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1.
{M[UO2¦AsO4]2 · nH2O} with M=Cu2+, Co2+, Ni2+ has been synthesized from reagent grade chemicals and by ion exchange of trögerite {HUO2AsO4 · 4 H2O}. Synthetic meta-zeunerite (M=Cu2+), meta-kirchheimerite (M=Co2+) and nickel-uranylarsenate are all tetragonal. The cell parameters determined from Guinier-Hägg diffraction data for {Cu[UO2¦AsO4]2 · 8 H2O} are a=b=7.10 Å and c=17.42 Å, with Z=2 and the measured density 3.70 g cm?3. The cell parameters for {Co[UO2¦AsO4]2 · 7 H2O} and {Ni[UO2¦AsO4]2 · 7 H2O} are a=b=20.25 Å and c=17.20 Å, with Z=16 and the measured density 3.82 and 3.74 g cm?3, respectively. The solubility products for synthetic Cu-, Co- and Ni-uranylarsenate at 25° C are 10?49.20, 10?45.34 and 10?45.10, respectively. The zeta-potential remains negative between pH=2 and pH=9 and is strongly affected by the presence of different cations. 相似文献
2.
Manganoan lipscombite (Fe x /2+ , M y /2+ ) Fe 3?(x +y)/3+ [OH)3?(x+y)(PO4)2] was synthesized from pure chemicals. From the study of the Mn2+/Fe2+ atomic ratio by Mössbauer spectra, solubility, and electrokinetic properties, it was found that the crystal structure of lipscombite is not changed substantially by the manganese substitution. The unit cell parameters were determined from Guinier-Hägg X-ray diffraction patterns, which are identical for both synthetic ferrous-ferric and manganoan lipscombite. The two compounds crystallize in the tetragonal system with a=5.3020±0.0005 Å and c=12.8800±0.0005 Å. 相似文献
3.
Grain size- and crystallographic direction-dependence are among the fundamental characteristics of crystal solubility. However, such important material properties are routinely ignored and solubility is often conveniently approximated by a solubility product. In this study, we attempt to outline the relationship between solubility and solubility product using thermodynamic arguments, and to provide observations that demonstrate the occurrence of circumstances where the solubility product cannot properly approximate crystal solubility. Theoretical analysis shows that solubility is always greater than solubility product, but the difference is inversely related to the grain size. Furthermore, the difference can be crystallographic direction specific if the total surface energy change upon the attachment of an individual growth unit is nonequivalent for each symmetrically unrelated crystal faces. In situ AFM experiments conducted on the cleavage face of calcite demonstrate that the steps exhibit direction- and length-dependent behavior. Specifically, the measured critical step lengths are consistent with the predicted inverse relationship to saturation states. Moreover, step retreat at and advance at are observed simultaneously in a narrow range of saturation at near equilibrium conditions, indicating the existence of direction specific solubility. Whereas these findings justify the rationale for approximating solubility by solubility product in cases where large crystals are concerned, the results imply that the size and direction effect should not be ignored if nanocrystal growth/dissolution is the subject of interest. 相似文献
4.
A discussion is given concerning the transformation of curite into meta-torbernite in an acid environment. Crystallographic data together with differential thermal analysis show that the end-product obtained by this method is identical with meta-torbernite. Measurements of the zeta-potential on these meta-torbernite specimens result in negative values, which are strongly influenced by pH and NaCl concentrations. The surface conductivity is calculated from the measured zeta-potential. 相似文献
5.
Claire Chaïrat Eric H. Oelkers Jacques Schott 《Geochimica et cosmochimica acta》2007,71(24):5888-5900
The surface chemistry of fluorapatite in aqueous solution was investigated using electrokinetic techniques, potentiometric titrations, solubility measurements, and attenuated total reflection infrared spectroscopy. All methods indicate the formation of Ca/F depleted, P enriched altered layer via exchange reactions between H+ and Ca2+, and OH− and F− at the fluorapatite (FAP) surface. Observations suggest that this leached layer has a di-calcium phosphate (CaHPO4) composition and that it controls the apparent solubility of FAP. Electrokinetic measurements yield an iso-electric point value of 1 ± 0.5 consistent with a negatively charged FAP surface at pH > 1. In contrast, surface titrations give an apparent pH of point of zero charge of ∼7.7, consistent with a positively charged surface at pH < 7.7. These differences are shown to stem from proton consumption by both proton exchange and dissolution reactions at the FAP surface. After taking account for these effects, FAP surface charge is shown to be negative to at least pH 4 by surface titration analysis. 相似文献
6.
Fabrice Fraysse Oleg S. Pokrovsky Jacques Schott 《Geochimica et cosmochimica acta》2006,70(8):1939-1951
Although phytoliths, constituted mainly by micrometric opal, exhibit an important control on silicon cycle in superficial continental environments, their thermodynamic properties and reactivity in aqueous solution are still poorly known. In this work, we determined the solubility and dissolution rates of bamboo phytoliths collected in the Réunion Island and characterized their surface properties via electrophoretic measurements and potentiometric titrations in a wide range of pH. The solubility product of “soil” phytoliths ( at 25 °C) is equal to that of vitreous silica and is 17 times higher than that of quartz. Similarly, the enthalpy of phytoliths dissolution reaction is close to that of amorphous silica but is significantly lower than the enthalpy of quartz dissolution. Electrophoretic measurements yield isoelectric point pHIEP = 1.2 ± 0.1 and 2.5 ± 0.2 for “soil” (native) and “heated” (450 °C heating to remove organic matter) phytoliths, respectively. Surface acid-base titrations allowed generation of a 2-pK surface complexation model. Phytoliths dissolution rates, measured in mixed-flow reactors at far from equilibrium conditions at 2 ? pH ? 12, were found to be intermediate between those of quartz and vitreous silica. The dissolution rate dependence on pH was modeled within the concept of surface coordination theory using the equation:
7.
X. Mao F. X. Han X. Shao K. Guo J. McComb S. Njemanze Z. Arslan Z. Zhang 《International Journal of Environmental Science and Technology》2016,13(7):1641-1652
The objectives of this study were to investigate fractionation, solubility and potential bioavailability of Pb, As and Cs in Mississippi River Delta paddy soil under an electrokinetic field (EKF). Effects of EKF on soil pH changes and solid-phase distributions of metal(loid)s were examined. Results showed that fractionation of Pb, As and Cs was largely determined by the nature of elements, loading levels and EKF treatment. Native Pb in the soil was mostly in the amorphous iron oxide, organic matter and residual fractions, native As in the amorphous iron oxide, easily reducible oxide and residue fractions while native Cs in the residue fraction. Added Pb, As and Cs showed distinguished solid-phase distributions: Pb dominantly in the organic matter fraction; As in the amorphous iron oxide fraction, and Cs in the residue with a significant water-soluble plus exchangeable fraction. EKF treatment is effective on lowering soil pH to 1.5 near the anode due to water electrolysis releasing proton which is beneficial for dissolution of metal(loid)s, increasing their overall solubility. The acidification in the anode soil efficiently increased the water-soluble Pb and the exchangeable Cs, implying enhanced solubility and elevated their overall potential bioavailability in the anode region while lower solubility in the cathode area. The building up of water-soluble As in the anode region may be from electromigration of As anion from the cathode. This study shows significant enhancement of redistribution, elevated solubility and overall bioavailability of Pb, As and Cs in Mississippi Delta paddy soil under the EKF. 相似文献
8.
Genesis of metaautinute [Ca(UO2/PO4)2 · 7H2O] starting from curite hints at the existence of an intermediate hydrogen autunite stage [HUO2PO4 · 4H2O]. The substitution of protons in hydrogen autunite by Ca2+ ions is proved by electrokinetic measurements. As a consequence of the similarity between X-ray powder patterns of hydrogen autunite and meta-autunite a glycolation method has been applied in order to distinguish the two species. The cell dimensions have been determined from Guinier X-ray diffraction patterns. Both minerals are tetragonal with a=6.981±0.005 Å and c=8.448±0.005 Å for metaautunite and a=7.084±0.005 Å and c=8.777±0.005 Å for hydrogen autunite. For both minerals, the zeta-potential is mostly negative and is strongly influenced by temperature, pH and concentration of cations in the suspension. The surface conductivity has been calculated from the value of the zetapotential. The electrokinetic properties of metaautunite are very similar to those of metatorbernite. 相似文献
9.
Effects of various commonly used pretreatments such as desliming, ultrasonic scrubbing and leaching with dilute nitric, hydrofluoric and sodium hydroxide solutions on the electrokinetic properties of quartz in aqueous solutions are reported. The study showed that treatments with various reagents often used in mineral processing research in the past to clean minerals can affect, sometimes severly, the electrokinetic properties of quartz. The change in these properties during subsequent aging is also found to be governed by the type of treatment used. This study also shows the need in mineral research for standardization of mineral preparation techniques in order that the discrepancy in data reported for surface properties in literature can be minimized. 相似文献
10.
Dr. K. Mereiter 《Mineralogy and Petrology》1986,35(1):1-18
Summary The crystal structure of a schröckingerite from Joachimsthal, NaCa3[UO2(CO3)3](SO4) F·10H2O, triclinic, space groupP1,a=9.634(1),b=9.635(1),c=14.391(2) Å, -91.41(1), =92.33(1), =120.26(1)°,V=1151 Å3,Z=2, has been determined by X-ray diffraction and refined toR=0.026 for 5451 reflections. The structure contains NaCa3[UO2(CO3)3] (SO4) F·6H2O layers built up from UO2(CO3)
3
4–
anions, NaO3(H2O)3 octahedra, three kinds of CaO5F(H2O)2 polyhedra, Ca3F pyramids and Ca-bonded SO4 tetrahedra. These layers extend atz1/5 andz4/5 parallel to (001). They are linked parallel to c exclusively by hydrogen bonds, both directly as well as via interlayer H2O molecules. The structure shows a striking trigonal pseudosymmetry within the range 0.04<z<0.96. Atz0 these parts of the structure are dislocated relative to each other by a step of 1 Å parallel to [110]. Morphologic and optical properties of schröckingerite have been investigated in the light of the known crystal structure.
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Kristallstruktur und kristallographische Eigenschaften eines Schröckingerits von Joachimsthal
Zusammenfassung Die Kristallstruktur eines Schröckingerits von Joachimsthal, NaCa3[UO2(CO3)3](SO4) F·10H2O, triklin, RaumgruppeP1,a=9,634(1),b=9,635(1),c=14,391(2) Å, =91,41(1), =92,33(1), =120,26(1)°,V=1151 Å3,Z=2, wurde mit Röntgenbeugung bestimmt und für 5451 Reflexe aufR=0.026 verfeinert. Die Kristallstruktur enthält NaCa3[UO2(CO3)3] (SO4)I·6H2O Schichten, die aus UO2(CO3) 3 4– . Anionen, NaO3(H2O)3-Oktaedern, drei Arten von CaO5F(H2O)2-Polyedern, Ca3 F-Pyramiden und an Ca gebundenen SO4-Tetraedern aufgebaut sind. Diese Schichten erstrecken sich inz1/5 undz4/5 parallel zu (001). Sie sind parallel zuc ausschließlich durch Wasserstoffbrücken verknüpft, und zwar sowohl direkt als auch indirekt durch zwischen den Schichten gelegene Wassermoleküle. Die Struktur zeigt im Bereich 0,04<z<0,96 eine ausgeprägte trigonale Pseudosymmetrie. Derartige Bereiche sind inz0 um etwa 1 Å parallel zu [110] stufenartig gegeneinander versetzt. Morphologische und optische Eigenschaften von Schröckingerit wurden im Licht der bekannten Kristallstruktur untersucht.
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11.
Hideki Murakami Naoto Oshiman Satoru Yamaguchi Takeshi Hashimoto Ryokei Yoshimura 《Tectonophysics》2007,443(3-4):200
The Nojima Fault Zone Probe was designed to study the properties and healing processes of the Nojima fault, which is the surface fault rupture of the Hyogo-ken Nanbu earthquake (M7.2) of 1995 (1995 Kobe earthquake). In this project, water injection experiments were conducted in a borehole of 1800 m depth at the Nojima fault. We set up electrodes around the borehole and observed self-potential variations to investigate the magnitude of electrokinetic and hydraulic parameters around the Nojima fault zone. In the 1997 experiment, self-potential variations were in the range of a few to about 20 mV across 320–450 m electrode dipoles with hydraulic pressure variations from 3.5 to 4 MPa. In the 2000 experiment, self-potential variations were in the range of a few to about 85 mV across 160–260 m electrode dipoles with the hydraulic pressure variations from 3 to 4.5 MPa. In the 2003 experiment, self-potential variations were in the range of a few to about 30 mV across 20–80 m electrode dipoles with hydraulic pressure of 4 MPa. These observed self-potential variations were explained well with an electrokinetic effect due to the underground flow of the injected water. From the observed results, we estimated that the ratio of hydraulic parameters (permeability, porosity, and tortuosity) to electrokinetic parameters (zeta potential and dielectric constant) decreased approximately 40% during eight years after the earthquake. This result suggests that the healing process around the fault zone progress. 相似文献
12.
The gravitational signal of the upper mantle density structures is investigated in the refined gravity data which are corrected for the gravitational contributions of the crust density structures and the Moho geometry. The gravimetric forward modeling is applied to compute these refined gravity data globally on a 1 × 1 arcdeg grid using the global geopotential model (EGM2008), the global topographic/bathymetric model (DTM2006.0) including the ice-thickness data, and the global crustal model (CRUST2.0). The characteristics of the upper mantle density structures are further analyzed in association with the Moho parameters (i.e., Moho depths and density contrast). The 1 × 1 arcdeg global data of the Moho parameters are estimated by applying the combined least-squares approach based on solving Moritz’s generalization of the Vening–Meinesz inverse problem of isostasy. The refined gravity data exhibit mainly the mantle lithosphere structures attributed to the global mantle convection. A significant correlation found over oceans between the refined gravity data and the Moho density contrast is explained by the increasing density of the oceanic lithosphere with age. Despite the lithosphere structures attributed to the global mantle convection are confirmed also in the refined gravity data over continents, the significant correlation between the refined gravity data and the Moho parameters is in this case absent. Instead, the significant proportion of lateral variations of the Moho density contrast within the continental lithosphere is attributed to the depth-dependant density changes due to pressure and thermal gradient. 相似文献
13.
对航磁和航空TEM数据精细化处理手段——磁化强度矢量反演和Maxwell板状体反演进行了简单介绍,并以黑龙江嘎来奥伊地区矽卡岩型铅锌矿为例,阐述了两种处理手段在该地区实测数据的处理结果,总结出一套数据处理、分析及解释的思路,即磁化强度矢量反演加视电阻率剖面能够分析成矿环境,分析提取矿致异常,继而采用Maxwell对异常地段进行板状体反演,模拟矿体(低阻体)在地下的分布位置,从而指导钻孔布设,在已知矿区的试验效果较好. 相似文献
14.
Lei Chen Jian-Wei Li R. O. Rye W. M. Benzel H. A. Lowers Ming-Zhong He 《Mineralogy and Petrology》2013,107(4):487-499
Supergene jarosite-group minerals are widespread in weathering profiles overlying Pb-Zn sulfide ores at Xitieshan, northern Tibetan Plateau, China. They consist predominantly of K-deficient natrojarosite, with lesser amounts of K-rich natrojarosite and plumbojarosite. Electron microprobe (EMP) analyses, scanning electron microcopy (SEM) investigation, and X-ray mapping reveal that the jarosite-group minerals are characterized by spectacular oscillatory zoning composed of alternating growth bands of K-deficient and K-bearing natrojarosite (K2O >1 wt.%). Plumbojarosite, whenever present, occurs as an overgrowth in the outermost bands, and its composition can be best represented by K0.29Na0.19Pb0.31Fe2.66Al0.22(SO4)1.65(PO4)0.31(AsO4)0.04(OH)7.37. The substitution of monovalent for divalent cations at the A site of plumbojarosite is charge balanced by the substitution of five-valent for six-valent anions in XO4 at the X site. Thermogravimetric analysis (TGA) of representative samples reveal mass losses of 11.46 wt.% at 446.6 °C and 21.42 wt.% at 683.4 °C due to dehydroxylation and desulfidation, respectively. TGA data also indicate that the natrojarosite structure collapses at 446.6 °C, resulting in the formation of NaFe(SO4)2 and minor hematite. The decomposition products of NaFe(SO4)2 are hematite and Na2SO4. Powder X-ray diffraction (XRD) analyses show that the jarosite-group minerals have mean unit-cell parameters of a?=?7.315 Å and c?=?016.598 Å. XRD and EMP data support the view that substitutions of Na for K in the A site and full Fe occupancy in the B site can considerably decrease the unit-cell parameter c, but only slightly increase a. The results from this study suggest that the observed oscillatory zoning of jarosite-group minerals at Xitieshan resulted mainly from substitutions of K for Na at the A site and P for S at the X site. 相似文献
15.
S.K. Mishra 《International Journal of Mineral Processing》1979,6(2):119-132
Electrokinetic and flotation studies on apatites and calcite show that under certain conditions these minerals are floatable with dodecylamine chloride (DDACl) and the possible mode of DDACl adsorption is due to Coulombic and Van der Waals forces. The results indicate hemi-micelle formation of dodecylamine ions and suggest involvement of neutral molecular amine in the hemi-micelle structure, the critical hemi-micelle concentration being influenced by the nature of charge at the mineral surface. 相似文献
16.
《地学前缘(英文版)》2024,15(1):101688
Utilizing both borehole and Cone Penetration Testing (CPT) data in soil stratification helps to get more convincing soil stratification results. However, the soil classification results revealed by borehole (Unified Soil Classification System, USCS) and CPT tests (soil behavior type, SBT) are commonly not consistent. This study proposes a feasible solution to integrate the borehole and CPT data with the tree-based method. The tree-based method is naturally suitable for soil stratification tasks as it aims to divide the subsurface space into several clusters based on the similarities of the soil types. A novel boundary dictionary method is proposed to enhance the model performance on complex soil layer conditions. A probabilistic mapping matrix between the USCS-SBT system is built based on a collected municipal database with collocated borehole and CPT data. The optimal soil stratification results can be selected based on considering multiple borehole information and pruning the structure of trees. The structure of the trees can be optimized in a back analysis perspective with the Sequential Model-Based Global Optimization (SMBO) algorithm which aims to maximize the possibility of observing the borehole information based on the USCS-SBT probabilistic mapping matrix. The uncertainties of the optimal soil stratification results can be estimated based on a weighted Gini index method. The performance of the proposed method is validated based on a real case in New Zealand with a cross-validation method. The results indicate that the proposed method is robust and effective. 相似文献
17.
River water (Water of Luce, Scotland) is used in laboratory experiments designed to investigate physical and chemical properties of Fe. Mn, Cu, Ni, Co, Cd and humic acids in riverine and estuarine systems. Using NaCl, MgCl2 and CaCl2 as coagulating agents, coagulation of dissolved (0.4 μm filtered) Fe, Cu, Ni, Cd and humic acids increases in a similar matter with increasing salt molarily: Ca2+ is the most dominant coagulating agent. Removal by coagulation with Ca2+ at seawater concentrations ranges from large (Fe-80%. HA-60%, Cu-40%) to small (Ni, Cd-15%) to essentially nothing (Cd, Mn-3%). Destabilization of colloids is the indicated mechanism. Solubility-pH measurements show that between a pH of 3 and 9, Fe, Cu, Ni, Mn, Co and Cd are being held in the dissolved phase by naturally occurring organic substances. Between pH of 2.2 and 1.2 a large proportion of dissolved Fe, Cu. Ni and Cd (72, 35,44 and 36% respectively) is precipitated along with the humic acids; in contrast, Mn and Co show little precipitation (3%). Adsorption-pH experiments, using unfiltered river water spiked with Cu, indicate that adsorption of Cu onto suspended particles is inhibited to a large extent by the formation of dissolved Cu-organic complexes.The experimental results demonstrate that solubilities and adsorption properties of certain trace metals in freshwaters can be opposite to those observed with artificial solutions or predicted with chemical models. Interaction with organic substances is a critical factor. 相似文献
18.
A point-dipole calculation which incorporates an expression for the Lorentz-factor tensor has been used to model the effect of chemical substitution on refractive index and optic axial angle (2V). Isotropic electronic polarizabilities for the sodium D line are refined by least-squared methods from lattice dipole sums and observed refractive indices. Although the assumption of isotropic polarizability is unrealistic for many mineral structures, the model is useful in interpreting the relationship between structure, chemical composition, and optical properties. 相似文献
19.
The transformation of vivianite and the direct synthesis starting from pure chemicals lead to the formation of lipscombite {Fe x 2+ Fe 3?x 3+ [(OH)3?x/(PO4)2]} with varying Fe2+/Fe3+ molar ratios. The influence of this ratio on the Mössbauer spectra, solubility, electrokinetic potential and infrared spectra has been studied. By means of Mössbauer spectroscopy, the distribution of the Fe2+ and Fe3+ ions between the octahedral sites I and II has been investigated. The unit cell dimensions have been determined from Guinier-Hägg X-ray diffraction patterns. The crystal system is tetragonal for synthetic lipscombite with a=5.3020±0.0005 Å and c=12.8800±0.0005 Å. Lipscombite has been found to show a negative and time-dependent zeta-potential which, moreover, is influenced by the pH of the suspension and the Fe2+/Fe3+ molar ratio. An explanation of the time-dependence of the zeta-potential on variations of solubility is proposed. Infrared absorption spectrum only is characterized by two absorption bands: v OH(3,500 cm?1) and v P?O(1,100-960 cm?1). The density at 25° C is determined in toluene as 3.36±0.01 g·cm?3. 相似文献
20.
The stability and solubility of natural arsenopyrite (FeAsS) in pure water and moderately acid to slightly basic aqueous solutions buffered or not with H2 and/or H2S were studied at temperatures from 300 to 450°C and pressures from 100 to 1000 bar. The solubilities of FeAsS in pure water and dilute HCl/NaOH solutions without buffering are consistent with the formation of the As(OH)30(aq) species and precipitation of magnetite. At more acid pH (pH ≤2), arsenopyrite dissolves either stoichiometrically or with formation of the As-FeAsS assemblage. In H2S-rich and H2-rich aqueous solutions, arsenopyrite dissolution results in the formation of pyrrhotite (±pyrite) and iron arsenide(s), respectively, which form stable assemblages with arsenopyrite.Arsenic concentrations measured in equilibrium with FeAsS in slightly acid to neutral aqueous solutions with H2 and H2S fugacities buffered by the pyrite-pyrrhotite-magnetite assemblage are 0.0006 ± 0.0002, 0.0055 ± 0.0010, 0.07 ± 0.01, and 0.32 ± 0.03 mol/kg H2O at 300°C/400 bar, 350°C/500 bar, 400°C/500 bar, and 450°C/500 bar, respectively. These values were combined with the available thermodynamic data on As(OH)30(aq) (Pokrovski et al., 1996) to derive the Gibbs free energy of FeAsS at each corresponding temperature and pressure. Extrapolation of these values to 25°C and 1 bar, using the available heat capacity and entropy data for FeAsS (Pashinkin et al., 1989), yields a value of −141.6 ± 6.0 kJ/mol for the standard Gibbs free energy of formation of arsenopyrite. This value implies a higher stability of FeAsS in hydrothermal environments than was widely assumed.Calculations carried out using the new thermodynamic properties of FeAsS demonstrate that this mineral controls As transport and deposition by high-temperature (>∼300°C) crustal fluids during the formation of magmatic-hydrothermal Sn-W-Cu-(Au) deposits. The equilibrium between As-bearing pyrite and the fluid is likely to account for the As concentrations measured in modern high- and moderate-temperature (150 ≤ T ≤ 350°C) hydrothermal systems. Calculations indicate that the local dissolution of arsenopyrite creates more reducing conditions than in the bulk fluid, which is likely to be an effective mechanism for precipitating gold from hydrothermal solutions. This could be a possible explanation for the gold-arsenopyrite association commonly observed in many hydrothermal gold deposits. 相似文献