Composition and solubility of precipitated copper(II) arsenates     

Hanna Nelson  Andrey Shchukarev  Staffan Sjberg  Lars Lvgren 《Applied Geochemistry》2011,26(5):696-704

Equilibrium reactions involving Cu(II) and As(V) have been studied with respect to formation of complexes in aqueous solutions as well as formation of solid phases. Potentiometric titrations performed at 25 °C (I = 0.1 M Na(Cl)) and at different Cu to As ratios gave no evidence for the existence of Cu(II) arsenate complexes in solution below the pH of the precipitation boundaries (pH ≈ 4), irrespective of the Cu to As ratio and pH. Mixing of solutions of Cu(II) and As(V) at different proportions and adjusting pH to values ranging from 4 to 9 resulted in precipitation of five different solid phases. The elemental composition of the solids was determined using X-ray Photoelectron Spectroscopy, and Environmental Scanning Microscopy-Field Emission Gun equipped with an energy dispersive spectroscopy detector. The average Cu/As ratio was determined by dissolving the solids. Total soluble concentrations of the components Cu(II) and As(V), as well as the basicity of the solid phases were determined by analysis of aqueous solutions. Based upon these experimental data the stoichiometric composition of the solid phases and their stability were determined. The resulting equilibrium model includes the solid phases Cu₃(AsO₄)₂, Cu₃(AsO₄)(OH)₃, Cu₂(AsO₄)(OH), Cu₅Na(HAsO₄)(AsO₄)₃ and Cu₅Na₂AsO₄)₄, where Cu₅Na(HAsO₄)(AsO₄)₃ and Cu₅Na₂(AsO₄)₄ have not been reported previously. In 0.1 M Na(Cl), Na⁺ was found to be a significant component in two of the solid phases. The Cu₅Na₂(AsO₄)₄ was formed in weakly alkaline conditions with pNa < 2.5. Stability constants for all solid phases have been determined. Distribution diagrams as well as predominance area (pNa-pH) diagrams are presented to illustrate stability fields of the different solid phases.  相似文献   

Towards a model for the in situ origin of PGE reefs in layered intrusions: insights from chromitite seams of the Rum Eastern Layered Intrusion, Scotland     

Rais Latypov  Brian O’Driscoll  Andrey Lavrenchuk 《Contributions to Mineralogy and Petrology》2013,166(1):309-327

The current debate on the origin of platinum-group element (PGE) reefs in layered intrusions centres mostly on gravity settling of sulphide liquid from overlying magma versus its introduction with interstitial melt/fluids migrating upward from the underlying cumulate pile. Here, we show that PGE-rich chromitite seams of the Rum Eastern Layered Intrusion provide evidence for an alternative origin of such deposits in layered intrusions. These laterally extensive 2-mm-thick chromitite seams occur at the bases of several cyclic mafic–ultramafic units and show lithological and textural relationships suggesting in situ growth directly at a crystal–liquid interface. This follows from chromitite development along the edges of steeply inclined culminations and depressions at unit boundaries, even where these are vertically oriented or overhanging. High concentrations of PGE (up to 2–3 ppm Pd + Pt) are controlled by fine-grained base-metal sulphides, which are closely associated with chromitite seams. The following sequence of events explains the origin of the PGE-rich chromitite seams: (a) emplacement of picritic magma that caused thermal and mechanical erosion of underlying cumulate, followed by in situ growth of chromite against the base, (b) precipitation of sulphide droplets on chromite grains acting as favourable substrate or catalyst for sulphide nucleation, (c) the scavenging of PGE by sulphide droplets from fresh magma continuously brought towards the base by convection. Since the rate of magma convection is 10⁵–10⁷ times higher than that of the solidification (km/year to km/day versus 0.5–1.0 cm/year), the in situ formed sulphide droplets can equilibrate with picritic magma of thousands to million times their own volume. As a result, the sulphide-bearing rocks are able to reach economic concentrations of PGE (several ppm). We tentatively suggest that the basic principles of our model may be used to explain the origin of PGE-rich chromitites and classical PGE reefs in other layered mafic–ultramafic intrusions.  相似文献   

Hydrothermal synthesis of pyrochlores and their characterization     

Alexander F. Redkin  Andrey M. Ionov  Nataliya P. Kotova 《Physics and Chemistry of Minerals》2013,40(9):733-745

Pyrochlores, microlites, and U-betafites of pyrochlore group minerals were obtained from mixing experiments of the corresponding oxides and fluorides by hydrothermal synthesis at T = 800 °C and P = 200 MPa in the solution of 1.0 M NaF. The presence of U⁴⁺ in pyrochlore does not affect the cell parameter, which for the phases of pyrochlore–microlite series is 10.42 ± 0.01 Å. In a system with an excess of UO₂, pyrochlores and microlites, containing uranium up to 0.2–0.3 atoms per formula unit (apfu), are formed. In the uranium-free system of betafites composition, perovskites and Ti-bearing pyrochlores are formed. U-pyrochlores of betafite series, containing 2Ti = Nb + Ta in moles, have cubic cell parameters of 10.26 ± 0.02 Å and U⁴⁺ isomorphic capacity of 0.4–0.5 apfu. In the pyrochlore structure, U⁴⁺ may substitute for Ca²⁺ and Na⁺ cations in the eightfold site. In pyrochlores of pyrochlore–microlite series, Ca²⁺ is replaced by U⁴⁺, while in pyrochlores of betafite series, U⁴⁺ replaces Na⁺. Phases with pyrochlore structure, containing U⁵⁺ and U⁶⁺ in the sixfold site, usually occupied by Nb⁵⁺, Ta⁵⁺, and Ti⁴⁺, are formed under oxidizing conditions (Cu–Cu₂O buffer). They are characterized by low content of Nb⁵⁺, Ta⁵⁺ (<0.1 apfu), and anomalous behavior of the crystal lattice (compression, instead of expansion). Under natural conditions, the formation of pyrochlores containing a significant amount of U⁵⁺ and U⁶⁺ is unlikely.  相似文献   

Nickel Isotope Variations in Terrestrial Silicate Rocks and Geological Reference Materials Measured by MC‐ICP‐MS     

Bleuenn Gueguen  Olivier Rouxel  Emmanuel Ponzevera  Andrey Bekker  Yves Fouquet 《Geostandards and Geoanalytical Research》2013,37(3):297-317

Although initial studies have demonstrated the applicability of Ni isotopes for cosmochemistry and as a potential biosignature, the Ni isotope composition of terrestrial igneous and sedimentary rocks, and ore deposits remains poorly known. Our contribution is fourfold: (a) to detail an analytical procedure for Ni isotope determination, (b) to determine the Ni isotope composition of various geological reference materials, (c) to assess the isotope composition of the Bulk Silicate Earth relative to the Ni isotope reference material NIST SRM 986 and (d) to report the range of mass‐dependent Ni isotope fractionations in magmatic rocks and ore deposits. After purification through a two‐stage chromatography procedure, Ni isotope ratios were measured by MC‐ICP‐MS and were corrected for instrumental mass bias using a double‐spike correction method. Measurement precision (two standard error of the mean) was between 0.02 and 0.04‰, and intermediate measurement precision for NIST SRM 986 was 0.05‰ (2s). Igneous‐ and mantle‐derived rocks displayed a restricted range of δ^60/58Ni values between ?0.13 and +0.16‰, suggesting an average BSE composition of +0.05‰. Manganese nodules (Nod A1; P1), shale (SDO‐1), coal (CLB‐1) and a metal‐contaminated soil (NIST SRM 2711) showed positive values ranging between +0.14 and +1.06‰, whereas komatiite‐hosted Ni‐rich sulfides varied from ?0.10 to ?1.03‰.  相似文献   

Astro-WISE and Grid     

Kor Begeman  Andrey N. Belikov  Fokke Dijkstra  Zheng Meyer-Zhao  Edwin A. Valentijn  Willem-Jan Vriend 《Experimental Astronomy》2013,35(1-2):355-366

The paper reviews the Astro-WISE infrastructure and demonstrates that the Astro-WISE Information System provides a Grid itself. We describe the integration of Astro-WISE with an external Grid infrastructure (BiGGrid). The integration is performed on all infrastructural layers (data storage, metadata and processing layers) with Astro-WISE as a “master” infrastructure. We report the use of the integrated infrastructure for the processing of Astro-WISE hosted data and for the future development of Astro-WISE and Target projects.  相似文献   

Sequentially sampled gas hydrate water,coupled with pore water and bottom water isotopic and ionic signatures at the Kukuy mud volcano,Lake Baikal: ambiguous deep-rooted source of hydrate-forming water     

Hirotsugu Minami  Akihiro Hachikubo  Hirotoshi Sakagami  Satoshi Yamashita  Yusuke Soramoto  Tsuyoshi Kotake  Nobuo Takahashi  Hitoshi Shoji  Tatyana Pogodaeva  Oleg Khlystov  Andrey Khabuev  Lieven Naudts  Marc De Batist 《Geo-Marine Letters》2014,34(2-3):241-251

The isotopic and ionic composition of pure gas hydrate (GH) water was examined for GHs recovered in three gravity cores (165–193 cm length) from the Kukuy K-9 mud volcano (MV) in Lake Baikal. A massive GH sample from core St6GC4 (143–165 cm core depth interval) was dissociated progressively over 6 h in a closed glass chamber, and 11 sequentially collected fractions of dissociated GH water analyzed. Their hydrogen and oxygen isotopic compositions, and the concentrations of Cl^– and HCO₃ ^– remained essentially constant over time, except that the fraction collected during the first 50 minutes deviated partly from this pattern. Fraction #1 had a substantially higher Cl^– concentration, similar to that of pore water sampled immediately above (135–142 cm core depth) the main GH-bearing interval in that core. Like the subsequent fractions, however, the HCO₃ ^– concentration was markedly lower than that of pore water. For the GH water fractions #2 to #11, an essentially constant HCO₃ ^–/Cl^– ratio of 305 differed markedly from downcore pore water HCO₃ ^–/Cl^– ratios of 63–99. Evidently, contamination of the extracted GH water by ambient pore water probably adhered to the massive GH sample was satisfactorily restricted to the initial phase of GH dissociation. The hydrogen and oxygen isotopic composition of hydrate-forming water was estimated using the measured isotopic composition of extracted GH water combined with known isotopic fractionation factors between GH and GH-forming water. Estimated δD of ?126 to ?133‰ and δ¹⁸O of ?15.7 to ?16.7‰ differed partly from the corresponding signatures of ambient pore water (δD of ?123‰, δ¹⁸O of ?15.6‰) and of lake bottom water (δD of ?121‰, δ¹⁸O of ?15.8‰) at the St6GC4 coring site, suggesting that the GH was not formed from those waters. Observations of breccias in that core point to a possible deep-rooted water source, consistent with published thermal measurements for the neighboring Kukuy K-2 MV. By contrast, the pore waters of core St6GC4 and also of the neighboring cores GC2 and GC3 from the Kukuy K-9 MV show neither isotopic nor ionic evidence of such a source (e.g., elevated sulfate concentration). These findings constrain GH formation to earlier times, but a deep-rooted source of hydrate-forming water remains ambiguous. A possible long-term dampening of key deep-water source signatures deserves further attention, notably in terms of diffusion and/or advection, as well as anaerobic oxidation of methane.  相似文献   

Short‐period static correction without Normal Move Out†     

Andrey V. Masjukov  Igor S. Murzov 《Geophysical Prospecting》2013,61(1):92-103

Static correction is a common step in a seismic data proccessing flowchart for land data. Here we propose a new algorithm for automatic short‐period static correction. The algorithm is based on the assumption that seismic events after short‐period static correction should be locally plane nearly everywhere. No other assumptions are made. Therefore the proposed method does not require a preliminary velocity analysis. The algorithm consists in two main parts: evaluation of second spatial differences of trajectories and subsequent regularized integration of these differences. The proposed method proves its robustness and shows results comparable with conventional residual static correction based on improving common‐midpoint stacking. In contrast to the conventional residual static, the proposed algorithm can estimate short‐period statics in complex cases where common‐midpoint stacking fails because of non‐hyperbolic events.  相似文献   

Morphometry of upper cheek teeth of cave bears (Carnivora,Ursidae)     

Gennady F. Baryshnikov  Andrey Y. Puzachenko 《Boreas: An International Journal of Quaternary Research》2019,48(3):581-604

Univariate and multivariate statistics were applied to analyse the morphometrical variability of 4920 upper cheek teeth (P4, M1 and M2) of cave bears from 123 geographical sites (180 samples) of different Pliocene – Pleistocene ages. The analysed specimens included those belonging to the big cave bears Ursus kudarensis, U. deningeri, U. spelaeus (three subspecies) and U. kanivetz (including U. ingressus), as well as the small cave bear U. rossicus. The information‐theoretical parameters (Shannon entropy and orderliness (Von Foerster, 1960: On self‐organizing systems and their environments. In Self‐Organizing Systems, 31–50. Pergamon Press, London) were used to estimate tooth diversity in different teeth, different taxa and in selected local chrono‐populations. Multivariate allometry coefficients (Klingenberg, 1996: Multivariate allometry. In Advances in Morphometrics, 23‐49. Plenum Press, New York) were used to describe the relationships of different ‘parts’ of a tooth and to compare allometric patterns amongst species or selected local samples. A multivariate analysis showed a significant overlap of the size/shape parameter ranges in deningeroid and spelaeoid bears within morphological spaces. Within the cave bear lineage, the Deninger's bear has the greatest morphological diversity index (entropy) of all the teeth overall, and the lowest diversity is observed in the final taxon of this lineage – U. kanivetz (=ingressus). The P4 and M2 diversity showed multidirectional correlations with elevation above sea level amongst several ‘local’ populations of Late Pleistocene cave bears. The morphological disparities between the studied taxa are in close agreement with the distances in the available schemes of genetic differentiation based on ancient mitochondrial DNA. The split of U. kudarensis and U. deningeri has a good bootstrap support, which corresponds to the hypothesis about their parallel evolution. The small cave bear U. rossicus is placed between U. arctos and U. deningeri. The phylogenetic signal is more pronounced in the variability of teeth in comparison with other skeletal remains of cave bears (cranium, mandible, or metapodial bones).  相似文献   

Tsunami–tide interactions: A Cook Inlet case study     

Zygmunt Kowalik  Andrey Proshutinsky 《Continental Shelf Research》2010

First, we investigated some aspects of tsunami–tide interactions based on idealized numerical experiments. Theoretically, by changing total ocean depth, tidal elevations influence the speed and magnitude of tsunami waves in shallow regions with dominating tidal signals. We tested this assumption by employing a simple 1-D model that describes propagation of tidal waves in a channel with gradually increasing depth and the interaction of the tidal waves with tsunamis generated at the channel's open boundary. Important conclusions from these studies are that computed elevations by simulating the tsunami and the tide together differ significantly from linear superposing of the sea surface heights obtained when simulating the tide and the tsunami separately, and that maximum tsunami–tide interaction depends on tidal amplitude and phase. The major cause of this tsunami–tide interaction is tidally induced ocean depth that changes the conditions of tsunami propagation, amplification, and dissipation. Interactions occur by means of momentum advection, bottom friction, and variable water flux due to changing total depth and velocity. We found the major cause of tsunami–tide interactions to be changing depth. Secondly, we investigate tsunami–tide interactions in Cook Inlet, Alaska, employing a high-resolution 2-D numerical model. Cook Inlet has high tides and a history of strong tsunamis and is a potential candidate for tsunami impacts in the future. In agreement with previous findings, we find that the impacts of tsunamis depend on basin bathymetries and coastline configurations, and they can, in particular, depend on tsunami–tide interactions. In regions with strong tides and tsunamis, these interactions can result in either intensification or damping of cumulative tsunami and tide impacts, depending on mean basin depth, which is regulated by tides. Thus, it is not possible to predict the effect of tsunami–tide interaction in regions with strong tides without making preliminary investigations of the area. One approach to reduce uncertainties in tsunami impact in regions with high tides is to simulate tsunamis together with tidal forcing.  相似文献   

Scale effects on information theory-based measures applied to streamflow patterns in two rural watersheds     

Feng Pan  Yakov A. Pachepsky  Andrey K. Guber  Brian J. McPherson  Robert L. Hill 《Journal of Hydrology》2012

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