Applied Geochemistry (v.17, #6)

Current Lit Survey (III-VII).

by Mel Gascoyne; Zell E. Peterman (657).

The geohydrologic setting of Yucca Mountain, Nevada by John S. Stuckless; William W. Dudley (659-682).
This paper provides a geologic and hydrologic framework of the Yucca Mountain region for the geochemical papers in this volume. The regional geologic units, which range in age from late Precambrian through Holocene, are briefly described. Yucca Mountain is composed of dominantly pyroclastic units that range in age from 11.4 to 15.2 Ma. The principal focus of study has been on the Paintbrush Group, which includes two major zoned and welded ash-flow tuffs separated by an important hydrogeologic unit referred to as the Paintbrush non-welded (PTn). The regional structural setting is currently one of extension, and the major local tectonic domains are presented together with a tectonic model that is consistent with the known structures at Yucca Mountain. Streamflow in this arid to semi-arid region occurs principally in intermittent or ephemeral channels. Near Yucca Mountain, the channels of Fortymile Wash and Amargosa River collect infrequent runoff from tributary basins, ultimately draining to Death Valley. Beneath the surface, large-scale interbasin flow of groundwater from one valley to another occurs commonly in the region. Regional groundwater flow beneath Yucca Mountain originates in the high mesas to the north and returns to the surface either in southern Amargosa Desert or in Death Valley, where it is consumed by evapotranspiration. The water table is very deep beneath the upland areas such as Yucca Mountain, where it is 500–750 m below the land surface, providing a large thickness of unsaturated rocks that are potentially suitable to host a nuclear-waste repository. The nature of unsaturated flow processes, which are important for assessing radionuclide migration, are inferred mainly from hydrochemical or isotopic evidence, from pneumatic tests of the fracture systems, and from the results of in situ experiments. Water seeping down through the unsaturated zone flows rapidly through fractures and more slowly through the pores of the rock matrix. Although capillary forces are expected to divert much of the flow around repository openings, some may drip onto waste packages, ultimately causing release of radionuclides, followed by transport down to the water table.

The compositional variability of the phenocryst-poor member of the 12.8 Ma Topopah Spring Tuff at the potential repository level was assessed by duplicate analysis of 20 core samples from the cross drift at Yucca Mountain, Nevada. Previous analyses of outcrop and core samples of the Topopah Spring Tuff showed that the phenocryst-poor rhyolite, which includes both lithophysal and nonlithophysal zones, is relatively uniform in composition. Analyses of rock samples from the cross drift, the first from the actual potential repository block, also indicate the chemical homogeneity of this unit excluding localized deposits of vapor-phase minerals and low-temperature calcite and opal in fractures, cavities, and faults. The possible influence of vapor-phase minerals and calcite and opal coatings on rock composition at a scale sufficiently large to incorporate these heterogeneously distributed deposits was evaluated and is considered to be relatively minor. Therefore, the composition of the phenocryst-poor member of the Topopah Spring Tuff is considered to be adequately represented by the analyses of samples from the cross drift. The mean composition as represented by the 10 most abundant oxides in wt.% or g/100 g is: SiO2, 76.29; Al2O3, 12.55; FeO, 0.14; Fe2O3, 0.97; MgO, 0.13; CaO, 0.50; Na2O, 3.52; K2O, 4.83; TiO2, 0.11; and MnO, 0.07.

Mineralogical heterogeneity in fractured, porous media and its representation in reactive transport models by William E. Glassley; Ardyth M. Simmons; James R. Kercher (699-708).
Reactive transport models that simulate processes in porous media have, generally, required abstracted representation of porosity, permeability, and mineralogy. This study compares abstracted, homogeneous representations of porosity and permeability, mineral surface areas and distributions, to discrete distribution representation of these same properties. Discretization was accomplished by high-resolution (ca. 1 μm2) characterization of fractured tuffaceous rock from Yucca Mountain, Nevada, using optical microscopy and X-ray fluorescence spectroscopy. A sample area of 106 μm2 was mapped in detail, and the resulting element and porosity maps were digitized. The domain was decomposed into 12,208 cells that were 8.77 × 10−6 m on a side. Simulations were conducted in which a dilute fluid enters the discretized porous medium at modest flow rates. Simulation results using a discrete mineral distribution point to the conclusion that slow flow rates, in which fluid residence times are on the order of days, provide fluid composition results that are very similar to those obtained from the homogeneous mineral distribution representation. At higher flow rates, where fluid residence times are on the order of hours, contrasts in fluid composition persist throughout the flow domain. The results demonstrate that the fluid composition characteristics in the homogeneous and discrete mineral representations will be similar only when the bulk average contact times for the individual mineral phases along the flow paths are approximately equivalent (within a few percent) for the two cases.

Uranium, Th and Pb isotopes were analyzed in layers of opal and chalcedony from individual mm- to cm-thick calcite and silica coatings at Yucca Mountain, Nevada, USA, a site that is being evaluated for a potential high-level nuclear waste repository. These calcite and silica coatings on fractures and in lithophysal cavities in Miocene-age tuffs in the unsaturated zone (UZ) precipitated from descending water and record a long history of percolation through the UZ. Opal and chalcedony have high concentrations of U (10 to 780 ppm) and low concentrations of common Pb as indicated by large values of 206Pb/204Pb (up to 53,806), thus making them suitable for U-Pb age determinations. Interpretations of U-Pb isotope systems in opal samples at Yucca Mountain are complicated by the incorporation of excess 234U at the time of mineral formation, resulting in reverse discordance of U-Pb ages. However, the 207Pb/235U ages are much less affected by deviation from initial secular equilibrium and provide reliable ages of most silica deposits between 0.6 and 9.8 Ma. For chalcedony subsamples showing normal age discordance, these ages may represent minimum times of deposition. Typically, 207Pb/235U ages are consistent with the microstratigraphy in the mineral coating samples, such that the youngest ages are for subsamples from outer layers, intermediate ages are from inner layers, and oldest ages are from innermost layers. 234U and 230Th in most silica layers deeper in the coatings are in secular equilibrium with 238U, which is consistent with their old age and closed system behavior during the past ∼0.5 Ma. The ages for subsamples of silica layers from different microstratigraphic positions in individual calcite and silica coating samples collected from lithophysal cavities in the welded part of the Topopah Spring Tuff yield slow long-term average growth rates of 1 to 5 mm/Ma. These data imply that the deeper parts of the UZ at Yucca Mountain maintained long-term hydrologic stability over the past 10 Ma. despite significant climate variations. U-Pb ages for subsamples of silica layers from different microstratigraphic positions in individual calcite and silica coating samples collected from fractures in the shallower part of the UZ (welded part of the overlying Tiva Canyon Tuff) indicate larger long-term average growth rates up to 23 mm/Ma and an absence of recently deposited materials (ages of outermost layers are 3–5 Ma.). These differences between the characteristics of the coatings for samples from the shallower and deeper parts of the UZ may indicate that the nonwelded tuffs (PTn), located between the welded parts of the Tiva Canyon and Topopah Spring Tuffs, play an important role in moderating UZ flow.

Calcite and silica form coatings on fracture footwalls and cavity floors in the welded tuffs at Yucca Mountain, the potential site of a high-level radioactive waste repository. These secondary mineral deposits are heterogeneously distributed in the unsaturated zone (UZ) with fewer than 10% of possible depositional sites mineralized. The paragenetic sequence, compiled from deposits throughout the UZ, consists of an early-stage assemblage of calcite±fluorite±zeolites that is frequently capped by chalcedony±quartz. Intermediate- and late-stage deposits consist largely of calcite, commonly with opal on buried growth layers or outermost crystal faces of the calcite. Coatings on steep-dipping fractures usually are thin (⩽3 mm) with low-relief outer surfaces whereas shallow-dipping fractures and lithophysal cavities typically contain thicker, more coarsely crystalline deposits characterized by unusual thin, tabular calcite blades up to several cms in length. These blades may be capped with knobby or corniced overgrowths of late-stage calcite intergrown with opal. The observed textures in the fracture and cavity deposits are consistent with deposition from films of water fingering down fracture footwalls or drawn up faces of growing crystals by surface tension and evaporated at the crystal tips. Fluid inclusion studies have shown that most early-stage and some intermediate-stage calcite formed at temperatures of 35 to 85 °C. Calcite deposition during the past several million years appears to have been at temperatures <30 °C. The elevated temperatures indicated by the fluid inclusions are consistent with temperatures estimated from calcite δ18O values. Although others have interpreted the elevated temperatures as evidence of hydrothermal activity and flooding of the tuffs of the potential repository, the authors conclude that the temperatures and fluid-inclusion assemblages are consistent with deposition in a UZ environment that experienced prolonged heat input from gradual cooling of nearby plutons. The physical restriction of the deposits (and, therefore, fluid flow) to fracture footwalls and cavity floors and the heterogeneous and limited distribution of the deposits provides compelling evidence that they do not reflect flooding of the thick UZ at Yucca Mountain. The textures and isotopic and chemical compositions of these mineral deposits are consistent with deposition in a UZ setting from meteoric waters percolating downward along fracture flow paths.

234U/238U evidence for local recharge and patterns of ground-water flow in the vicinity of Yucca Mountain, Nevada, USA by James B Paces; Kenneth R Ludwig; Zell E Peterman; Leonid A Neymark (751-779).
Uranium concentrations and 234U/238U ratios in saturated-zone and perched ground water were used to investigate hydrologic flow and downgradient dilution and dispersion in the vicinity of Yucca Mountain, a potential high-level radioactive waste disposal site. The U data were obtained by thermal ionization mass spectrometry on more than 280 samples from the Death Valley regional flow system. Large variations in both U concentrations (commonly 0.6–10 μg l−1) and 234U/238U activity ratios (commonly 1.5–6) are present on both local and regional scales; however, ground water with 234U/238U activity ratios from 7 up to 8.06 is restricted largely to samples from Yucca Mountain. Data from ground water in the Tertiary volcanic and Quaternary alluvial aquifers at and adjacent to Yucca Mountain plot in 3 distinct fields of reciprocal U concentration versus 234U/238U activity ratio correlated to different geographic areas. Ground water to the west of Yucca Mountain has large U concentrations and moderate 234U/238U whereas ground water to the east in the Fortymile flow system has similar 234U/238U, but distinctly smaller U concentrations. Ground water beneath the central part of Yucca Mountain has intermediate U concentrations but distinctive 234U/238U activity ratios of about 7–8. Perched water from the lower part of the unsaturated zone at Yucca Mountain has similarly large values of 234U/238U. These U data imply that the Tertiary volcanic aquifer beneath the central part of Yucca Mountain is isolated from north-south regional flow. The similarity of 234U/238U in both saturated- and unsaturated-zone ground water at Yucca Mountain further indicates that saturated-zone ground water beneath Yucca Mountain is dominated by local recharge rather than regional flow. The distinctive 234U/238U signatures also provide a natural tracer of downgradient flow. Elevated 234U/238U in ground water from two water-supply wells east of Yucca Mountain are interpreted as the result of induced flow from 40 a of ground-water withdrawal. Elevated 234U/238U in a borehole south of Yucca Mountain is interpreted as evidence that natural downgradient flow is more likely to follow southerly paths in the structurally anisotropic Tertiary volcanic aquifer where it becomes diluted by regional flow in the Fortymile system.

Samples of tuff from boreholes drilled into fault zones in the Exploratory Studies Facility (ESF) and relatively unfractured rock of the Cross Drift tunnels, at Yucca Mountain, Nevada, have been analysed by U-series methods. This work is part of a project to verify the finding of fast flow-paths through the tuff to ESF level, indicated by the presence of ‘bomb’ 36Cl in pore fluids. Secular radioactive equilibrium in the U decay series, (i.e. when the radioactivity ratios 234U/238U, 230Th /234U and 226Ra/230Th all equal 1.00) might be expected if the tuff samples have not experienced radionuclide loss due to rock-water interaction occurring within the last million years. However, most fractured and unfractured samples were found to have a small deficiency of 234U (weighted mean 234U/238U=0.95±0.01) and a small excess of 230Th (weighted mean 230Th/234U 1.10±0.02). The 226Ra/230Th ratios are close to secular equilibrium (weighted mean=0.94±0.07). These data indicate that 234U has been removed from the rock samples in the last ∼350 ka, probably by pore fluids. Within the precision of the measurement, it would appear that 226Ra has not been mobilized and removed from the tuff, although there may be some localised 226Ra redistribution as suggested by a few ratio values that are significantly different from 1.0. Because both fractured and unfractured tuffs show approximately the same deficiency of 234U, this indicates that pore fluids are moving equally through fractured and unfractured rock. More importantly, fractured rock appears not to be a dominant pathway for groundwater flow (otherwise the ratio would be more strongly affected and the Th and Ra isotopic ratios would likely also show disequilibrium). Application of a simple mass-balance model suggests that surface infiltration rate is over an order of magnitude greater than the rate indicated by other infiltration models and that residence time of pore fluids at ESF level is about 400 a. Processes of U sorption, precipitation and re-solution are believed to be occurring and would account for these anomalous results but have not been included in the model. Despite the difficulties, the U-series data suggest that fractured rock, specifically the Sundance and Drill Hole Wash faults, are not preferred flow paths for groundwater flowing through the Topopah Spring tuff and, by implication, rapid-flow, within 50 a, from the surface to the level of the ESF is improbable.

The natural waters associated with Yucca Mountain include precipitation (rain and melted snow), ephemeral surface waters, soil waters, vadose zone pore waters, perched waters and saturated zone ground waters. Using precipitation compositions as a starting point, chemical and isotopic data for the other water types are evaluated to identify significant processes that may control their compositions. The ratios of Cl to each of the other major constituents in precipitation waters are used to evaluate gains or losses of major ions in the other waters. Evapotranspiration of precipitation waters in the soil zone appears to be a very important process in the control of vadose zone pore waters, perched waters and saturated zone ground water compositions. In the desert climate associated with the Yucca Mountain site, this process leads to the precipitation of salts and silica in the soil zone. Surface waters sampled near the site have preferentially dissolved soil zone chlorides, sulfates, carbonates, and silica. Pore waters extracted from bedded tuffs of the upper Paint Brush Tuff in Yucca Mountain have ratios of Ca, Na, HCO3 and SO4 to Cl that are all lower than those found in precipitation. The lower ratios likely reflect precipitation of alkaline earth carbonates and possibly sulfates in the soil zone. Pore waters extracted from the Calico Hills Tuff also appear to reflect the precipitation of alkaline earth sulfates in the soil zone. Alternatively, the low SO4 to Cl ratios observed in these waters reflect variations in precipitation compositions with time. Perched waters are more dilute than vadose zone pore waters but appear to have gained their solutes by similar mechanisms. For perched waters, sulfates were dissolved in the soil zone in addition to carbonates and chlorides. The dissolution of the less soluble phases (i.e. alkaline earth carbonates and sulfates) in the soil zone implies perched waters were infiltrated under wetter climatic conditions. Saturated zone waters originated by processes similar to those that formed the perched waters except that the former were subject to more extensive ion exchange reactions. Ground waters in the shallow saturated zone beneath Yucca Mountain appear to include a significant component that was locally infiltrated. Deeper saturated zone waters likely infiltrated further upgradient in the direction of Pahute Mesa.

The percolation flux for borehole USW UZ-14 was calculated from 14C residence times of pore water and water content of cores measured in the laboratory. Transport velocity is calculated from the depth interval between two points divided by the difference in 14C residence times. Two methods were used to calculate the flux and velocity. The first method uses the 14C data and cumulative water content data directly in the incremental intervals in the Paintbrush nonwelded unit and the Topopah Spring welded unit. The second method uses the regression relation for 14C data and cumulative water content data for the entire Paintbrush nonwelded unit and the Topopah Spring Tuff/Topopah Spring welded unit. Using the first method, for the Paintbrush nonwelded unit in borehole USW UZ-14 percolation flux ranges from 2.3 to 41.0 mm/a. Transport velocity ranges from 1.2 to 40.6 cm/a. For the Topopah Spring welded unit percolation flux ranges from 0.9 to 5.8 mm/a in the 8 incremental intervals calculated. Transport velocity ranges from 1.4 to 7.3 cm/a in the 8 incremental intervals. Using the second method, average percolation flux in the Paintbrush nonwelded unit for 6 boreholes ranges from 0.9 to 4.0 mm/a at the 95% confidence level. Average transport velocity ranges from 0.6 to 2.6 cm/a. For the Topopah Spring welded unit and Topopah Spring Tuff, average percolation flux in 5 boreholes ranges from 1.3 to 3.2 mm/a. Average transport velocity ranges from 1.6 to 4.0 cm/a. Both the average percolation flux and average transport velocity in the PTn are smaller than in the TS/TSw. However, the average minimum and average maximum values for the percolation flux in the TS/TSw are within the PTn average range. Therefore, differences in the percolation flux in the two units are not significant. On the other hand, average, average minimum, and average maximum transport velocities in the TS/TSw unit are all larger than the PTn values, implying a larger transport velocity for the TS/TSw although there is a small overlap.

Lithium sorption to Yucca Mountain tuffs by I. Anghel; H.J. Turin; P.W. Reimus (819-824).
The Li ion has been used as a reactive tracer in field tests performed in the saturated and unsaturated-zone in volcanic tuffs at Yucca Mountain, Nevada. Lithium sorbs weakly by cation exchange and permits field-scale testing of laboratory-based predictions of reactive-solute transport. A series of laboratory studies show that Li sorption is nonlinear and varies with lithology in the different horizons of the tuff. In particular, both Li sorption and Li-specific cation-exchange capacity vary as functions of tuff mineralogy, and can be predicted given quantitative X-ray diffraction data. These results indicate that Li sorption is dominated by clay and zeolite minerals, and that sorption coefficients can be predicted given mineralogic analysis results.

Tracer and radionuclide sorption to vitric tuffs of Busted Butte, Nevada by H.J. Turin; A.R. Groffman; L.E. Wolfsberg; J.L. Roach; B.A. Strietelmeier (825-836).
Field-scale unsaturated-zone tracer tests have been performed at Busted Butte, Nevada, near the potential high-level radioactive waste repository at Yucca Mountain. These tests are intended to improve our understanding of unsaturated-zone transport processes, and to test our ability to predict field-scale behavior using laboratory-scale measurements. The field tests use a mixture of nonreactive and reactive tracers. Nonreactive tracers include Br, I, 5 different fluorobenzoic acids, Na fluorescein, and a pyridone derivative. Reactive tracers include the metals Li, Mn, Co, and Ni, and the organic dye rhodamine WT. Rock samples from 3 different stratigraphic units at the Busted Butte test facility have been extensively characterized lithologically and mineralogically, and analyzed for Fe and Mn oxide content. Sorption of Np, Pu, Am and the field tracers onto these 3 rocks has been measured using batch techniques. Results confirm that the nonreactive tracers are indeed nonreactive, and show that sorption of radionuclides and sorbing tracers increases with increasing degree of rock alteration, as evidenced by increasing levels of smectite and Fe and Mn oxides. Among the radionuclides, Am and Pu sorb much more strongly than Np; the tracers' degree of sorption is rhodamine WTLi⪡Mn<Ni<Co. Pu, Co, Mn, Ni and rhodamine WT exhibits strongly nonlinear sorption; Mn and Ni behavior may reflect competition with Co for sorption sites.

Solubility and sorption of redox-sensitive radionuclides (Np, Pu) in J-13 water from the Yucca Mountain site: comparison between experiment and theory by Wolfgang Runde; Steve D Conradson; D Wes Efurd; NingPing Lu; Craig E VanPelt; C.Drew Tait (837-853).
This study presents the characterization of Pu-bearing precipitates and the results from uptake studies of Np and Pu on inorganic colloidal particulates in J-13 water from the Yucca Mountain site. Plutonium solubilities determined experimentally at pH values of 6, 7, and 8.5 are about two orders of magnitude higher than those calculated using the existing thermodynamic database indicating the influence of colloidal Pu(IV) species. Solid phase characterization using X-ray diffraction revealed primarily Pu(IV) in all precipitates formed at pH 6, 7, and 8.5. The solubility controlling Pu-bearing solids precipitated at ambient temperature consisted of amorphous Pu(OH)4(s) with several Pu–O distances between 2.3 and 2.7 Å that are characteristic for Pu(IV) colloids. High temperature (90 °C) increased solid phase crystallinity and produced Pu(IV) solids that contained Pu oxidation state impurities. X-ray absorption spectroscopic studies revealed diminished Pu–O and Pu–Pu distances that were slightly different from those in crystalline PuO2(s). A Pu–O bond of 1.86 Å was identified that is consistent with the plutonyl(V) distance of 1.81 Å in PuO2 +(aq). Hematite, montmorillonite, and silica colloids were used for uptake experiments with 239Pu(V) and 237Np(V). The capacity of hematite to sorb Pu significantly exceeded that of montmorillonite and silica. A low desorption rate was indicative of highly stable Pu-hematite colloids, which may facilitate Pu transport to the accessible environment. Neptunium uptake on all mineral phases was far less than Pu(V) uptake suggesting that a potential Pu(V)–Pu(IV) reductive sorption process was involved. The temperature effect on Pu solubility and pseudocolloid formation is also discussed.