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1.
In situ U-Pb SHRIMP analysis of hydrothermal monazite virtually free of Th and poor in U (<0.2 ppm Th, 40-103 ppm U) from the world-class Llallagua tin porphyry deposit in Bolivia defines a mineralization age of 23.4 ± 2.2 Ma (MSWD 0.48) confirming earlier K-Ar sericite alteration age data. These ages are, however, in contrast with a weighted mean single crystal 207Pb/206Pb evaporation age of 39.3 ± 6.0 Ma, and a related Pb-Pb inverse isochron age of 42.4 ± 4.0 Ma (MSWD 0.66) on zircon from a post-porphyry dike, as well as with an earlier single crystal Sm-Nd apatite isochron age.Our data points to a significant time gap between emplacement of the ore-hosting porphyry intrusion (magmatism) and its hydrothermal overprint (tin mineralization), suggesting long-lived magmatic-hydrothermal activity in this part of the Andean back-arc crust. The decoupling of porphyry magmatism and hydrothermal activity may explain the unusual occurrence of relatively little fractionated felsic rocks together with extensive tin mineralization.Our study demonstrates the usefulness of the application of the U-Pb SHRIMP method to direct age determination of ore mineralization using Th-poor hydrothermal monazite even when dealing with geological young events. The common assumption of synchronous magmatism and hydrothermal ore formation in porphyry systems may not always be warranted.  相似文献   

2.
We performed in situ Th-Pb dating of monazite in upper amphibolite facies pelitic schist from the Grouse Creek Mountains in northwest Utah. Sixty-six ages from inclusions in four garnet grains range from 37 to 72 Ma and decrease with radial distance from garnet cores. The age range of 30 matrix monazite grains overlaps and extends to younger ages than inclusions (25-58 Ma). The monazite grains are not intersected by cracks in the garnets, through which dissolution, reprecipitation or Pb loss might occur, and are generally too small (<20 μm) to allow for more than one age determination on any one grain. Processes that might explain inclusion ages that decrease with radial distance from garnet cores include: (1) Pb diffusion in monazite, (2) dissolution and reprecipitation of monazite, and (3) co-crystallization of monazite and garnet. After consideration of these possibilities, it is concluded that the co-crystallization of monazite and garnet is the most plausible, with monazite neoblasts deriving REEs from the breakdown of muscovite. Garnet ages derived by regression of the inclusion ages and assuming a constant rate of volume increase during garnet growth yield model ages with a maximum difference between core and rim of 22 m.y.  相似文献   

3.
Rapid Pb-Pb dating of natural rutile crystals by laser ablation multiple-collector inductively coupled plasma mass spectrometry (LA-MC-ICPMS) is investigated as a tool for constraining geological temperature-time histories. LA-MC-ICPMS was used to analyse Pb isotopes in rutile from granulite-facies rocks from the Reynolds Range, Northern Territory, Australia. The resultant ages were compared with previous U-Pb zircon and monazite age determinations and new mica (muscovite, phlogopite, and biotite) Rb-Sr ages from the same metamorphic terrane. Rutile crystals ranging in size from 3.5 to 0.05 mm with ?20 ppm Pb were ablated with a 300-25 μm diameter laser beam. Crystals larger than 0.5 mm yielded sufficiently precise 206Pb/204Pb and 207Pb/204Pb ratios to correct for the presence of common Pb, and individual rutile crystals often exhibited sufficient Pb isotopic heterogeneity to allow isochron calculations to be performed on replicate analyses of a single crystal. The mean of 12 isochron ages is 1544 ± 8 Ma (2 SD), with isochron ages for single crystals having uncertainties as low as ±1.3 Myr (2 SD). The 207Pb-206Pb ages calculated without correction for common Pb are typically <0.5% higher than the common-Pb-corrected isochron ages reflecting the very minor amounts of common Pb present in the rutile. The LA-MC-ICPMS method described samples only the outer 0.1-0.2 mm of the rutile crystals, resulting in a grain size-independent apparent closure temperature (Tc) for Pb diffusion in rutile that is less than the Tc of monazite ?0.1 mm in diameter, but significantly higher than the Rb-Sr system in muscovite (550 °C), phlogopite (435 °C) and biotite (400 °C). Even small rutile crystals are extremely resistant to isotopic resetting. For the established slow cooling rate of ca. 3 °C/Myr, the Tc for Pb diffusion in the analysed rutile is ca. 630 °C. This is in excellent agreement with recent experimental results that indicate that rutile has a higher Tc than previously thought (ca. 600-640 °C for rutile 0.1-0.2 mm diameter cooled at 3 °C/Myr; near 600 °C [Cherniak D.J., 2000. Pb diffusion in rutile. Contrib. Mineral. Petrol. 139, 198-207], versus 400 °C [Mezger, K., Hanson G.N., Bohlen S.R., 1989a. High precision U-Pb ages of metamorphic rutile: applications to the cooling history of high-grade terranes. Earth Planet. Sci. Lett. 96, 106-118.] for 1 °C/Myr), and with current Tc estimates for monazite and other high temperature geochronometers, which have been revised upwards in recent years. The new rutile ages, together with the other geochronological data from the region, support the interpretation that the Reynolds Range underwent prolonged slow cooling on a conductive geotherm, under nearly steady-state conditions. Slow cooling at ca. 3 °C/Myr persisted for at least 40 Myr followed the peak of high-T/low-P metamorphism to granulite-facies conditions, and probably continued at ca. 2-3 °C/Myr for ca. 200 Myr overall.  相似文献   

4.
We have performed experiments to evaluate Au solubility in natural, water-saturated basaltic melts as a function of oxygen fugacity. Experiments were carried out at 1000 °C and 200 MPa, and oxygen fugacity was controlled at the fayalite-magnetite-quartz (FMQ) oxygen fugacity buffer and FMQ + 4. All experiments were saturated with a metal-chloride aqueous solution loaded initially as a 10 wt% NaCl eq. fluid. The stable phase assemblage at FMQ consists of basalt melt, olivine, clinopyroxene, a single-phase aqueous fluid, and metallic Au. The stable phase assemblage at FMQ + 4 consists of basalt melt, clinopyroxene, magnetite-spinel solid solution, a single-phase aqueous fluid, and metallic Au. Silicate glasses (i.e., quenched melt) and their contained crystalline material were analyzed by using both electron probe microanalysis (EPMA) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Measured Au concentrations in the quenched melt range from 4.8 μg g−1 to 0.64 μg g−1 at FMQ + 4, and 0.54 μg g−1 to 0.1 μg g−1 at FMQ. The measured solubility of Au in olivine and clinopyroxene was consistently below the LA-ICP-MS limit of detection (i.e., 0.1 μg g−1). These melt solubility data place important limitations on the dissolved Au content of water-saturated, Cl- and S-bearing basaltic liquids at geologically relevant fO2 values. The new data are compared to published, experimentally-determined values for Au solubility in dry and hydrous silicate liquids spanning the compositional range from basalt to rhyolite, and the effects of melt composition, oxygen fugacity, pressure and temperature are discussed.  相似文献   

5.
Two samples of produced-water collected from a storage tank at US Geological Survey research site B, near Skiatook Lake in northeastern Oklahoma, have activity concentrations of dissolved 226Ra and 228Ra that are about 1500 disintegrations/min/L (dpm/L). Produced-water also contains minor amounts of small (5–50 μm) suspended grains of Ra-bearing BaSO4 (barite). Precipitation of radioactive barite scale in the storage tank is probably hindered by low concentrations of dissolved SO4 (2.5 mg/L) in the produced-water. Sediments in a storage pit used to temporarily collect releases of produced-water have marginally elevated concentrations of “excess” Ra (several dpm/g), that are 15–65% above natural background values. Tank and pit waters are chemically oversaturated with barite, and some small (2–20 μm) barite grains observed in the pit sediments could be transferred from the tank or formed in place. Measurements of the concentrations of Ba and excess Ra isotopes in the pit sediments show variations with depth that are consistent with relatively uniform deposition and progressive burial of an insoluble Ra-bearing host (barite?). The short-lived 228Ra isotope (half-life = 5.76 a) shows greater reductions with depth than 226Ra (half-life = 1600 a), that are likely explained by radioactive decay. The 228Ra/226Ra activity ratio of excess Ra in uppermost pit sediments (1.13–1.17) is close to the ratio measured in the samples of produced-water (0.97, 1.14). Declines in Ra activity ratio (excess) with sediment depth can be used to estimate an average rate of burial of 4 cm/a for the Ra-bearing contaminant. Local shallow ground waters contaminated with NaCl from produced-water have low dissolved Ra (<20 dpm/L) and also are oversaturated with barite. Barite is a highly insoluble Ra host that probably limits the environmental mobility of Ra at site B.  相似文献   

6.
To evaluate in situ Pb dating by laser ablation multiple-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS), we analysed apatite, sphene, and monazite from Paleoproterozoic metamorphic rocks from West Greenland. Pb isotope ratios were also determined in the National Institute of Standards and Technology (NIST) 610 glass standard and were corrected for mass fractionation by reference to the measured thallium isotope ratio. The NIST 610 glass was used to monitor Pb isotope mass fractionation in the low Tl/Pb accessory minerals. Replicate analyses of the glass (1 to 2 min) yielded ratios with an external reproducibility comparable to conventional analyses of standard reference material 981 by thermal ionisation mass spectrometry (TIMS). Mineral grains were generally analysed with a 100-μm laser beam, although some monazite crystals were analysed at smaller spot sizes (10 and 25 μm). The common Pb isotope ratios required for age calculations were either measured on coexisting plagioclase by LA-MC-ICP-MS or could be ignored, as individual crystals exhibit sufficient Pb isotopic heterogeneity to perform isochron calculations on replicate analyses of single crystals. Mean mineral ages with the 204Pb ion beam measured in the multiplier were as follows: apatite, 1715 ± 23 m.y.; sphene, 1789 ± 11 m.y.; and monazite, 1783 to 1888 m.y., with relative uncertainties on individual monazite ages of <0.2% but highly reproducible age determinations on single monazite crystals (?1%). Isochron ages calculated from several mineral analyses without assumption of common Pb also yield precise age determinations. Apatite and monazite Pb ages determined by in situ Pb isotope analysis are identical to those determined by conventional TIMS analysis of bulk mineral separates, and the analytical uncertainties of these short laser analyses with no prior mechanical or chemical separation are comparable to those obtained by TIMS. Detailed examination of the sphene in situ age data does, however, show a small discrepancy between the LA-MC-ICP-MS and TIMS ages (∼1% younger). High-resolution mass scans of the sphene during ablation clearly showed several small and as yet unidentified isobaric interferences that overlap with the 207Pb peak at the resolution conditions for measurement of isotope ratios. These might account for the age discrepancy between the LA-MC-ICP-MS and TIMS sphene ages. LA-MC-ICP-MS is a rapid, accurate, and precise method for in situ determination of Pb isotope ratios that can be used for geochronological studies in a manner similar to an ion microprobe, albeit currently at a somewhat degraded spatial resolution. Further modifications to the LA-MC-ICP-MS system, such as improved sensitivity, ion transmission, and LA methodology, may lead to this type of instrument becoming the method of choice for many types of in situ Pb isotope dating.  相似文献   

7.
Zircon was grown from trace-element doped hydrous peralkaline rhyolite melts with buffered oxygen fugacities in cold-seal experiments at 0.1 and 0.2 GPa and 800 °C and piston-cylinder experiments at 1.5 GPa and 900-1300 °C. Zircon and glass were present in all run products, and small monazite crystals were present in eight of the 12 experiments. Average diameters of zircon crystals ranged from 5 to 20 μm at 800 °C to 30-50 μm at 1300 °C. Zircon crystals have thin rims, and adjacent glass has a narrow (∼1 μm thick) compositional boundary layer. Concentrations obtained through in-situ analysis of cores of run product zircon crystals and melt pools were used to calculate trace-element partition coefficients Dzircon/melt for P, Sc, Ti, V, Y, La, Ce, Pr, Nd, Eu, Gd, Ho, Yb, Lu, Hf, Th, and U. In most cases Lu was the most (D 12-105) and La the least (0.06-0.95) compatible elements. D values from this study fall within the range of previously measured values for Rare Earth Elements (REE). However, D values measured experimentally show less fractionation than those recently measured using natural phenocryst/matrix pairs. For example, DLu/DLa measured experimentally in this study range between 27 and 206 compared to a value of 706,522 for a natural zircon/dacite pair [Sano, Y., Terada, K., and Fukuoka, T. 2002 High mass resolution ion microprobe analysis of rare earth elements in silicate glass, apatite and zircon: lack of matrix dependency. Chem. Geol.184, 217-230]. Although D values from this study show good agreement with the lattice strain model, D values from natural phenocryst/matrix pairs combined with measured zircon compositions better reproduce host-rock (magma) compositions of igneous rocks. They also yield more reasonable estimates of magma compositions when combined with compositions of ‘‘out-of-context” zircons. For example, compositions of the Hadean detrital zircons from Jack Hills, Australia yield LREE-enriched magmas when combined with D values from phenocryst/matrix pairs yields, but yield LREE-depleted magmas when experimentally determined D values are used. We infer that experimentally measured Dzircon/melt values represent disequilibrium partitioning resulting from rapid zircon growth during short laboratory timescales. Rapid growth causes development of observed diffusive boundary layers in the melt adjacent to zircon crystals. D values from phenocryst/matrix pairs are therefore recommended for petrogenetic modeling.  相似文献   

8.
The mineral barite (BaSO4) accommodates calcium in its crystal lattice, providing an archive of Ca-isotopes in the highly stable sulfate mineral. Holocene marine (pelagic) barite samples from the major ocean basins are isotopically indistinguishable from each other (δ44/40Ca = −2.01 ± 0.15‰) but are different from hydrothermal and cold seep barite samples (δ44/40Ca = −4.13 to −2.72‰). Laboratory precipitated (synthetic) barite samples are more depleted in the heavy Ca-isotopes than pelagic marine barite and span a range of Ca-isotope compositions, Δ44/40Ca = −3.42 to −2.40‰. Temperature, saturation state, , and aCa2+/aBa2+ each influence the fractionation of Ca-isotopes in synthetic barite; however, the fractionation in marine barite samples is not strongly related to any measured environmental parameter. First-principles lattice dynamical modeling predicts that at equilibrium Ca-substituted barite will have much lower 44Ca/40Ca than calcite, by −9‰ at 0 °C and −8‰ at 25 °C. Based on this model, none of the measured barite samples appear to be in isotopic equilibrium with their parent solutions, although as predicted they do record lower δ44/40Ca values than seawater and calcite. Kinetic fractionation processes therefore most likely control the extent of isotopic fractionation exhibited in barite. Potential fractionation mechanisms include factors influencing Ca2+ substitution for Ba2+ in barite (e.g. ionic strength and trace element concentration of the solution, competing complexation reactions, precipitation or growth rate, temperature, pressure, and saturation state) as well as nucleation and crystal growth rates. These factors should be considered when investigating controls on isotopic fractionation of Ca2+ and other elements in inorganic and biogenic minerals.  相似文献   

9.
High-purity synthetic barite powder was added to pure water or aqueous solutions of soluble salts (BaCl2, Na2SO4, NaCl and NaHCO3) at 23 ± 2 °C and atmospheric pressure. After a short pre-equilibration time (4 h) the suspensions were spiked either with 133Ba or 226Ra and reacted under constant agitation during 120-406 days. The pH values ranged from 4 to 8 and solid to liquid (S/L) ratios varied from 0.01 to 5 g/l. The uptake of the radiotracers by barite was monitored through repeated sampling of the aqueous solutions and radiometric analysis. For both 133Ba and 226Ra, our data consistently showed a continuous, slow decrease of radioactivity in the aqueous phase.Mass balance calculations indicated that the removal of 133Ba activity from aqueous solution cannot be explained by surface adsorption only, as it largely exceeded the 100% monolayer coverage limit. This result was a strong argument in favor of recrystallization (driven by a dissolution-precipitation mechanism) as the main uptake mechanism. Because complete isotopic equilibration between aqueous solution and barite was approached or even reached in some experiments, we concluded that during the reaction all or substantial fractions of the initial solid had been replaced by newly formed barite.The 133Ba data could be successfully fitted assuming constant recrystallization rates and homogeneous distribution of the tracer into the newly formed barite. An alternative model based on partial equilibrium of 133Ba with the mineral surface (without internal isotopic equilibration of the solid) could not reproduce the measured activity data, unless multistage recrystallization kinetics was assumed. Calculated recrystallization rates in the salt solutions ranged from 2.8 × 10−11 to 1.9 × 10−10 mol m−2 s−1 (2.4-16 μmol m−2 d−1), with no specific trend related to solution composition. For the suspensions prepared in pure water, significantly higher rates (∼5.7 × 10−10 mol m−2 s−1 or ∼49 μmol m−2 d−1) were determined.Radium uptake by barite was determined by monitoring the decrease of 226Ra activity in the aqueous solution with alpha spectrometry, after filtration of the suspensions and sintering. The evaluation of the Ra uptake experiments, in conjunction with the recrystallization data, consistently indicated formation of non-ideal solid solutions, with moderately high Margules parameters (WAB = 3720-6200 J/mol, a0 = 1.5-2.5). These parameters are significantly larger than an estimated value from the literature (WAB = 1240 J/mol, a0 = 0.5).In conclusion, our results confirm that radium forms solid solutions with barite at fast kinetic rates and in complete thermodynamic equilibrium with the aqueous solutions. Moreover, this study provides quantitative thermodynamic data that can be used for the calculation of radium concentration limits in environmentally relevant systems, such as radioactive waste repositories and uranium mill tailings.  相似文献   

10.
Since studies on deep-sea cores were carried out in the early 1990s it has been known that ambient temperature may have a marked affect on apatite fission track annealing. Due to sluggish annealing kinetics, this effect cannot be quantified by laboratory annealing experiments. The unknown amount of low-temperature annealing remains one of the main uncertainties for extracting thermal histories from fission track data, particularly for samples which experienced slow cooling in shallow crustal levels. To further elucidate these uncertainties, we studied volcanogenic sediments from five deep-sea drill cores, that were exposed to maximum temperatures between ∼10° and 70 °C over geological time scales of ∼15-120 Ma. Mean track lengths (MTL) and etch pit diameters (Dpar) of all samples were measured, and the chemical composition of each grain analysed for age and track length measurements was determined by electron microprobe analysis. Thermal histories of the sampled sites were independently reconstructed, based on vitrinite reflectance measurements and/or 1D numerical modelling. These reconstructions were used to test the most widely used annealing models for their ability to predict low-temperature annealing. Our results show that long-term exposure to temperatures below the temperature range of the nominal apatite fission track partial annealing zone results in track shortening ranging between 4 and 11%. Both chlorine content and Dpar values explain the downhole annealing patterns equally well. Low chlorine apatite from one drill core revealed a systematic relation between Si-content and Dpar value. The question whether Si-substitution in apatite has direct and systematic effects on annealing properties however, cannot be addressed by our data. For samples, which remained at temperatures <30 °C, and which are low in chlorine, the Laslett et al. [Laslett G., Green P., Duddy I. and Gleadow A. (1987) Thermal annealing of fission tracks in apatite. Chem. Geol. 65, 1-13] annealing model predicts MTL up to 0.6 μm longer than those actually measured, whereas for apatites with intermediate to high chlorine content, which experienced temperatures >30 °C, the predictions of the Laslett et al. (1987) model agree with the measured MTL data within error levels. With few exceptions, predictions by the Ketcham et al. [Ketcham R., Donelick R. and Carlson W. (1999) Variability of apatite fission-track annealing kinetics. III: Extrapolation to geological time scales. Am. Mineral. 84/9, 1235-1255] annealing model are consistent with the measured data for samples which remained at temperatures below ∼30 °C. For samples which experienced maximum temperatures between ∼30 and 70 °C, and which are rich in chlorine, the Ketcham et al. (1999) model overestimates track annealing.  相似文献   

11.
Rb-Sr and U-Pb isotopic data for granulite facies rocks, forming textural relics with respect to eclogite facies metamorphism in the Western Gneiss Region (WGR) of Norway, highlight the importance of textures and mineral reaction kinetics for the interpretation of geochronological data. Studied rocks from Bårdsholmen, southern WGR, were subjected to granulite facies metamorphism at 955 ± 3 Ma (U-Pb, zircon). Later on, they experienced a subduction-related, kinetically stranded eclogitization (T > 650 °C at ∼20 kbar) at 404 ± 2 Ma (Rb-Sr multimineral internal isochron data), followed by exhumation through amphibolite facies conditions. Full conversion of granulite to eclogite was restricted to zones of fluid infiltration and deformation. Despite the fact that metamorphic temperatures vastly exceeded the commonly assumed ‘closure temperature’ for Rb-Sr in submillimeter-sized biotite for several Ma during eclogite facies overprint, Sr-isotopic signatures of relic biotite have not been fully reset. Large biotite crystals nearly record their Sveconorwegian (Grenvillian) crystallization age. Sr signatures of other granulite facies phases (feldspar, pyroxenes, amphibole) remained unchanged, with the exception of apatite. The results imply that isotopic signatures much closer correspond to the P, T conditions of formation recorded by a dated phase and its paragenesis, than to a temperature history. In texturally well-equilibrated high-grade rocks which experienced no mineral reactions and remained devoid of free fluids during exhumation, like granulites or eclogites, isotopic resetting during cooling is either kinetically locked, or restricted to sluggish intermineral diffusion which demonstrably does not lead to full isotopic homogenization. In texturally unequilibrated rocks, textural relics are likely to represent isotopic relics. It is shown that for both high-grade rocks and for rocks with textural disequilibria, geologically meaningful isotopic ages based on isochron methods can only be derived from sub-assemblages in isotopic equilibrium, which have to be defined by analysis of all rock-forming minerals. Conventional two-point ‘mica ages’ for such rocks are a priori geochronologically uninterpretable, and valid multimineral isochron ages a priori do not record cooling but instead date recrystallization-inducing processes like fluid-rock interaction.  相似文献   

12.
Batch and column experiments were conducted to examine the capability of naturally formed hematite and siderite to remove As from drinking water. Results show that both minerals were able to remove As from aqueous solutions, but with different efficiencies. In general, each material removed arsenate much more efficiently than As–DMA (dimethylarsinic acid), with the lowest adsorption efficiency for arsenite. The best removal efficiency for As species was obtained using a hematite, with a grain size range between 0.25 and 0.50 mm. The adsorption capacity for inorganic As(V) reached 202 μg/g. The pH generally had a great impact on the arsenate removal by the Fe minerals studied, while arsenite removal was slightly dependent on the initial pH of between 3 and 10. The presence of phosphate always had a negative effect on arsenate adsorption, due to competitive adsorption between them. A column packed with hematite in the upper half and siderite in the lower half with a grain size range of 0.25–0.5 mm proved to be an efficient reactive filter for the removal of all As species, causing a decrease in As concentration from 500 μg/L (including 200 μg/L As(V) as arsenate, 200 μg/L As(III) as arsenite and 100 μg/L As(V) as DMA) to less than 10 μg/L after 1055 pore volumes of water were filtered at a flow rate of 0.51 mL/min. After 2340 pore volumes passed through the column filter, the total inorganic As in the effluent was less than 5 μg/L. The total As load in the column filter was estimated to be 0.164 mg/g. Results of μ-synchrotron X-ray fluorescence analysis (μ-XRFA) suggest that coatings of fresh Fe(III) oxides, formed on the surface of the siderite grains after two weeks of operation, greatly increased the adsorption capacity of the filling material towards As.  相似文献   

13.
Kinetics of isotopic equilibrium in the mineral radiometric systems of igneous and metamorphic rocks is an important issue in geochronology. It turns out that temperature is the most important factor in dictating isotopic equilibrium or disequilibrium with respect to diffusion mechanism. Contemporaneous occurrence of Mesozoic granites and gneisses in the Dabie orogen of China allows us to evaluate the thermal effect of magma emplacement and associated metamorphism on mineral radiometric systems. Zircon U-Pb, mineral Rb-Sr and O isotope analyses were carried out for a Cretaceous granite and its host gneiss (foliated granite) from North Dabie. Zircon U-Pb dating gave consistently concordant ages of 127 ± 3 Ma and 128 ± 2 Ma for the granite and the gneiss, respectively. A direct correspondence in equilibrium state is observed between the O and Rb-Sr isotope systems of both granitic and gneissic minerals. Mineral O isotope temperatures correlate with O diffusion closure temperatures under conditions of slow cooling, indicating attainment and preservation of O isotope equilibrium in these minerals. The mineral Rb-Sr isochron of granite, constructed by biotite, feldspar, apatite and whole-rock with the O isotope equilibrium, yields a meaningful age of 118 ± 3 Ma, which is in accordance with the mineral Rb-Sr isochron age of 122 ± 1 Ma for the host gneiss. The consistency in both U-Pb and Rb-Sr ages between the granite and the gneiss suggests a contemporaneous process of crystallizing the zircons and resetting the Rb-Sr radiometric systems during magma emplacement and granite foliation. Whereas the zircon U-Pb ages for both granite and gneiss are interpreted as the timing of magma crystallization, the young Rb-Sr isochron ages record the timing of Sr diffusion closure during the slow cooling. Protolith of the gneiss crystallized shortly before intrusion of the granite, so that it was able to be foliated by voluminous emplacement of coeval mafic to felsic magmas derived by anatexis of orogenic lithospheric keel. Therefore, extensional collapse of collision-thickened crust at Early Cretaceous is suggested to trigger the post-collisional magmatism, which in turn serves as an essential driving force for the contemporaneous high-T deformation/metamorphism.  相似文献   

14.
Due to the widespread contamination of groundwater resources with arsenic (As), controls on As mobility have to be identified. In this study we focused on the distribution of As in the dissolved, colloidal and particulate size fraction of experimental solutions rich in ferric iron, dissolved organic matter (DOM) and As(V). Size fractions between <5 kDa and >0.2 μm were separated by filtration and their elemental composition was analyzed. A steady-state particle size distribution with stable element concentration in the different size classes was attained within 24 h. The presence of DOM partly inhibited the formation of large Fe-(oxy)hydroxide aggregates, thus stabilized Fe in complexed and colloidal form, when initially adjusted molar Fe/C ratios in solution were <0.1. Dissolved As concentrations and the quantity of As bound to colloids (<0.2 μm) increased in the presence of DOM as well. At intermediate Fe/C ratios of 0.02-0.1, a strong correlation between As and Fe concentration occurred in all size fractions (R2 = 0.989). At Fe/C ratios <0.02, As was mainly present in the dissolved size fraction. These observations indicate that As mobility increased in the presence of DOM due to (I) competition between As and organic molecules for sorption sites on Fe particles; and (II) due to a higher amount of As bound to more abundant Fe colloids or complexes <0.2 μm in size. The amount of As contained in the colloidal size fractions also depended strongly on the initial size of the humic substance, which was larger for purified humic acids than for natural river or soil porewater samples. Arsenic in the particle size fraction >0.2 μm additionally decreased in the order of pH 4 ? 6 > 8. The presence of DOM likely increases the mobility of As in iron rich waters undergoing oxidation, a finding that has to be considered in the investigation of organic-rich terrestrial and aquatic environments.  相似文献   

15.
Geochemical variations in stream sediments (n = 54) from the Mahaweli River of Sri Lanka have been evaluated from the viewpoints of lithological control, sorting, heavy mineral concentration, influence of climatic zonation (wet, intermediate, and dry zones), weathering, and downstream transport. Compositions of soils (n = 22) and basement rocks (n = 38) of the catchment and those of <180 μm and 180–2000 μm fractions of the stream sediments were also examined. The sediments, fractions, soils and basement rocks were analyzed by X-ray fluorescence to determine their As, Pb, Zn, Cu, Ni, Cr, V, Sr, Y, Nb, Zr, Th, Sc, Fe2O3, TiO2, MnO, CaO, P2O5 and total sulfur contents. Abundances of high field strength and ferromagnesian elements in the sediments indicate concentration of durable heavy minerals including zircon, tourmaline, rutile, monazite, garnet, pyriboles, and titanite, especially in <180 μm fractions. The sediments show strong correlation between Ti and Fe, further suggesting presence of heavy mineral phases containing both elements, such as ilmenite and magnetite. The basement rocks range from mafic through to felsic compositions, as do the soils. The river sediments lack ultrabasic components, and overall have intermediate to felsic compositions. Elemental spikes in the confluences of tributary rivers and high values in the <180 μm fractions indicate sporadic inputs of mafic detritus and/or heavy minerals to the main channel. Al2O3/(K2O + Na2O) and K2O/Na2O ratios of the sediments and LOI values of the soils correlate well with the climatic zones, suggesting intense weathering in the wet zone, lesser weathering in the intermediate zone, and least weathering in the dry zone. Low Sr and CaO contents and Cr/V ratios in stream sediments in the wet zone also suggest climatic influence. Fe-normalized enrichment factors (EFs) for As, Pb, Zn, Cu, Ni and Cr in stream sediments in the main channel are nearly all <1.5, indicating there is no significant environmental contamination. The chemistry of the sediments, rocks and the soils in the Mahaweli River are thus mainly controlled by source lithotype, weathering, sorting, and heavy mineral accumulation.  相似文献   

16.
We report 39Ar-40Ar ages of whole rock (WR) and plagioclase and pyroxene mineral separates of nakhlites MIL 03346 and Y-000593, and of WR samples of nakhlites NWA 998 and Nakhla. All age spectra are complex and indicate variable degrees of 39Ar recoil and variable amounts of trapped 40Ar in the samples. Thus, we examine possible Ar-Ar ages in several ways. From consideration of both limited plateau ages and isochron ages, we prefer Ar-Ar ages of NWA 998 = 1334 ± 11 Ma, MIL 03346 = 1368 ± 83 Ma (mesostasis) and 1334 ± 54 Ma (pyroxene), Y-000593 = 1367 ± 7 Ma, and Nakhla = 1357 ± 11 Ma, (2σ errors). For NWA 998 and MIL 03346 the Ar-Ar ages are within uncertainties of preliminary Rb-Sr isochron ages reported in the literature. These Ar-Ar ages for Y-000593 and Nakhla are several Ma older than Sm-Nd ages reported in the literature. We conclude that the major factor in producing Ar-Ar ages slightly too old is the presence of small amounts of trapped martian or terrestrial 40Ar on weathered grain surfaces that was degassed along with the first several percent of 39Ar. A total K-40Ar isochron for WR and mineral data from five nakhlites analyzed by us, plus Lafayette data in the literature, gives an isochron age of 1325 ± 18 Ma (2σ). We emphasize the precision of this isochron over the value of the isochron age. Our Ar-Ar data are consistent with a common formation age for nakhlites. The cosmic-ray exposure (CRE) age for NWA 998 of ∼12 Ma is also similar to CRE ages for other nakhlites.  相似文献   

17.
We have employed Lu-Hf apatite chronology to determine the age of a magnetite-rich melatroctolite in southern Sweden, known as the Smålands Taberg Fe-Ti ore deposit. The melatroctolite is poor in incompatible elements and minerals forming at more advanced stages of differentiation, which precludes the use of minerals (baddeleyite, zircon, titanite or apatite) commonly used for dating the emplacement of igneous rocks. Enclaves of leucogabbro in the melatroctolite have REE patterns parallel with the host melatroctolite and identical initial Hf and Nd isotope compositions. These characteristics are conclusive evidence for a common parental magma. The leucogabbro is a slightly more evolved facies that underwent limited fractionation of olivine and titanomagnetite; the two major mineral phases in the melatroctolite. Apatite and plagioclase, separated from the leucogabbro, plus a whole-rock sample define a Lu-Hf isochron with a slope corresponding to an age of 1204.3 ± 1.8 Ma. This result is close to the lower age boundary previously reported for this magmatic event comprising dolerites, syenites and granites. The Lu-Hf apatite chronometer merits attention as a new tool in generating accurate and precise ages for igneous, silica-undersaturated rocks that may be difficult to date with traditional techniques.  相似文献   

18.
The heat of precipitation, the mean crystal size and the broadness of crystal size distribution of barium sulfate precipitating in aqueous solutions of different background electrolytes (KCl, NaCl, LiCl, NaBr or NaF), was shown to vary at constant thermodynamic driving force (supersaturation) and constant ionic strength depending on the salt present in solution. The relative inversion in the effect of respective background ions on the characteristics of barite precipitate was observed between two studied supersaturation (Ω) and ionic strength (IS) conditions. The crystal size variance (β2) increased in the presence of background electrolytes in the order LiCl < NaCl < KCl at Ω = 103.33 and IS = 0.03 M and KCl < NaCl < LiCl at Ω = 103.77 and IS = 0.09 M. At a given Ω and IS the respective size of barite crystals decreased with increasing β2 in chloride salts of different cations and remained constant in sodium salts of different anions.We suggest that ionic salts affect the kinetics of barite nucleation and growth due to their influence on water of solvation and bulk solvent structure. This idea is consistent with the hypothesis that the kinetic barrier for barium sulfate nucleation depends on the frequency of water exchange around respective building units that can be modified by additives present in solution. In electrolyte solution the relative switchover between long range electrostatic interactions and short range hydration forces, which influence the dynamics of solvent exchange between an ion solvation shell and bulk fluid, results in the observed inversion in the effect of differently hydrated salts on nucleation rates and the resulting precipitate characteristics.  相似文献   

19.
This paper mainly describes mineralogy and geochemistry of coals from the Weibei coalfield in the southeastern Ordos Basin, North China. A number of Al-hydroxide/oxyhydroxide minerals were detected in the Late Carboniferous coals (Nos. 5, 10 and 11 coals), especially in the No. 10 coal. Aluminum-hydroxide/oxyhydroxide minerals (nordstrandite, boehmite and diaspore) in the No. 10 coal are associated with kaolinite, suggesting that these minerals are derived from the breakdown of kaolinite. A model in which Al-hydroxide/oxyhydroxide minerals form from the incongruent dissolution of kaolinite is presented. Nordstrandite and boehmite mainly occur as massive lenses (<500 μm in length). Diaspore appears as massive aggregates and as single euhedral crystals (<50 μm in length) in a kaolinite matrix. The presence of high temperature quartz, and zircon indicates that there was input of felsic volcanic debris during accumulation of the Late Carboniferous coals. These volcanic materials have also had a significant influence on the enrichment of certain trace elements including Li, Be, Ga, Zr, Nb, Mo, Sn, W and U in the Late Carboniferous coals (Nos. 5, 10, and 11 coals). SEM-EDX results show that Ga in the No. 10 coal (whole coal average 33.4 μg/g; n = 2) mainly occurs within Al-hydroxide/oxyhydroxide minerals (nordstrandite, boehmite, and diaspore), kaolinite and organic matter.  相似文献   

20.
Helium diffusion from apatite is a sensitive function of the volume fraction of radiation damage to the crystal, a quantity that varies over the lifetime of the apatite. Using recently published laboratory data we develop and investigate a new kinetic model, the radiation damage accumulation and annealing model (RDAAM), that adopts the effective fission-track density as a proxy for accumulated radiation damage. This proxy incorporates creation of crystal damage proportional to α-production from U and Th decay, and the elimination of that damage governed by the kinetics of fission-track annealing. The RDAAM is a version of the helium trapping model (HeTM; Shuster D. L., Flowers R. M. and Farley K. A. (2006) The influence of natural radiation damage on helium diffusion kinetics in apatite. Earth Planet. Sci. Lett.249, 148-161), calibrated by helium diffusion data in natural and partially annealed apatites. The chief limitation of the HeTM, now addressed by RDAAM, is its use of He concentration as the radiation damage proxy for circumstances in which radiation damage and He are not accumulated and lost proportionately from the crystal.By incorporating the RDAAM into the HeFTy computer program, we explore its implications for apatite (U-Th)/He thermochronometry. We show how (U-Th)/He dates predicted from the model are sensitive to both effective U concentration (eU) and details of the temperature history. The RDAAM predicts an effective He closure temperature of 62 °C for a 28 ppm eU apatite of 60 μm radius that experienced a 10 °C/Ma monotonic cooling rate; this is 8 °C lower than the 70 °C effective closure temperature predicted using commonly assumed Durango diffusion kinetics. Use of the RDAAM is most important for accurate interpretation of (U-Th)/He data for apatite suites that experienced moderate to slow monotonic cooling (1-0.1 °C/Ma), prolonged residence in the helium partial retention zone, or a duration at temperatures appropriate for radiation damage accumulation followed by reheating and partial helium loss. Under common circumstances the RDAAM predicts (U-Th)/He dates that are older, sometimes much older, than corresponding fission-track dates. Nonlinear positive correlations between apatite (U-Th)/He date and eU in apatites subjected to the same temperature history are a diagnostic signature of the RDAAM for many but not all thermal histories.Observed date-eU correlations in four different localities can be explained with the RDAAM using geologically reasonable thermal histories consistent with independent fission-track datasets. The existence of date-eU correlations not only supports a radiation damage based kinetic model, but can significantly limit the range of acceptable time-temperature paths that account for the data. In contrast, these datasets are inexplicable using the Durango diffusion model. The RDAAM helps reconcile enigmatic data in which apatite (U-Th)/He dates are older than expected using the Durango model when compared with thermal histories based on apatite fission-track data or other geological constraints. It also has the potential to explain at least some cases in which (U-Th)/He dates are actually older than the corresponding fission-track dates.  相似文献   

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