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.     

Petrology of palagonite tuffs of Koko Craters,Oahu, Hawaii

Tuff deposits of the Koko Crater group consist largely of alkali basalt glass, either fresh or palagonitized. Most of the deposits are progressively palagonitized at depth, and topographic relations of palagonite on Koko Crater indicate that the palagonite was formed after the cone had been deeply eroded.The principal authigenic minerals in the palagonite tuffs were deposited in following sequence: phillipsite, chabazite, analcime, montmorillonite together with opal, and calcite. The amount of authigenic minerals in a given sample is generally proportional to the amount of palagonite, indicating that the authigenic minerals are produced in palagonitization of glass.Chemical analyses of sideromelane and associated palagonite by the electron microprobe show that about a quarter of the SiO₂, half of the Al₂O₃ and MgO, and three quarters or more of the CaO, Na₂O, and K₂O are lost in converting sideromelane to an equal volume of palagonite. A substantial proportion of these components lost from the sideromelane are precipitated nearby in zeolites, montmorillonite, opal, and calcite.Reaction of sideromelane with percolating ground water at low temperatures accounts for the vertical zoning from relatively fresh tuffs down into palagonite tuffs. The pH and ionic strength of percolating water probably increased with depth by solution and hydrolysis of glass, and where the pH and ionic strength became sufficiently high, the glass reacted to form palagonite and zeolites. Palagonite was formed by a microsolution-precipitation mechanism rather than by hydration or devitrification.     

Evaporative evolution of a Na–Cl–NO<Subscript>3</Subscript>–K–Ca–SO<Subscript>4</Subscript>–Mg–Si brine at 95 °C: Experiments and modeling relevant to Yucca Mountain,Nevada

A synthetic Topopah Spring Tuff water representative of one type of pore water at Yucca Mountain, NV was evaporated at 95°C in a series of experiments to determine the geochemical controls for brines that may form on, and possibly impact upon the long-term integrity of waste containers and drip shields at the designated high-level, nuclear-waste repository. Solution chemistry, condensed vapor chemistry, and precipitate mineralogy were used to identify important chemical divides and to validate geochemical calculations of evaporating water chemistry using a high temperature Pitzer thermodynamic database. The water evolved toward a complex "sulfate type" brine that contained about 45 mol % Na, 40 mol % Cl, 9 mol % NO₃, 5 mol % K, and less than 1 mol % each of SO₄, Ca, Mg, ∑CO₂(aq), F, and Si. All measured ions in the condensed vapor phase were below detection limits. The mineral precipitates identified were halite, anhydrite, bassanite, niter, and nitratine. Trends in the solution composition and identification of CaSO₄ solids suggest that fluorite, carbonate, sulfate, and magnesium-silicate precipitation control the aqueous solution composition of sulfate type waters by removing fluoride, calcium, and magnesium during the early stages of evaporation. In most cases, the high temperature Pitzer database, used by EQ3/6 geochemical code, sufficiently predicts water composition and mineral precipitation during evaporation. Predicted solution compositions are generally within a factor of 2 of the experimental values. The model predicts that sepiolite, bassanite, amorphous silica, calcite, halite, and brucite are the solubility controlling mineral phases.     

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.     

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.     

Diatomaceous deposits of Fayium, Egypt; characterization and evaluation for industrial application

The Holocene lacustrine diatomaceous earth of Fayium,South West of Cairo,has been studied to define its minerals,chemistry,petrography and physical properties.Minerals were processed by way of calcination at 550℃ ,followed by acid leaching to reduce levels of mineral impurities.The diatomite is of biogenic opal A.with calcite as the main ganue mineral,quartz and clay minerals(smectite followed by kaolinite in abundance and a trace amount of illite).Silica in the diatomaceous earth accounts for about 63% on average.Positive correlation between CaO and CO2 indicates that Ca is present mainly as calcite.Al2O3,Fe2O3,MgO and K2O are attributed mainly to clay minerals.However,the physical properties of the diatomaceous earth as filter-aids and filler for paints and plastics are poor because of general high levels of impurities.The technological performances of the diatomaceous earth have been significantly improved owing to upgrading of diatoms through mineral processing trical.     

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.     

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.     

Speleothems from Mawsmai and Krem Phyllut caves,Meghalaya, India: some evidences on biogenic activities

The Mawsmai cave and Krem Phyllut caves, East Khasi hills, Meghalaya, India has so far not yet attracted the attention of geomicrobiologists. Observations and hypotheses on the possible influence of identified microorganisms for speleothem formations in Meghalaya are reported for the first time. XRD studies identified calcite in speleothems and gypsum in cave wall deposits as the dominant minerals. SEM-EDAX showed interesting microfabric features showing strong resemblance with fossilised bacteria, calcified filaments, needle calcite and numerous nano scale calcite crystals, highly weathered and disintegrated crystals of calcite, that point towards a significant microbial influence in its genesis. Thin section petrography showed laminated stromatolitic features. The microorganisms identified by conventional isolation and further evaluation of isolates by molecular techniques include Bacillus cereus, Bacillus mycoides, Bacillus licheniformis, Micrococcus luteus, and Actinomycetes. Microscopic observations also showed unidentifiable cocci and four unidentifiable strains of CaSO₄ (gypsum) precipitating bacteria. Experimental studies confirmed that these bacteria are able to precipitate calcium minerals (calcite, gypsum, minor amounts of dolomite) in the laboratory. These results allow us to postulate that species like these may contribute to active biogenic influence in the cave formations at Meghalaya.     

Description and interpretation of the composition of fluid and alteration mineralogy in the geothermal system,at Svartsengi,Iceland

The bulk composition and mineralogy of hydrothermally altered tholeiite, along with the composition and speciation of fluid, have been determined for a well-defined alteration zone at 240°C and 110 bars at Svartsengi, Iceland. Mass balances between the geothermal fluid and altered tholeiite, relative to a seawater/fresh water mixture and unaltered tholeiite, indicate the overall reaction per 1000 cm³ is: 1325 gm plagioclase + 1228 gm pyroxene + 215 gm oxide-minerals break down to form 685 gm chlorite + 636 gm albite + 441 gm quartz + 249 gm epidote + 266 gm calcite + 201 gm oxide-minerals + 15 gm pyrite, requiring an influx of 123 gm CO₂, 10 gm H₂S and 4 gm Na₂O and a release of 57 gm SiO₂, 35 gm FeO, 21 gm CaO, 8 gm MgO and 4 gm K₂O.Principal reactions, deduced from textural evidence, include Na-Ca exchange in plagioclase, precipitation of quartz, calcite and anhydrite, and formation of chlorite and epidote by reactions between groundmass minerals and fluid.Thermodynamic analyses of authigenic minerals and downhole fluid indicate that the fluid maintains a state close to equilibrium with the secondary mineral phases chlorite, epidote, albite, quartz, calcite, prehnite, anhydrite, pyrite and magnetite, whereas remnant primary labradorite and augite are out of equilibrium with the fluid.Water/rock ratios for the system are determined under a variety of assumptions. However, the open nature of the system makes comparisons with experimental and theoretical closed system studies ambiguous.     

山东省归来庄金矿田卓家庄含碲金矿床的碲化物赋存状态研究

含碲金矿床中碲的赋存状态研究是对其进行综合开发利用的技术关键。文章采用高分辨率扫描电镜(SEM)结合X射线能谱(EDS)和元素面分布技术(EDS_Mapping),首次对山东省归来庄金矿田的卓家庄金矿床中金属类微细矿物及蚀变围岩进行元素空间分布及丰度分析,定性确定可能存在的矿物种类、形态特征及各矿物间的空间关系。在此基础上,采用EDS微区成分分析法分别对各含碲矿物进行了精确的成分测定,最终得到矿石中含碲矿物的化学式和空间分布特征。研究结果表明,山东卓家庄金矿床中含碲矿物均以浸染状的他形镶嵌分布于主矿物之间,颗粒大小从几微米到几百微米,总体以二十几微米最多,不同粒级的碲化物常相互伴生;含碲矿物种类有单质碲矿、PbTe、FeTe_2、AgAu_2Te_6和Cu_xAg_(1_x)Au_2Te_6,其中后两种矿物为本研究首次发现。     

Tonminerale in normalsedimenten,hydrothermal beeinflu\ten sedimenten und Erzschlämmen des Roten Meeres

From 14 deeps and other regions of the Red Sea totally 226 samples from 28 cores recovered during the VALDIVIA cruises (1971, 1972) were investigated according to their clay mineral content (<2μm resp. < 6.3 μm) after carbonate dissolution. Three facies groups are to distinguish:

1. normal sediments: dominance of chlorite, kaolinite, illite, small amounts of smectite and sepiolite. Two palygorskite types are present only in a few samples.
2. normal sediments with hydrothermal influence: clay mineral paragenesis similar like that of normal sediments; but increase of smectite and presence of goethite in each sample; partly small contents of talc.
3. heavy metal deposits: dominance of iron-bearing smectite, partly with amorphous components resp. pure ore mineral assemblages with authigenic silicates (talc, quartz, opal, chrysotile, sepiolite, palygorskite, chlorite).

Crystallinity of the clay and ore minerals is independent from sedimentary overburden. Sepiolite shows in small amounts a wide distribution; palygorskite₂ (d₁₁₀=11.3 Å) yields locally an increased concentration in the range of pteropod layers cemented by aragonite. The environment of ore deposits is characterized by iron-bearing smectite besides the ore minerals.     

赣南脉状钨矿的地球化学特征

赣南是世界著名的脉状钨矿产地,许多地学工作者对其作过详细研究。本文在前人工作的基础上,拟对脉状钨矿的某些地球化学特征及分布规律作进一步探讨。一、地质简况赣南位于南岭山系东段(图1)。泥盆纪以前,这里地壳大幅度下陷,沉积了巨厚的复理石建造、碎屑岩建造、碳酸盐建造及火山岩建造。区内震旦系、寒武系、奥陶系广泛分布。下古生代末期的强烈地壳运动,使泥盆纪以前的地层普遍上升褶皱,并伴有大规模酸性     

Origin of abundant moonmilk deposits in a subsurface granitic environment

Subsurface granitic environments are scarce and poorly investigated. A multi‐disciplinary approach was used to characterize the abundant moonmilk deposits and associated microbial communities coating the granite walls of the 16th Century Paranhos spring water tunnel in Porto city (north‐west Portugal). It is possible that this study is the first record of moonmilk in an urban subsurface granitic environment. The morphology and texture, mineralogical composition, stable isotope composition and microbial diversity of moonmilk deposits have been studied to infer the processes of moonmilk formation. These whitish secondary mineral deposits are composed of very fine needle‐fibre calcite crystals with different morphologies and density. Calcified filaments of fungal hyphae or bacteria were distinguished by field emission scanning electron microscopy. Stable isotope analysis revealed a meteoric origin of the needle‐fibre calcite, with an important contribution of atmospheric CO ₂, soil respiration and from weathering of Ca‐bearing minerals. The DNA ‐based analyses revealed the presence of micro‐organisms related to urban contamination, including Actinobacteria, mainly represented by Pseudonocardia hispaniensis , Thaumarchaeota and Ascomycota, dominated by Cladosporium . This microbial composition is consistent with groundwater pollution and contamination sources of the overlying urban area, including garages, petrol stations and wastewater pipeline leakage, showing that the Paranhos tunnel is greatly perturbed by anthropogenic activities. Whether the identified micro‐organisms are involved in the formation of the needle‐fibre calcite or not is difficult to demonstrate, but this study evidenced both abiotic and biogenic genesis for the calcite moonmilk in this subsurface granitic environment.     

Natural radionuclide mobility and its influence on U-Th-Pb dating of secondary minerals from the unsaturated zone at Yucca Mountain, Nevada

Extreme U and Pb isotope variations produced by disequilibrium in decay chains of ²³⁸U and ²³²Th are found in calcite, opal/chalcedony, and Mn-oxides occurring as secondary mineral coatings in the unsaturated zone at Yucca Mountain, Nevada. These very slowly growing minerals (mm my⁻¹) contain excess ²⁰⁶Pb and ²⁰⁸Pb formed from excesses of intermediate daughter isotopes and cannot be used as reliable ²⁰⁶Pb/²³⁸U geochronometers. The presence of excess intermediate daughter isotopes does not appreciably affect ²⁰⁷Pb/²³⁵U ages of U-enriched opal/chalcedony, which are interpreted as mineral formation ages.Opal and calcite from outer (younger) portions of coatings have ²³⁰Th/U ages from 94.6 ± 3.7 to 361.3 ± 9.8 ka and initial ²³⁴U/²³⁸U activity ratios (AR) from 4.351 ± 0.070 to 7.02 ± 0.12, which indicate ²³⁴U enrichment from percolating water. Present-day ²³⁴U/²³⁸U AR is ∼1 in opal/chalcedony from older portions of the coatings. The ²⁰⁷Pb/²³⁵U ages of opal/chalcedony samples range from 0.1329 ± 0.0080 to 9.10 ± 0.21 Ma, increase with microstratigraphic depth, and define slow long-term average growth rates of about 1.2-2.0 mm my⁻¹, in good agreement with previous results. Measured ²³⁴U/²³⁸U AR in Mn-oxides, which pre-date the oldest calcite and opal/chalcedony, range from 0.939 ± 0.006 to 2.091 ± 0.006 and are >1 in most samples. The range of ⁸⁷Sr/⁸⁶Sr ratios (0.71156-0.71280) in Mn-oxides overlaps that in the late calcite. These data indicate that Mn-oxides exchange U and Sr with percolating water and cannot be used as a reliable dating tool.In the U-poor calcite samples, measured ²⁰⁶Pb/²⁰⁷Pb ratios have a wide range, do not correlate with Ba concentration as would be expected if excess Ra was present, and reach a value of about 1400, the highest ever reported for natural Pb. Calcite intergrown with opal contains excesses of both ²⁰⁶Pb and ²⁰⁷Pb derived from Rn diffusion and from direct α-recoil from U-rich opal. Calcite from coatings devoid of opal/chalcedony contains ²⁰⁶Pb and ²⁰⁸Pb excesses, but no appreciable ²⁰⁷Pb excesses. Observed Pb isotope anomalies in calcite are explained by Rn-produced excess Pb. The Rn emanation may strongly affect ²⁰⁶Pb-²³⁸U ages of slow-growing U-poor calcite, but should be negligible for dating fast-growing U-enriched speleothem calcite.     

Unique Origin of Skarn at the Ohori Base Metal Deposit,Yamagata Prefecture,NE Japan: C,O and S Isotopic Study

The Ohori ore deposit is one of the Cu–Pb–Zn deposits in the Green Tuff region, NE Japan, and consists of skarn‐type (Kaninomata) and vein‐type (Nakanomata) orebodies. The former has a unique origin because its original calcareous rocks were made by hydrothermal precipitation during Miocene submarine volcanism. Carbon and oxygen isotope ratios of skarn calcite and sulfur isotope ratios of sulfides were measured in and around the deposit. Carbon and oxygen isotope ratios of the skarn calcite are δ¹³C = ?15.51 to ?5.1‰, δ¹⁸O = +3.6 to +22.5‰. δ¹³C values are slightly lower than those of the Cretaceous skarn deposits in Japan. These isotope ratios of the Kaninomata skarn show that the original calcareous rocks resemble the present submarine hydrothermal carbonates at the CLAM Site, Okinawa Trough, than Cenozoic limestones, even though some isotopic shifts had occurred during later skarnization. δ³⁴S ratios of the sulfide minerals from the Kaninomata and Nakanomata orebodies are mostly in a narrow range of +4.0 to +7.0‰ and they resemble each other, suggesting the same sulfur origin for the both deposits. The magnetite‐series Tertiary Kaninomatasawa granite is distributed just beneath the skarn layer and has δ³⁴S ratios of +7.5 to 8.1‰. The heavy sulfur isotope ratio of the skarn sulfides may have been affected by the Kaninomatasawa granite.     

Investigation of the hydrogeochemical processes in an alluvial channel aquifer located in a typical Karoo Basin of Southern Africa

An investigation was conducted to assess the hydrogeochemical processes of an alluvial channel aquifer located in a typical Karoo Basin of Southern Africa. The investigation was aimed at identifying and describing the groundwater chemistry evolution and its contribution to the overall groundwater quality. X-ray fluorescent spectrometry (XRF) and X-ray diffractometry (XRD) analyses were performed on geological samples to identify and quantify the major element oxides and minerals. The study utilises the conventional Piper diagram, bivariate plots and PHREEQC hydrogeochemical model to analyse groundwater chemistry data obtained during the wet (February and May) and dry seasons (August and December) of 2011. The XRF and XRD results show that the channel deposits are dominated by SiO₂ element oxides and quartz minerals, thus elevated concentrations of silicon (Si⁴⁺) were found in the groundwater. Dolomite and calcite minerals were also detected in the unconsolidated aquifer sediments. The detailed study of the alluvial aquifer system has shown that dissolution of dolomite and calcite minerals and ion exchange are the dominant hydrogeochemical processes influencing the groundwater quality. The groundwater evolves from Ca²⁺–Mg²⁺–HCO₃ ^? recharge water that goes through ion exchange with Na⁺ in the clay-silt sediment to give a Na⁺–HCO₃ ^? water type. The groundwater is supersaturated with respect to quartz, dolomite and calcite minerals. The study shows the potential usefulness of simple bivariate plots as a complimentary tool to the conventional methods for analyzing groundwater hydrogeochemical processes.     

Overview of calcite/opal deposits at or near the proposed high-level nuclear waste site,Yucca Mountain,Nevada, USA: Pedogenic,hypogene, or both?

Calcite/opal deposits (COD) at Yucca Mountain were studied with respect to their regional and field geology, petrology and petrography, chemistry and isotopic geochemistry, and fluid inclusions. They were also compared with true pedogenic deposits (TPD), groundwater spring deposits (GSD), and calcite vein deposits (CVD) in the subsurface. Some of the data are equivocal and can support either a hypogene or pedogenic origin for these deposits. However, Sr-, C-, and O-isotope, fluid inclusion, and other data favor a hypogene interpretation. A hypothesis that may account for all currently available data is that the COD precipitated from warm, CO₂-rich water that episodically upwelled along faults during the Pleistocene, and which, upon reaching the surface, flowed downslope within existing alluvial, colluvial, eluvial, or soil deposits. Being formed near, or on, the topographic surface, the COD acquired characteristics of pedogenic deposits. This subject relates to the suitability of Yucca Mountain as a high-level nuclear waste site.     

Mineralogy and chemistry of bentonite (?) deposits at Minjingu, Lake Manyara, North Tanzania

Olive green clays likely to be bentonitic in composition have been mineralogically and chemically studied. They occur in association with other lacustrine sediments at Lake Manyara. Radiocarbon dates from four diatom horizons indicate ages ranging from 12 Ka to 135 Ka suggesting a Mid-Holocene age. Middle Pleistocene age have been assigned to the ridged oncolites of Lake Manyara. The olive green coloured clays in the Manyara basin are known to occur in association with other lake beds including phosphorite deposits, stromatolites, bioturbated silty clays, partly silicified marls, conglomerates and olive green coloured opal beds. The results presented herein are from the olive green coloured clays. The olive green clays (bentonite?) are a result of devitrification or alteration of volcanic ashes and/or pyroclasts. The green clays occur in different forms as they are separated from each other by other lacustrine sediments. The alteration might have taken place in slightly different environments in terms of salinity and alkalinity. One of the top layer is friable and shows conchoidal fractures when dry. The other beds below in the lacustrine sequence are cemented with calcite and some dolomite as well as zeolites. The lowermost layer in the sequence is friable and shows cracks filled with coarse crystalline calcite. Mineralogically the bentonite is composed of the clay minerals illite, illite-smectite mixed layer clays, and chlorite. Other authigenic minerals include various zeolites (analcime, clinoptilolite, erionite and some traces of mordenite), opal, and fluorapatite. The clays have magnesium contents varying from 3.01% to 7.43%. The calcium contents vary widely due to presence or absence of one of the two minerals calcite or apatite. Trace elements like Ba, Ce, Sr, Zr are equally attributed to the presence of calcite and apatite. The formation of the illite-smectite mixed layer clays in an alternating manner with other lake sediments depicts different episodes of volcanic eruptions in the area. The mineralogical composition of smectites, zeolites, and opal in the green clays suggests a deposition of pyroclasts and volcanic ashes in a closed lake system with fluctuating levels. Due to evaporation alkalinity and salinity levels were fluctuating. The clays might have been bentonite which have undergone illitisation, a phenomena noted in other neighbouring rift basins.     

Compositional Evolution of Pyrochlore-Group Minerals in Carbonatites of the Belaya Zima Pluton,Eastern Sayan

Pyrochlore-group minerals are the main concentrators of niobium in carbonatites of the Belaya Zima alkaline pluton. Fluorcalciopyrochlore, kenopyrochlore and hydropyrochlore were identified in chemical composition. Their main characteristics are given: compositional variation, morphology, and zoning. During evolution from early calcite to late ankerite carbonatites, the UO₂, TiO₂, REE, and Y contents gradually increased. All carbonatite types are suggested to contain initial fluorcalciopyrochlore. However, in calcite–dolomite and ankerite carbonatites, it is partially or completely hydrated due to hydrothermal processes at the late stage of the pluton. This hydration resulted in the appearance of kenopyrochlore and hydropyrochlore due to removal of Ca, Na and F, and input of Ba, H₂O, K, Si, Fe, and probably U and REE. At the last stage of the pluton, this hydrated pyrochlore was replaced by Fe-bearing columbite.