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1.
Reduced and intermediate S species (sulfide, thiosulfate, sulfite) were determined in 26 thermal water samples from the granitic massifs of south-west Bulgaria. Analysis of these S species was performed in the field, using a potentiometric-titration technique. Reduced and intermediate S species were found to enhance the solubility of Cu, Zn and Pb to an appreciable extent. According to thermodynamic equilibrium calculations, the prevailing complexes for sulfide-containing waters are CuS(HS)−, Zn(OH)(HS)0, ZnS(HS)− and PbS(HS)−. For waters which do not contain sulfide S, Cu(S2O3)−, Cu(SO3)−, Zn(OH)+, Zn(OH)20, HZnO2−, ZnCO30, ZnSO40, Zn2+ and PbCO30 are the important species. Whereas Cu and Pb are found to be controlled by their respective endmember sulfide phases, Zn appears to be controlled by formation of an FeZnS solid solution.  相似文献   

2.
Summary The crystal structure of arsentsumebite, ideally, Pb2Cu[(As, S)O4]2(OH), monoclinic, space group P21/m, a = 7.804(8), b = 5.890(6), c = 8.964(8) ?, β = 112.29(6)°, V = 381.2 ?3, Z = 2, dcalc. = 6.481 has been refined to R = 0.053 for 898 unique reflections with I> 2σ(I). Arsentsumebite belongs to the brackebuschite group of lead minerals with the general formula Pb2 Me(XO4)2(Z) where Me = Cu2+, Mn2+, Zn2+, Fe2+, Fe3+; X = S, Cr, V, As, P; Z = OH, H2O. Members of this group include tsumebite, Pb2Cu(SO4)(PO4)(OH), vauquelinite, Pb2Cu(CrO4)(PO4)(OH), brackebuschite, Pb2 (Mn, Fe)(VO4)2(OH), arsenbracke buschite, Pb2(Fe, Zn)(AsO4)2(OH, H2O), fornacite, Pb2Cu(AsO4)(CrO4)(OH), and feinglosite, Pb2(Zn, Fe)[(As, S)O4]2(H2O). Arsentsumebite and all other group members contain M = M–T chains where M = M means edge-sharing between MO6 octahedra and M–T represents corner sharing between octahedra and XO4 tetrahedra. A structural relationship exists to tsumcorite, Pb(Zn, Fe)2(AsO4)2 (OH, H2O)2 and tsumcorite-group minerals Me(1)Me(2)2(XO4)2(OH, H2O)2. Received June 24, 2000; revised version accepted February 8, 2001  相似文献   

3.
In the Rocca Busambra area (mid-west Sicily, Italy), from November 1999 to July 2002, 23 water points including wells and springs were sampled and studied for their chemical and isotopic compositions. Two rain gauges were also installed at different altitudes, and rainwater was collected monthly to determine the isotopic composition. The obtained results revealed the Rocca Busambra carbonate complex as being the main recharge area on account of its high permeability value. From a chemical view point, two main groups of water can be distinguished: calcium–magnesium–bicarbonate-type and calcium–magnesium–chloride–sulphate-type waters. The first group reflects the dissolution of the carbonate rocks; the second group probably originates from circulation within flyschoid sediments. Three water wells differ from the other samples due to their relatively high Na and K content, which probably is to be referred to a marked interaction with the “Calcareniti di Corleone” formation, which is rich in glauconite [(K, Na)(Fe3+, Al, Mg)2(Si, Al)4O10(OH)2]. In accordance with WHO guidelines for drinking water (2004), almost all the samples collected can be considered drinkable, with the exception of four of them, whose NO3 −, F− and Na+ contents exceed the limits. On the contrary, the sampled groundwater studied is basically suitable for irrigation.  相似文献   

4.
Growing recognition of triple-chain silicates in nature has prompted experimental research into the conditions under which they can form and the extent of solid solution that is feasible for some key chemical substitutions. Experiments were done primarily in the range of 0.1–0.5 GPa and 200–850 °C for durations of 18–1,034 h. A wide range of bulk compositions were explored in this study that can be classified broadly into two groups: those that are Na free and involve various possible chemical substitutions into jimthompsonite (Mg10Si12O32(OH)4), and those that are Na bearing and involve chemical substitutions into the ideal end-member Na4Mg8Si12O32(OH)4. Numerous attempts to synthesize jimthompsonite or clinojimthompsonite were unsuccessful despite the type of starting material used (reagent oxides, magnesite + SiO2, talc + enstatite, or anthophyllite). Similarly, the chemical substitutions of F− for OH−, Mn2+, Ca2+, or Fe2+ for Mg2+, and 2Li+ for Mg2+ and a vacancy were unsuccessful at nucleating triple-chain silicates. Conversely, nearly pure yields of monoclinic triple-chain silicate could be made at temperatures of 440–630 °C and 0.2 GPa from the composition Na4Mg8Si12O32(OH)4, as found in previous studies, though its composition is most likely depleted in Na as evidenced by electron microprobe and FTIR analysis. Pure yields of triple-chain silicate were also obtained for the F-analog composition Na4Mg8Si12O32F4 at 550–750 °C and 0.2–0.5 GPa if a flux consisting of Na-halide salt and water in a 2:1 ratio by weight was used. In addition, limited chemical substitution could be documented for the substitutions of 2 Na+ for Na+ + H+ and of Mg2+ + vacancy for 2Na+. For the former, the Na content appears to be limited to 2.5 cations giving the ideal composition of Na2.5Mg8Si12O30.5(OH)5.5, while for the latter substitution the Na content may go as low as 1.1 cations giving the composition Na1.1Mg9.4Si12O31.9(OH)4.1 based on a fixed number of Si cations. Further investigation involving Mg for Na cation exchange may provide a pathway for the synthesis of Na-free clinojimthompsonite. Fairly extensive solid solution was also observed for triple-chain silicates made along the compositional join Na4Mg8Si12O32(OH)4–Ca2Mg8Si12O32(OH)4 where the limit of Ca substitution at 450 °C and 0.2 GPa corresponds to Na0.7Ca1.8Mg7.8Si12O31.9(OH)4.1 (with the OH content adjusted to achieve charge balance). Aside from the Na content, this composition is similar to that observed as wide-chain lamellae in host actinolite. The relative ease with which Na-rich triple chains can be made experimentally suggests that these phases might exist in nature; this study provides additional insights into the range of compositions and formation conditions at which they might occur.  相似文献   

5.
 Groundwater in alluvial aquifers of the Wakatipu and Wanaka basins, Central Otago, New Zealand, has a composition expressed in equivalent units of Ca2+≫Mg2+≅Na+>K+ for cations, and HCO3 –≫SO4 2->NO3 –≅Cl– for anions. Ca2+ and HCO3 – occur on a 1 : 1 equivalent basis and account for >80% of the ions in solution. However, some groundwater has increased proportions of Na+ and SO4 2-, reflecting a different source for this water. The rock material of the alluvial aquifers of both basins is derived from the erosion and weathering of metamorphic Otago Schist (grey and green schists). Calcite is an accessory mineral in both the grey and green schists at <5% of the rock. Geological mapping of both basins indicates that dissolution of calcite from the schist is the only likely mechanism for producing groundwater with such a constant composition dominated by Ca2+ and HCO3 – on a 1 : 1 equivalent basis. Groundwater with higher proportions of Na+ and SO4 2- occurs near areas where the schist crops out at the surface, and this groundwater represents deeper and possibly older water derived from basement fluids. Anomalously high K+ in the Wakatipu basin and high NO3 – concentrations in the Wanaka basin cannot be accounted for by interaction with basement lithologies, and these concentrations probably represent the influence of anthropogenic sources on groundwater composition. Received, June 1996 Revised, March 1997, July 1997 Accepted, July 1997  相似文献   

6.
金在黄铁矿表面沉淀机理的实验研究   总被引：6，自引：0，他引：6       下载免费PDF全文
为了研究金在黄铁矿表面沉淀的机理,于室温、常压,在氯化物溶液中进行了黄铁矿粉末吸附金的实验。在不同pH的溶液中,黄铁矿均可吸附金,而且pH值明显地影响吸附速率。扫描电镜观察表明,反应后黄铁矿粒表面有金晶体形成。XPS研究得知,黄铁矿光片与含金氯化物溶液反应后表面有A0存在;硫在反应初期为S0、S2O32-,随后转变为SO42-,而铁成为Fe3+.黄铁矿中的Fe2+和S22-是溶液中金的还原剂。金在黄铁矿表面沉淀可能涉及吸附、还原和晶体生长等过程。  相似文献   

7.
The solubility and incorporation mechanisms of hydrogen in synthetic stishovite as a function of Al2O3 content have been investigated. Mechanisms for H incorporation in stishovite are more complex than previously thought. Most H in stishovite is incorporated via the Smyth et al. (Am Mineral 80:454–456, 1995) model, where H docks close to one of the shared O–O edges, giving rise to an OH stretching band in infrared (IR) spectra at 3,111–3,117 cm−1. However, careful examination of IR spectra from Al-stishovite reveals the presence of an additional OH band at 3,157–3,170 cm−1. All H is present on one site, with interstitial H both coupled to Al3+ substitutional defects on adjacent octahedral (Si4+) sites, and decoupled from other defects, giving rise to two distinct absorption bands. Trends in IR data as a function of composition are consistent with a change in Al incorporation mechanism in stishovite, with Al3+ substitution for Si4+ charge-balanced by oxygen vacancies at low bulk Al2O3 contents, and coupled substitution of Al3+ onto octahedral (Si4+) and interstitial sites at high bulk Al2O3 contents. Trends in OH stretching frequencies as a function of Al2O3 content suggest that any such change in Al incorporation mechanism could alter the effect that Al incorporation has on the compressibility of stishovite, as noted by Ono et al. (Am Mineral 87:1486–1489, 2002).  相似文献   

8.
1ＩｎｔｒｏｄｕｃｔｉｏｎＴｈｅＤｕｏｌａｎａｓａｙｉｇｏｌｄｄｅｐｏｓｉｔ,6 0ｋｍＮＷｏｆＨａｂａｈｅＣｏｕｎｔｙｉｎＸｉｎｊｉａｎｇ ,ｉｓｓｉｔｕａｔｅｄｏｎｔｈｅｎｏｒｔｈ ｗｅｓｔｅｒｎｍａｒｇｉｎｏｆｔｈｅＶａｒｉｓｃｉａｎＥｒｔｉｘｏｒｏｇｅｎｉｃｂｅｌｔ.Ｉｔｉｓａｍｅｄｉｕｍ ｌａｒｇｅｓｃａｌｅｇｏｌｄｄｅｐｏｓｉｔｃｏｎｔｒｏｌｌｅｄｂｙｔｈｅｃｏｕｐｌｅｄｏｒｅ ｆｏｒｍｉｎｇｐｒｏｃｅｓｓｅｓｉｎｖｏｌｖｉｎｇｂｒｉｔｔｌｅ ｄｕｃｔｉｌｅｓｈｅａｒｉｎｇ ,ａｌｂｉｔｉｔｅｖｅ…  相似文献   

9.
 Amphiboles were synthesized from bulk compositions prepared along the join Ca1.8Mg5.2Si8O22(OH)2–Ca1.8Mg3Ga4Si6O22(OH)2 hydrothermally at 750–850 °C and 1.0–1.8 GPa, and along the join Ca2Mg5Si8O22F2–Ca2Mg3Ga4Si6O22F2, anhydrously at 1000 °C and 0.7 GPa to document how closely the tschermak-type substitution is obeyed in these analogues of aluminous amphiboles. Electron-microprobe analyses and Rietveld X-ray diffraction structure refinements were performed to determine cation site occupancies. The extent of Ga substitution was found to be limited in both joins, but with the fluorine series having about twice the Ga content (0.6 atoms per formula unit, apfu) of the hydroxyl-series amphiboles (0.3 apfu). The tschermak-type substitution was followed very closely in the hydroxyl series with essentially equal partitioning of Ga between tetrahedral and octahedral sites. The fluorine-series amphiboles deviated significantly from the tschermak-type substitution and, instead, appeared to follow a substitution that is close to a Ca-pargasite substitution of the type: [6]Ga3++2[4]Ga3++1/2[A] Ca2+ = [6]Mg2++2[4]Si4++1/2[A]□. Infrared spectroscopy revealed an inverse correlation between the intensity of the OH-stretching bands and the Ga content for the hydroxyl- and fluorine-series amphiboles. The direct correlation between the Ga and F content and inverse relationship between the Ga and OH content may be a general phenomenon present in other minerals and suggests, for example, that high F contents in titanite are controlled by the Al content of the host rock and that there may be similar direct Al–F correlations in tschermakitic amphiboles. Evidence for the possibility that Al (Ga) might substitute onto only a subset of the tetrahedral sites in tschermakitic amphiboles was sought but not observed in this study. Received: 5 March 2001 / Accepted: 31 July 2001  相似文献   

10.
We measured the adsorption of Cu(II) onto kaolinite from pH 3-7 at constant ionic strength. EXAFS spectra show that Cu(II) adsorbs as (CuO4Hn)n−6 and binuclear (Cu2O6Hn)n−8 inner-sphere complexes on variable-charge ≡AlOH sites and as Cu2+ on ion exchangeable ≡X--H+ sites. Sorption isotherms and EXAFS spectra show that surface precipitates have not formed at least up to pH 6.5. Inner-sphere complexes are bound to the kaolinite surface by corner-sharing with two or three edge-sharing Al(O,OH)6 polyhedra. Our interpretation of the EXAFS data are supported by ab initio (density functional theory) geometries of analog clusters simulating Cu complexes on the {110} and {010} crystal edges and at the ditrigonal cavity sites on the {001}. Having identified the bidentate (≡AlOH)2Cu(OH)20, tridentate (≡Al3O(OH)2)Cu2(OH)30 and ≡X--Cu2+ surface complexes, the experimental copper(II) adsorption data can be fit to the reactions
  相似文献   

11.
It is shown the possibility to determine the coordination of paramagnetic ions in disordered solid structures, e.g., in barium borate glasses. For this purpose the electron paramagnetic resonance (EPR) method was used to study α-and β-BaB2O4 crystals and glasses of 45·BaO × 55·B2O3 and 40·BaO × 60·B2O3 (mol%) composition activated by Ag+ and Pb2+ ions. After the samples were exposed to X-rays at 77 K, different EPR centers were observed in them. In α-and β-BaB2O4 crystals and glasses the EPR centers Ag2+, Ag0, Pb+, Pb3+, and hole centers of O− type were studied. The EPR parameters of these centers and their arrangement in crystal structure were determined. It is shown that Pb3+ ions in β-BaB2O4 crystals occupy Ba2+ position in an irregular polyhedron from the eight oxygen, whereas in α-BaB2O4 crystals they occupy Bа2 position in a sixfold coordination. Pb+ ions in α-BaB2O4 crystals occupy Bа1 position in a ninefold coordination from oxygen. In barium borate glasses, Pb3+ ions were studied in coordination polyhedron from six oxygen atoms and in a polyhedron from nine to ten oxygen atoms. It is assumed that the established difference in the structural position of Pb3+ ions in glasses is due to their previous incorporation in associative cation–anion complexes (AC) and “free” structure-forming cations (FC). Computer simulations have been performed to analyze the stability of specific associative complexes and to compare their bond lengths with experimental data.  相似文献   

12.
This paper systematically deals with the geochemical features of major gold deposits in the Shaoxing-Longquan Uplift Zone, Zhejiang Province, including the content and association of ore-forming elements and trace elements, stable isotopic characteristics, the existing forms of gold, and the composition of ore fluids. The authors consider that the ore-bearing formations in this zone are a good supply of necessary elements and ore fluids for the gold deposits in this area. It is also considered that some Au+-Cl− and Au+-HS− or Au+-CO2 coordinated ions are the main transport forms of gold in ore fluids and the metallogenesis of gold involves two stages: formation of pyrite and mineralization of Cu, Pb and Zn. In this paper is also presented a comprehensive geochemical model for the formation of gold deposits in this uplift zone.  相似文献   

13.
Structures, stabilities and vibrational spectra have been calculated using molecular quantum mechanical methods for As(OH)3, AsO(OH)3, As(SH)3, AsS(SH)3 and their conjugate bases and for several species with partial substitution of S for O. Properties for the neutral gas-phase molecules are calculated with state-of-the-art methods which yield AsL distances within 0. 01 Å and AsL stretching frequencies within 10 cm−1 of experiment. Similar accuracy is obtained for neutral molecules in solution using a polarizable continuum model (PCM). For monoanions such as and frequencies can be calculated to within 20 cm−1 of experiment using the polarizable continuum model. Multiply charged anions remain a challenge for accurate frequency calculations, but we have obtained results within the PCM model which at least semiquantitatively reproduce the available data. This allows us to assign the controversial features D, E and F in the Raman data of (Wood S. A., Tait C. D. and Janecky D. R. (2002) A Raman spectroscopic study of arsenite and thioarsenite species in aqueous solution at 25 °C. Geochem. Trans. 3, 31-39).To help in the assignment of the arsenic sulfide spectra we have also calculated energetics for the oxidation of As(III) to As(V) compounds by polysulfides, disproportionation of As(III) compounds and for the dissociation of the oxo- and thio-acids. We have determined that As(III) oxyacids can be transformed to thioacids which can in turn be oxidized to As(V) sulfides by polysulfides and that the pKa1s of the acids involved can be ordered as follows: AsS(SH)3 < As(SH)3 < AsO(OH)3 < As(OH)3 in order of increasing pKa1. We have also established from the calculated energies that the most stable form of the As(III) oxyacid in acidic aqueous solution is indeed As(OH)3, consistent with previous assignments.  相似文献   

14.
《Applied Geochemistry》1988,3(5):523-533
The transition metals Fe, Cu, Zn and Pb have diffused only 10–20 cm into the clay barrier at the Confederation Road landfill compared to 130 cm for porewater chloride. Other major dissolved species, including the alkali and alkaline earth metals, have also diffused out of waste landfill and into clay subsoils more rapidly than the metals. Redox potentials, Eh, indicate strongly reducing conditions (Eh= − 130 mV) in the clayey soil at the subsoil/waste interface and increase to +50 mV at a depth of 45 cm below the interface. pH values are close to 8 within the subsoil but the slightly lower values (7.8–8) near the interface may result from production of organic acids during degradation of the wastes. Thermodynamic analysis of subsoil pore waters indicates that Fe, Cu, Zn and Pb exist primarily as metal-hydroxy complexes of the forms [MeOH]+ and [Me(OH)2]0, although a complex of [PbCl]+ may be significant, but not predominant. The analysis also demonstrates that the dissolved transition metal concentrations of the subsoil pore waters are controlled at carbonate mineral saturation levels, whereas Fe concentrations in leachate solutions associated with the wastes are controlled at FeS2 saturation levels.Thermodynamic calculations and Eh-pH diagrams suggest that Fe(OH)2, Zn(OH)2 and Pb(OH)2 are not stable phases in the solids of the subsoil. This means that observed “hydroxide” phases reported in the selective dissolution analysis by Yanful and Quigley (1986) have to be re-evaluated.  相似文献   

15.
The hydrolysis of the Pd2+ ion in HClO4 solutions was examined at 25–70°C, and the thermodynamic constants of equilibrium K (1)0 and K (2)0were determined for the reactions Pd2+ + H2O = PdOH+ + H+ and Pd2+ + 2H2O = Pd(OH)20 + 2H+, respectively. The values of log K (1)0 = −1.66 ± 0.5 (25°C) and −0.65 ± 0.25 (50°C) and log K (2)0 = −4.34 ± 0.3 (25°C) and −3.80 ± 0.3 (50°C) were derived using the solubility technique at 0.95 confidence level. The values of log K (1)0 = −1.9 ± 0.6 (25°C), −1.0 ± 0.4 (50°C), and −0.5 ± 0.3 (70°C) were obtained by spectrophotometric techniques. The palladium ion is significantly hydrolyzed at elevated temperatures (50–70°C) even in strongly acidic solutions (pH 1–1.5), and its hydrolysis is enhanced with increasing temperature.  相似文献   

16.
A novel complex continuous system of solid solutions involving vauquelinite Pb2Cu(CrO4)(PO4)(OH), bushmakinite Pb2Al(VO4)(PO4)(OH), ferribushmakinite Pb2Fe3+(VO4)(PO4)(OH), and a phase with the endmember formula Pb2Cu(VO4)(PO4)(H2O) or Pb2Cu(VO4)(РО3ОН)(ОН) is studied based on samples from the oxidation zone of the Berezovskoe, Trebiat, and Pervomaisko-Zverevsky deposits in the Urals, Russia. This is the first natural system in which chromate and vanadate anions show a wide range of substitutions and the most extensive solid solution system involving (CrO4)2– found in nature. The major couple substitution is Cr6+ + Cu2+ ? V5+ + M3+, where M = Fe, Al. The correlation coefficients calculated from 125 point analyses are: 0.96 between V and (Fe + Al), 0.96 between Cr and (Cu + Zn),–0.96 between V and (Cu + Zn),–0.97 between Cr and (Fe + Al), and–0.97 between (Fe + Al) and (Cu + Zn). The substitutions V5+ ? Cr6+ (correlation coefficient–0.98) and to a lesser extent P5+ ? As5+ (correlation coefficient–0.86) occur at two types of tetrahedral sites, whereas the metal–nonmetal/metalloid substitutions, i.e., V or Cr for P or As, are minor. The substitution Fe3+ ? Al3+ is also negligible in this solid solution system.  相似文献   

17.
Uraninite solubility in 0.001–2.0 m HCl solutions was experimentally studied at 500°C, 1000 bar, and hydrogen fugacity corresponding to the Ni/NiO buffer. It was shown that the following U(IV) species dominate in the aqueous solution: U(OH)40, U(OH)2Cl20, and UOH Cl30 Using the results of uraninite solubility measurement, the Gibbs free energies of U(IV) species at 500°C and 1000 bar were calculated (kJ/mol): −9865.55 for UO2(aq), −1374.57 for U(OH)2 Cl20, and −1265.49 for UOH Cl30, and the equilibrium constants of uraninite dissolution in water and aqueous HCl solutions were estimated: UO2(cr) = UO2(aq), pK 0 = 6.64; UO2(cr) + 2HCl0 = U(OH)2 Cl20, pK 2 = 3.56; and UO2(cr) + 3HCl0 = UOHcl30 + H2O, pK 3 = 3.05. The value pK 1 ≈ 5.0 was obtained as a first approximation for the equilibrium UO2(cr) + H2O + HCl0 = U(OH)3Cl0. The constant of the reaction UO2(cr) + 4HCl0 = UCl40 + 2H2O (pK 4 = 7.02) was calculated taking into account the ionization constants of U Cl40 and U(OH)40, obtained by extrapolation from 25 to 500°C at 1000 bar using the BR model. Intense dissolution and redeposition of gold (material of experimental capsules) was observed in our experiments. The analysis and modeling of this phenomenon suggested that the UO2 + x /UO2 redox pair oxidized Au(cr) to Au+(aq), which was then reduced under the influence of stronger reducers.  相似文献   

18.
 An integrated geological, geoelectrical and hydrochemical investigation of shallow groundwater occurrence in the Ibadan area, southwestern Nigeria, is presented. The primary objective was to characterise the groundwater in a typical low-latitude environment underlain by Precambrian crystalline basement complex rocks. The dominant rocks comprise suites of gneisses and quartzites. Chemical analyses of the groundwater show that the mean concentration of the cations is in the order Na>Ca>Mg>K while that for the anions is Cl>HCO3>NO3>SO4. Statistical analyses, using the product-moment coefficient of correlation, indicate positive correlations between the following pairs of parameters: TDS and conductivity (r=0.96); Na++Mg2+ and Cl– (r=0.95); Na++K+ and Ca2+ (r=0.43); Na++K+ and HCO3 – (r=0.17); Ca2+ and Mg2+ (r=0.74); Ca2+ and HCO3 – (r=0.33); Ca2++Mg2+ and HCO3 – (r=0.31) and pH and HCO3 – (r=0.54). A very weak negative correlation was recorded between pH and Cl–, with r=–0.003. Five groundwater groups have been identified, namely, (1) the Na-Cl, Na-Ca-Cl, Na-Ca-(Mg)-Cl; (2) the Ca-(Mg)-Na-HCO3-Cl, Na-Ca-HCO3-Cl, and Ca-HCO3-Cl; (3) the Ca-(Mg)-Na-HCO3, Ca-Na-HCO3; (4) Ca-Na-Cl-(SO4)-HCO3 and (5) the Ca-(Mg)-Na-SO4-HCO3. The different groups reflect the diversity of bedrock types and consequently also of the products of weathering. Most of the water sampled is unfit for drinking on account of the high NO3 – content. It can, however, be used for irrigation purposes as the sodium hazard is low while the salinity hazard ranges from low to medium. Resistivity soundings indicate the presence of a thick weathering profile, which could be up to 60 m. Such sites should be the target for any long-term and sustainable groundwater development in the area. Received: 15 April 1998 · Accepted: 4 July 1998  相似文献   

19.
Titanium complexation in hydrothermal systems   总被引：3，自引：0，他引：3  
The solubility of rutile in aqueous solutions of HCl, HF, H2SO4, NaOH, and NaF was determined at 500°C, 1000 bar, and hydrogen fugacity from 8 × 10−12 to 10.3 bar (Mn3O4/Mn2O3 and Ni/NiO buffers, dissolution of an Al batch weight). The experimentally determined solubility values were used to calculate the constants of the following equilibria at 500°C and 1 kbar pressure: TiO2(rutile) + H2O + HCl0 = Ti(OH)3Cl0 (pK = 4.89); TiO2(rutile) + 2HCl0 = Ti(OH)2Cl 2 0 (pK = 4.69), TiO2(rutile) + HS O 4 − + H+ = Ti(OH)2SO 4 0 (pK = 1.98), TiO2(rutile) + 2HSO 4 − + 2H+ = Ti(SO4) 2 0 + 2H2O (pK = −1.50), TiO2(rutile) + 2H2O + OH− = Ti(OH) 5 − (pK = 3.17), TiO2(rutile) + 2H2O + 2OH− = Ti(OH) 6 2− (pK = 1.46), TiO2(rutile) + 2H2O + F− = Ti(OH)3F0 + OH− (pK = 5.86), TiO2(rutile) + 2HF0 = Ti(OH)2F 2 0 (pK = 2.99), and TiO2(rutile) + 2H2O + F− = Ti(OH)4F− (pK = 3.69). Based on the results obtained on the composition of volcanic emanations whose Ti concentrations were determined, we evaluated the constants of the equilibria TiO2(rutile) + H2O + HCl0 = Ti(OH)3Cl0 (pK = 2.74) and TiO2(rutile) + HSO 4 − + H+ = Ti(OH)2SO 4 0 (pK = 3.40) at 25°C. The electrostatic model of electrolyte ionization was used to calculate the ionization constants and the Gibbs free energy values for the following Ti species in aqueous fluids at the parameters of postmagmatic processes: Ti(OH) 3 + , Ti(OH) 4 0 , Ti(OH) 5 − , Ti(OH) 6 2− , Ti(OH)3F0, Ti(OH)2F 2 0 , Ti(OH)4F−, Ti(OH)3Cl0, Ti(OH)2Cl 2 0 , Ti(OH)2SO 4 0 , and Ti(SO4) 2 0 . As follows from our data on Ti complexation with Cl, F, and SO4, fluids the most favorable for Ti migration are aqueous acid F-rich solutions with Ti concentrations of no higher than a few fractions of a milligram per kilogram of water. Original Russian Text ? B.N. Ryzhenko, N.I. Kovalenko, N.I. Prisyagina, 2006, published in Geokhimiya, 2006, No. 9, pp. 950–966.  相似文献   

20.
Electron density distributions, bond paths, Laplacian and local-energy density properties have been calculated for a number of As4S n (n = 3, 4 and 5) thioarsenide molecular crystals. On the basis of the distributions, the intramolecular As–S and As–As interactions classify as shared bonded interactions, and the intermolecular As–S, As–As and S–S interactions classify as closed-shell van der Waals (vdW) bonded interactions. The bulk of the intermolecular As–S bond paths link regions of locally concentrated electron density (Lewis-base regions) with aligned regions of locally depleted electron density (Lewis-acid regions) on adjacent molecules. The paths are comparable with intermolecular paths reported for several other molecular crystals that link aligned Lewis base and acid regions in a key–lock fashion, interactions that classified as long-range Lewis acid–base-directed vdW interactions. As the bulk of the intermolecular As–S bond paths (~70%) link Lewis acid–base regions on adjacent molecules, it appears that molecules adopt an arrangement that maximizes the number of As–S Lewis acid–base intermolecular bonded interactions. The maximization of the number of Lewis acid–base interactions appears to be connected with the close-packed array adopted by molecules: distorted cubic close-packed arrays are adopted for alacránite, pararealgar, uzonite, realgar and β-AsS and the distorted hexagonal close-packed arrays adopted by α- and β-dimorphite. A growth mechanism is proposed for thioarsenide molecular crystals from aqueous species that maximizes the number of long-range Lewis acid–base vdW As–S bonded interactions with the resulting directed bond paths structuralizing the molecules as a molecular crystal.  相似文献   

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