrinkage fractures) and a driving force (fluid pressure) for release of radionuclides to the biosphere. These reactions may be avoided by keeping zeolite-bearing horizons saturated with water and below about 85{sup 0}C. This may restrict allowable gross thermal loadings in waste repositories in volcanic rocks

Further description of the petrology of the Topopah Spring member of the paintbrush tuff in drill holes UE25A-1 and USW-G1 and of the lithic-rich tuff in USW-G1, Yucca Mountain, Nevada

The Topopah Spring Member of the Paintbrush Tuff and the Lithic-rich tuff and two Tertiary volcanic units that occur in cores from drill holes UE25a-1 and USW-G1 at Yucca Mountain, Nevada. Recently they have been suggested as possibly suitable for the permanent storage of high-level radioactive waste. Earlier petrologic characterization of these units is augmented here. The Topopah Spring Member (approximately 350 m thick) has two compound cooling units. The upper, thinner unit is densely welded to vitrophyric. The lower unit ranges from nonwelded to vitrophyric, and its nonwelded base is extensively zeolitized to clinoptilolite and mordenite. Heulandite occurs as fracture fill in the overlying vitrophyric part, but zeolites are absent above that vitrophyre. Here primary devitrification plus vapor-phase crystallization dominate the mineralogy. Vapor-phase effects are especially prominent between the two vitrophyres in both cores and include numerous large lithophysal cavities throughout most of this moderately to densely welded tuff. The Lithic-rich tuff extends from 1203 to 1506 m in the USW-G1 drill core. It is nonwelded to partly welded but is well indurated due to pervasive intergrowths of authigenic minerals. These phases are analcime, albite, alkali feldspar, sericite, chlorite and quartz. The transition from analcime to secondary albite corresponds to Iijima`s zeolite Zone IV boundary, and this boundary appears in USW-G1 at 1326 m. However, analcime remains as a prominent phase through most of the Lithic-rich tuff. Further work is necessary to assess the suitability of either of these horizons for a waste repository. In the Topopah Spring Member, both mechanical and hydrologic properties of thick lithophysal zone must be studied, as well as the complete sequence of fracture fill. For both units, zeolite and clay mineral stabilities need to be investigated