U-Pb ages of secondary silica at Yucca Mountain,Nevada: implications for the paleohydrology of the unsaturated zone

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.     

Percolation flux and transport velocity in the unsaturated zone,Yucca Mountain,Nevada

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.     

Feldspar dissolution rates in the Topopah Spring Tuff, Yucca Mountain, Nevada

Two different field-based methods are used here to calculate feldspar dissolution rates in the Topopah Spring Tuff, the host rock for the proposed nuclear waste repository at Yucca Mountain, Nevada. The center of the tuff is a high silica rhyolite, consisting largely of alkali feldspar (60 wt%) and quartz polymorphs (35 wt%) that formed by devitrification of rhyolitic glass as the tuff cooled. First, the abundance of secondary aluminosilicates is used to estimate the cumulative amount of feldspar dissolution over the history of the tuff, and an ambient dissolution rate is calculated by using the estimated thermal history. Second, the feldspar dissolution rate is calculated by using measured Sr isotope compositions for the pore water and rock. Pore waters display systematic changes in Sr isotopic composition with depth that are caused by feldspar dissolution. The range in dissolution rates determined from secondary mineral abundances varies from 10⁻¹⁶ to 10⁻¹⁷ mol s⁻¹ kg tuff⁻¹ with the largest uncertainty being the effect of the early thermal history of the tuff. Dissolution rates based on pore water Sr isotopic data were calculated by treating percolation flux parametrically, and vary from 10⁻¹⁵ to 10⁻¹⁶ mol s⁻¹ kg tuff⁻¹ for percolation fluxes of 15 mm a⁻¹ and 1 mm a⁻¹, respectively. Reconciling the rates from the two methods requires that percolation fluxes at the sampled locations be a few mm a⁻¹ or less. The calculated feldspar dissolution rates are low relative to other measured field-based feldspar dissolution rates, possibly due to the age (12.8 Ma) of the unsaturated system at Yucca Mountain; because oxidizing and organic-poor conditions limit biological activity; and/or because elevated silica concentrations in the pore waters (50 mg L⁻¹) may inhibit feldspar dissolution.     

Thermal history of the unsaturated zone at Yucca Mountain,Nevada, USA

Secondary calcite, silica and minor amounts of fluorite deposited in fractures and cavities record the chemistry, temperatures, and timing of past fluid movement in the unsaturated zone at Yucca Mountain, Nevada, the proposed site of a high-level radioactive waste repository. The distribution and geochemistry of these deposits are consistent with low-temperature precipitation from meteoric waters that infiltrated at the surface and percolated down through the unsaturated zone. However, the discovery of fluid inclusions in calcite with homogenization temperatures (T_h) up to ∼80 °C was construed by some scientists as strong evidence for hydrothermal deposition. This paper reports the results of investigations to test the hypothesis of hydrothermal deposition and to determine the temperature and timing of secondary mineral deposition. Mineral precipitation temperatures in the unsaturated zone are estimated from calcite- and fluorite-hosted fluid inclusions and calcite δ¹⁸O values, and depositional timing is constrained by the ²⁰⁷Pb/²³⁵U ages of chalcedony or opal in the deposits. Fluid inclusion T_h from 50 samples of calcite and four samples of fluorite range from ∼35 to ∼90 °C. Calcite δ¹⁸O values range from ∼0 to ∼22‰ (SMOW) but most fall between 12 and 20‰. The highest T_h and the lowest δ¹⁸O values are found in the older calcite. Calcite T_h and δ¹⁸O values indicate that most calcite precipitated from water with δ¹⁸O values between −13 and −7‰, similar to modern meteoric waters.     

Monazite solubility and dissolution kinetics: implications for the thorium and light rare earth chemistry of felsic magmas

A series of monazite dissolution experiments was conducted in a hydrous (1–6 wt.%) granitic melt at 8 kbar over the temperature range 1,000–1,400° C. A polished cube of monazite was immersed in a natural obsidian melt and allowed to partially dissolve. Electron microprobe traverses perpendicular to the crystal-melt interface revealed concentration gradients in the LREEs and P. Diffusivities of the LREEs and P were calculated from these profiles, yielding the following Arrhenius relations for the LREEs: D=0.23 exp(–60.1 kcal mol^–1/RT) at 6% water D=2.30×10⁷ exp(–122.1 kcal mol^–1/RT) at 1% water These results demonstrate the importance of dissolved water on REE diffusion. Phosphorus diffusivities are nearly identical to those of the rare-earths, suggesting that P diffusion charge-compensates REE diffusion. The concentration of LREEs required for monazite saturation in these melts is given by the level of dissolved LREEs at the crystal-melt interface. These values also show a dependence on dissolved water, with LREE_sat=60 ppm at 6% H₂O when extrapolated down to 700° C, and LREE_sat=30 ppm at 1% H₂O. Calculated dissolution rates based on the above parameters indicate that minute (<30 m diameter) monazite crystals will be readily digested by an enclosing anatectic magma under reasonable geologic conditions (i.e., T=700–800° C and >2% H₂O), whereas larger (> 50 m) crystals will likely be residual over the duration of an anatectic event. The low solubility of monazite in this melt suggests that the LREE depletion observed in some felsic differentiation suites may be the result of monazite crystallization. Limited experimental and geochemical/petrologic evidence indicates that compositional changes in the melt accompanying differentiation decrease the solubility of monazite drastically. Kinetic and chemical constraints may also lead to localized monazite saturation and inclusion in major phases or even other accessories. Variations in the REE composition of monazite from different parageneses probably reflects the REE pattern of the parent melt, and may be due to gradational differences in the stability of individual or subgroup REE-complexes as a function of melt composition. Particularly important in this regard seems to be the lime+alkali/alumina balance of the melt and its volatile content.     

Geochemistry of rock units at the potential repository level,Yucca Mountain,Nevada

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.     

Potential contaminant transport in the regional Carbonate Aquifer beneath Yucca Mountain, Nevada, USA

Yucca Mountain, Nevada is the site of the proposed US geologic repository for spent nuclear fuel and high-level radioactive waste. The repository is to be a mine, sited approximately 300 m below the crest of the mountain, in a sequence of variably welded and fractured mid-Miocene rhylolite tuffs, in the unsaturated zone, approximately 300 m above the water table. Beneath the proposed repository, at a depth of 2 km, is a thick sequence of Paleozoic carbonate rocks that contain the highly transmissive Lower Carbonate Aquifer. In the area of Yucca Mountain the Carbonate Aquifer integrates groundwater flow from north of the mountain, through the Amargosa Valley, through the Funeral Mountains to Furnace Creek in Death Valley, California where the groundwater discharges in a set of large springs. Data that describe the Carbonate Aquifer suggest a concept for flow through the aquifer, and based upon the conceptual model, a one-layer numerical model was constructed to simulate groundwater flow in the Carbonate Aquifer. Advective transport analyses suggest that the predicted travel time of a particle from Yucca Mountain to Death Valley through the Carbonate Aquifer might be as short as 100 years to as long 2,000 years, depending upon the porosity.     

Physical and stable-isotope evidence for formation of secondary calcite and silica in the unsaturated zone,Yucca Mountain,Nevada

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.     

New techniques in rock mass classification: application to welded tuffs at the Nevada Yucca Mountain

Summary Many rock mass classification systems exist to assist the engineer in assessing the rock support requirements for underground design. On-going research in this area is directed at attempting to utilize the fractal dimension and the acoustic emission response of the tuffs at the Nevada Yucca Mountain to further aid in rock mass classification. Acoustic emission response is shown to be correlated with the porosity of the sample. Engineering behaviour of the rock varies dramatically with porosity; events and peak amplitude offer a means to distinguish between fracture porosity and pore porosity and consequently the engineering behaviour of the rock. Fractal dimension is used to characterize the roughness of fracture surfaces. Two fractal dimension calculation methods, one based on the semi-variogram for the surface and the other based on the use of dividers, are applied for this purpose. The divider method is shown to resolve deviation from a straight line; the semi-variogram method is shown to identify statistical similarity to various types of noise.Nomenclature D fractal dimension - AE acoustic emission - b b-value determined from log(frequency) against log(amplitude) plots - (h) semi-variogram function - h lag distance for semi-variogram function - H an exponent term related to fractal dimension asD=2 –H     

Pb and rare earth element diffusion in xenotime

Diffusion of Pb and the rare earth elements Sm, Dy and Yb have been characterized in synthetic xenotime under dry conditions. The synthetic xenotime was grown via a Na₂CO₃–MoO₃ flux method. The sources of diffusant for the rare earth diffusion experiments were REE phosphate powders, with experiments run using sources containing a single REE. For Pb, the source consisted a mixture of YPO₄ and PbTiO₃. Experiments were performed by placing source and xenotime in Pt capsules, and annealing capsules in 1 atm furnaces for times ranging from 30 min to several weeks, at temperatures from 1000 to 1500 °C. The REE and Pb distributions in the xenotime were profiled by Rutherford Backscattering Spectrometry (RBS).The following Arrhenius relations are obtained for diffusion in xenotime, normal to (101):

Diffusivities among the REE do not differ greatly in xenotime over the investigated temperature range, in contrast to findings for the REE in zircon [Cherniak, D.J., Hanchar, J.M., Watson, E.B., 1997. Rare earth diffusion in zircon. Chem. Geol. 134, 289–301.], where the LREE diffuse more slowly, and with higher activation energies for diffusion, than the heavier rare earths. In zircon, these differences among diffusion of the rare earths are attributed to the relatively large size of the REE with respect to Zr, for which they likely substitute in the zircon lattice. With the systematic increase in ionic radius from the heavy to lighter REE, this size mismatch becomes more pronounced and diffusivities of the LREE are as consequence slower. Although xenotime is isostructural with zircon, the REE are more closely matched in size to Y, so in xenotime this effect appears much smaller and the REE diffuse at similar rates. In addition, the process of diffusion in xenotime likely involves simple REE^+ 3 → Y^+ 3 exchange, without charge compensation as needed for REE^+ 3 → Zr^+ 4 exchange in zircon. This latter factor may also contribute to the large activation energies for diffusion of the REE in zircon (i.e., 691–841 kJ mol^− 1, [Cherniak, D.J., Hanchar, J.M., Watson, E.B., 1997. Rare earth diffusion in zircon. Chem. Geol. 134, 289–301.]), in comparison with those for xenotime.For Pb, the following Arrhenius relation is obtained (also normal to (101)):

These measurements suggest that Pb diffusion in xenotime is quite slow, even slower than Pb diffusion in monazite and zircon, and considerably slower than diffusion of the REE in xenotime. Xenotime may therefore be even more retentive of Pb isotope signatures than either monazite or zircon in cases where Pb isotopes are altered solely by volume diffusion. However, because the activation energy for Pb diffusion in xenotime is lower than those for monazite and zircon, Pb diffusion may be somewhat faster at many temperatures of geologic interest in xenotime than in monazite or zircon.     

Origin, timing, and temperature of secondary calcite-silica mineral formation at Yucca Mountain, Nevada

The origin of secondary calcite-silica minerals in primary and secondary porosity of the host Miocene tuffs at Yucca Mountain has been hotly debated during the last decade. Proponents of a high-level nuclear waste repository beneath Yucca Mountain have interpreted the secondary minerals to have formed from cool, descending meteoric fluids in the vadose zone; critics, citing the presence of two-phase fluid inclusions, argued that the minerals could only have formed in the phreatic zone from ascending hydrothermal fluids. Understanding the origin, temperature, and timing of these minerals is critical in characterizing geologically recent fluid flux at the site, and has significant implications to whether waste should be stored at Yucca Mountain.Petrographic and paragenetic studies of 155 samples collected from the Exploratory Studies Facility (ESF) and repository block cross drift (ECRB) tunnels indicate that heterogeneously distributed calcite with lesser chalcedony, quartz, opal, and fluorite comprise the oldest secondary minerals. These are typically overgrown by intermediate-aged calcite, often exhibiting distinctive bladed habits. The youngest event recorded across the site is the deposition of Mg-enriched (up to ∼1 wt%) and depleted, growth-zoned calcite intergrown with U-enriched opal. The cyclical variation in Mg enrichment and depletion is probably related to climate changes that have occurred during the last few million years. The distribution of secondary minerals is consistent with precipitation in the vadose zone.Fluid inclusion petrography of sections from the 155 samples determined that 96% of the fluid inclusion assemblages (FIAs) contained liquid-only inclusions that formed at ambient temperatures (<35°C). However, 50% of the samples (n = 78) contained relatively rare FIA that contain both liquid-only and liquid plus vapor inclusions (herein termed two-phase FIAs) that formed at temperatures above 35°C. Virtually all of these two-phase FIAs occur in paragenetically old calcite; rare two-phase inclusion assemblages were also observed in early fluorite and quartz, and early-intermediate calcite. Homogenization temperatures (≡ trapping temperatures) across Yucca Mountain are generally 45 to 60°C, but higher temperatures reaching 83°C were recorded in calcite from the north portal and ramp of the ESF. Cooler temperatures of ∼35 to 45°C were recorded in the intensely fractured zone. Multiple populations of two-phase FIAs from lithophysal cavities in the ESF and ECRB cross drift indicate early fluid cooling with time from temperatures >45°C in early calcite, to <35 to 45°C in paragenetically younger calcite. Freezing point depressions range from −0.2 to −1.6°C, indicating trapping of a low salinity fluid. The majority of intermediate calcite and all outermost Mg-enriched calcite contains rare all-liquid inclusions and formed from ambient temperature (<35°C) fluids.Carbon and oxygen isotope data reveal a consistent trend of decreasing δ¹³C (from 9.5 to −8.5‰) and increasing δ¹⁸O (from 5.2 to 22.1‰) values from paragenetically early calcite to Mg-enriched growth-zoned calcite. Depleted δD values (−131 to −90‰) of inclusion fluids from intermediate and the youngest Mg-enriched calcite indicate derivation from surface meteoric fluids. Recalculation of δ¹⁸O_H2O values of −12 to −10‰ is consistent with derivation from paleometeoric fluids.Results of integrated U-Pb dating (opal and chalcedony) and fluid inclusion microthermometry indicate that two-phase FIAs that trapped fluids of >50°C are older than 6.29 ± 0.30 Ma. Two-phase FIAs in paragenetically later calcite, which formed from fluids of 35 to 45°C, are older than 5.32 ± 0.02 Ma. There is no evidence for trapping of fluids with elevated temperatures during the past 5.32 my. The youngest Mg-enriched calcite intergrown with opal began to precipitate between about 1.9 to 2.9 Ma and has continued to precipitate within the past half million years. The presence of liquid-only inclusions and the consistent occurrence of Mg-enriched calcite and opal as the youngest event indicate a minor, but chemically distinct, ambient temperature (<35°C) fluid flux during the past 2 to 3 my.     

Comparison of the behaviour of rare earth elements in surface waters,overburden groundwaters and bedrock groundwaters in two granitoidic settings,Eastern Sweden

This work, which was done within the Swedish nuclear waste management program, was carried out in order to increase the understanding of the mobility and fate of rare earth elements (REEs) in natural boreal waters in granitoidic terrain. Two areas were studied, Forsmark and Simpevarp, one of which will be selected as a site for spent nuclear fuel. The highest REE concentrations were found in the overburden groundwaters, in Simpevarp in particular (median ∑REE 52 μg/L), but also in Forsmark (median ∑REE 6.7 μg/L). The fractionation patterns in these waters were characterised by light REE (LREE) enrichment and negative Ce and Eu anomalies. In contrast, the surface waters had relatively low REE concentrations. They were characterised either by an increase in relative concentrations throughout the lanthanide series (Forsmark which has a carbonate-rich till) or flat patterns (Simpevarp with carbonate-poor till), and had negative Ce and Eu anomalies. In the bedrock groundwaters, the concentrations and fractionation patterns of REEs were entirely different from those in the overburden groundwaters. The median La concentrations were low (just above 0.1 μg/L in both areas), only in a few samples were the concentrations of several REEs (and in a couple of rare cases all REEs) above the detection limit, and there was an increase in the relative concentrations throughout the lanthanide series. In contrast to these large spatial variations, the temporal trends were characterised by small (or non existent) variations in REE-fractionation patterns but rather large variations in concentrations. The Visual MINTEQ speciation calculations predicted that all REEs in all waters were closely associated with dissolved organic matter, and not with carbonate. In the hydrochemical data for the overburden groundwater in particular, there was however a strong indication of association with inorganic colloids, which were not included in the speciation model. Overall the results showed that within a typical boreal granitoidic setting, overburden groundwaters are enriched in REEs, organic complexes are much more important than carbonate complexes, there is little evidence of significant mixing of REEs between different water types (surface, overburden, bedrock) and spatial variations are more extensive than temporal ones.     

Rare earth element sources and modification in the Lower Kittanning coal bed, Pennsylvania: implications for the origin of coal mineral matter and rare earth element exposure in underground mines

In this study, we examine the variations in rare earth elements (REE) from the Lower Kittanning coal bed of eastern Ohio and western Pennsylvania, USA, in an attempt to understand the factors that control mineral matter deposition and modification in coal, and to evaluate possible REE mixed exposure hazards facing underground mine workers. The results of this study suggest that the Lower Kittanning coal mineral matter is derived primarily from a clastic source similar to that of the shale overburden. While highly charged cations like silicon, aluminum, and titanium remained relatively immobile within the coal mineral matter, iron (primarily as pyrite) was added from nonclastic sources, either during deposition of the coal mire vegetation or subsequent to burial. Other mobile cations (e.g., alkali and alkaline earth elements) appear to have been added to and/or leached from the originally deposited clastic mineral matter. Most of the sulfur in the Lower Kittanning coal bed is bound as FeS₂ in the mineral matter, but a majority of samples contain a small excess of S that is most likely organically bound.In general, the total rare earth element content (TREE) in coal ash is greater than that in the shale overburden. If the primary source of mineral matter is the same as that for the overlying shale, then REE must have been enriched in the coal mineral matter subsequent to deposition. The total rare earth element content of Lower Kittanning coals correlates strongly with Si concentration ([TREE]≈0.0024 [Si]), which provides a threshold for evaluating possible mixed exposure health effects. Chondrite-normalized REE patterns reveal a shale-like light rare earth element (LREE) enrichment for the coal, similar to that of the shale overburden, again suggesting a primarily clastic REE source. However, when normalized to the shale overburden, most of the coal ash samples display a small but distinct heavy rare earth element (HREE) enrichment. We surmise that the HREE were added and/or preferentially retained during epigenesis, possibly associated with groundwater flow through the coal unit, but not necessarily in close association with the addition of iron. At least some of the “excess” HREE could be organically bound within the Lower Kittanning coal.     

Speciation of adsorbed yttrium and rare earth elements on oxide surfaces

The distribution of yttrium and the rare earth elements (YREE) between natural waters and oxide mineral surfaces depends on adsorption reactions, which in turn depend on the specific way in which YREE are coordinated to mineral surfaces. Recent X-ray studies have established that Y³⁺ is adsorbed to the rutile (1 1 0) surface as a distinctive tetranuclear species. However, the hydrolysis state of the adsorbed cation is not known from experiment. Previous surface complexation models of YREE adsorption have suggested two to four cation hydrolysis states coexisting on oxide surfaces. In the present study, we investigate the applicability of the X-ray results to rare earth elements and to several oxides in addition to rutile using the extended triple-layer surface complexation model. The reaction producing a hydrolyzed tetranuclear surface species

     

A Spatial-Temporal/3-D Model for Volcanic Hazard Assessment: Application to the Yucca Mountain Region, Nevada

We present a 3-D Poisson model that permits identification and quantification of volcanic phenomena distributed through space and evolving in time (i.e., spatiotemporal data). Specifically, the model: (1) is volcanologically informative in solving problems of volcanic risk/hazard which depends on the location and time of future events; (2) contains model fitting computation algorithms that are efficient; and (3) is flexible enough to handle a large class of volcanic risk/hazard studies. Furthermore, we apply the model fitting techniques developed in this paper to the volcanic data from the Yucca Mountain project to demonstrate a unified volcanic hazard analysis. This study also evaluates the sensitivity of the statistical models developed by experts who have addressed the volcanic hazard/risk assessment problem near the Yucca Mountain region.     

Sensitivity analysis of hydrological parameters in modeling flow and transport in the unsaturated zone of Yucca Mountain, Nevada, USA

The unsaturated fractured volcanic deposits at Yucca Mountain in Nevada, USA, have been intensively investigated as a possible repository site for storing high-level radioactive waste. Field studies at the site have revealed that there exist large variabilities in hydrological parameters over the spatial domain of the mountain. Systematic analyses of hydrological parameters using a site-scale three-dimensional unsaturated zone (UZ) flow model have been undertaken. The main objective of the sensitivity analyses was to evaluate the effects of uncertainties in hydrologic parameters on modeled UZ flow and contaminant transport results. Sensitivity analyses were carried out relative to fracture and matrix permeability and capillary strength (van Genuchten α) through variation of these parameter values by one standard deviation from the base-case values. The parameter variation resulted in eight parameter sets. Modeling results for the eight UZ flow sensitivity cases have been compared with field observed data and simulation results from the base-case model. The effects of parameter uncertainties on the flow fields were evaluated through comparison of results for flow and transport. In general, this study shows that uncertainties in matrix parameters cause larger uncertainty in simulated moisture flux than corresponding uncertainties in fracture properties for unsaturated flow through heterogeneous fractured rock.     

Distribution of rare earth elements in crystalline bedrock groundwaters: Oslo and Bergen regions,Norway

One hundred and fifty Norwegian bedrock groundwater samples, from Bergen and from Vestfold (Oslofjord), have been analysed by ICP-MS techniques at two laboratories for a large suite of trace elements including rare earth elements (REEs) and Y. The bedrock lithologies include granites (dominated by the Permian Drammen Granite) and Permian latites/rhomb porphyries from Oslofjord, and Caledonian/Precambrian granitic and gneissic lithologies in the Bergen area. The REEs show good correlation with each other, with the exception of Eu. REEs generally show a weak negative correlation with pH. REE concentrations are highest in waters in acidic lithologies and generally decrease with increasing atomic weight. Yttrium, La, Ce and Nd are the most abundant REEs in the waters, with median concentrations exceeding 0.1 μg/l. On crustal (PAAS)-normalised plots, distinct geochemical signatures are observed for the different lithologies. Most groundwaters exhibit negative Eu anomalies on such plots, except for latitic waters from the Oslo area which show a positive Eu anomaly. Aquifer host-rock-normalised plots for groundwaters from Vestfold indicate minor enrichment in heavier REEs and depletion in Ce during water–rock interaction.     

非洲稀土资源研究进展

稀土是现代高科技产业发展的关键金属,被世界主要经济体列为关键矿产资源。虽然中国稀土资源丰富,但2017年以来中国稀土资源进口量呈现出明显的上升趋势。总结中国稀土资源的进口数据,以及非洲稀土项目分布、储量及资源量、矿床类型、成矿时代、典型矿床特征及勘查投资等情况,以提升对非洲稀土资源的认识。研究表明,非洲稀土资源丰富,稀土氧化物的高级资源量超过1000×104 t,近年来勘探及开发进度提升迅速。稀土储量及资源量主要集中于坦桑尼亚等12个国家,成矿类型可划分为火成碳酸岩型及离子吸附型等8种（成矿时代跨度大）,其中火成碳酸岩型和离子吸附型稀土矿床是目前勘探及开发的重点。非洲稀土矿床勘查投资规模2012年达到顶峰,之后持续下降,2017年降至低谷,2018年开始迅速反弹。未来,随着国际上稀土矿项目逐步投产,由中国主导全球稀土市场价格的局面将面临挑战。非洲稀土矿成矿条件优越,中资企业可利用地-采-选-冶的技术优势,积极引导并推动非洲稀土生产进入中国产业链。     

内蒙古河套平原高砷地下水中稀土元素含量及分异特征

高砷地下水是世界范围内的一个重大环境问题。尽管已有工作在高砷地下水的地球化学特征、形成条件和富砷机理等方面取得了很大进展,但其稀土元素(REE)含量及分异特征却一直不清楚,这就限制了稀土方法在评价此类地下水中的应用。在对内蒙古河套盆地地下水样品进行现场测试、实验室分析检测的基础上,我们发现高砷地下水的REE浓度较低。对地下水REE浓度依照北美页岩平均组分(NASC)进行归一化处理后,我们发现大部分水样富集重稀土元素(HREEs),而贫化轻稀土元素(LREEs)。HREEs的富集与地下水中碳酸根对于REE的络合作用密切相关,而弱碱性环境下REE的再吸附可导致LREEs的贫化。所有地下水样表现为Eu正异常,其中大部分表现为Ce负异常。Eu正异常似乎与铁锰氧化物的还原性溶解和解吸附有关,地下水As浓度随[Eu]NASC的升高而升高。从某种意义上说,还原性含水系统中Eu正异常的程度也许可以反映地下水As的富集程度。     

Temporal variation of isotope and rare earth element abundances in volcanic rocks from Guam: implications for the evolution of the Mariana Arc

Volcanic rocks exposed on Guam were erupted during the Late Middle Eocene (Facpi Fm.), Late Eocene-Oligocene (Alutom Fm.) and Miocene (Umatac Fm.). Four magma series are recognized: the boninite series (44 m.y.b.p.), the tholeiite and calc-alkaline series, which were erupted along with boninite series lavas at 32–36 m.y.b.p. and high-K lavas of the Umatac Fm. (14 m.y.b.p.). Isotope and and rare earth element (REE) characteristics of the four magma series are distinct. Boninite series lavas have U-shaped REE patterns, relatively low ¹⁴³Nd/¹⁴⁴Nd (0.51294–0.51298), and high ²⁰⁶Pb/²⁰⁴Pb (19.0–19.2). Tholeiite series lavas are LREE (light REE) depleted, and have high ¹⁴³Nd/¹⁴⁴Nd (0.51304–0.51306) and low ²⁰⁶Pb/²⁰⁴Pb (18.4–18.5). Calc-alkaline series lavas have Sr, Nd and Pb isotope ratios similar to tholeiite series lavas, but flat to U-shaped REE patterns. Umatac Fm. lavas are strongly LREE-enriched, and have higher ⁸⁷Sr/ ⁸⁶Sr (0.70375–0.70380) and ²⁰⁷Pb/²⁰⁴Pb relative to ²⁰⁶Pb/ ²⁰⁴Pb than Facpi and Alutom Fm. lavas. Boninite and tholeiite series magmas, erupted in the position of the Palau-Kyushu Ridge, were probably derived from distinct mantle sources having OIB and N-MORB-like isotopic characteristics, together with fluids derived from subducted Pacific plate basalt. Calc-alkaline series lavas were most likely derived from the tholeiite series by extensive crystal fractionation, wallrock contamination and magma mixing. Lavas of the Umatac Fm., erupted in the position of the West Mariana Ridge, may include up to 2–3% subducted sediment, similar to some active Mariana arc lavas.