Hydrotalcite-like solid solutions with variable SO 4 2− and CO 3 2− contents at 50° C

Hydrotalcite-like solid solutions have been synthesized by coprecipitation in basic solutions with variable SO ₄ ^2? /CO ₃ ^2? ratios. Chemical determination of CO ₃ ^2? in the interlayer was impossible because of the presence of minor hydromagnesite. SO ₄ ^2? was determined both by chemical analysis and X-ray photoelectron spectroscopy (XPS), the two methods giving similar results. A Raman spectrometry gave additional data on the SO ₄ ^2? /CO ₃ ^2? ratio. Then, the stoichiometry of the anionic interlayers, X _s , X _c , and X _OH were determined, and the influence of X _s on the c′ parameter (increasing from c′=7.97 Å to c′=8.63 Å between X _s =0 and X _s =1) was characterized. In addition, a partitioning curve of SO ₄ ^2? and CO ₃ ^2? between aqueous solutions and hydrotalcite-like compounds was established. Its general shape strongly suggests a miscibility gap between a sulfate-rich end and a carbonate-rich solid solution (maximum SO ₄ ^2? /CO ₃ ^2? about 0.2). This result explains why most of the hydrotalcites synthesized during experimental alteration of basaltic glasses by sea-water (a sulfate-rich solution) are CO ₃ ^2? -rich solid solutions.     

A new Cu-rich variety of lyonsite from fumarolic sublimates of the Tolbachik volcano (Kamchatka, Russia) and its crystal structure

A new Cu-rich variety of lyonsite has been found from fumarolic sublimates of the Tolbachik volcano (Kamchatka, Russia). The empirical formula is Cu_4.33Fe _2.37 ³⁺ Ti_0.26Al_0.26Zn_0.07(V_5.85As_0.07Mo_0.07P_0.01S_0.01)O₂₄. The crystal structure was studied on single crystal using synchrotron radiation, R = 0.0514. The mineral is orthorhombic, Pnma, a = 5.1736(7), b =10.8929(12), c = 18.220(2) Å, V = 1026.8(2) ų, and Z = 2. The structural formula is (Cu_0.6Ti_0.3Al_0.3Fe _0.2 ³⁺ □_0.6)_Σ2Cu₂(Fe _2.2 ³⁺ Cu_1.8)_Σ4(V_5.8As_0.1Mo_0.1)_Σ6O₂₄. It is proposed to recast the simplified formula of lyonsite as Cu_3+x (Fe _4?2x ³⁺ Cu_2x )(VO₄)₆, where 0 ≤ x ≤ 1.     

A theoretical study of bond distances,X-ray spectra and electron density distributions in borate polyhedra

The borate polyhedra BO ₃ ^3? , B(OH)₃, BO ₄ ^5? , and B(OH) ₄ ^? are studied using the ab initio and multiple scattering Xα quantum mechanical methods. The ab initio self-consistent-field (SCF) molecular orbital (MO) method, at the minimum basis set level, predicts equilibrium B-O distances within 0.04 Å of their average values in solids so long as the polyhedron charge is small. Orbital energies from double zeta basis set ab initio calculations and analogies with isoelectric compounds are used to assign the X-ray spectra of BO ₃ ^3? and to predict the valence region spectra of BO ₄ ^5? . Contour maps of the difference between molecular and superimposed free atom electron densities show charge buildup along the B-O bond which is only slightly smaller than that observed in CO ₃ ^2? .     

The effect of medium chemistry on the solubility and morphology of brushite crystals

An experimental study of the particulars of the solubility and crystallization of brushite Ca(HPO₄) · 2H₂O from aqueous solution in conditions of a variable pH (6.0–3.0) and the contents of impurity ions (K⁺, Na⁺, NH ₄ ⁺ , Mg²⁺, SO ₄ ^2? , CO ₃ ^2? ) has been conducted. It is established that brushite solubility markedly rises with a decrease in pH from 6 to 3 and slightly rises with an increase in Mg²⁺ and SO ₄ ^2? concentrations. The enrichment in K⁺, Na⁺, and NH ₄ ⁺ does not affect brushite solubility. The changeable chemistry of the medium results in variation of the synthetic crystal habit, from rhombic tabular to thickened prismatic crystals.     

First principles quantum mechanical calculation of the electric dipole polarizabilities of the borate,carbonate, nitrate and related ions

Electric dipole polarizabilities have been calculated from first principles of quantum mechanics for the BO ₃ ^3? , CO ₃ ^2? , NO ₃ ^? series and for NO ₂ ^? and LiNO₃(g). Calculated trends in average polarizability and polarizability anisotropy in the BO ₃ ^3? -NO ₃ ^? series are in agreement with experiment and can be qualitatively interpreted in terms of the varying energies of the a₁′, a₂″ and e′ symmetry unoccupied MO's of the oxyanions. Embedding a CO ₃ ^2? ion in a D_3h symmetry array of divalent cations reduces both the average polarizability and its anisotropy, particularly when diffuse s and p functions are included in the calculation. Calculations on the gas phase LiNO₃ molecule and on the free NO ₃ ^? ion in the distorted geometry found in LiNO₃(g) allow us to separate polarizability contributions internal to the NO ₃ ^? and Li⁺ ions from those which arise from the Li⁺-NO ₃ ^? interaction. The Li⁺-NO ₃ ^? interaction term so obtained is much smaller than the NO ₃ ^? contribution but is in turn larger than the Li⁺ contribution, suggesting that the inclusion of this interaction term is essential for obtaining accurate results for ion pairs. Although static polarizabilities are in reasonable agreement with experiment for NO ₃ ^? the wavelength dispersion of the polarizability is underestimated by about a factor of two, apparently as a result of inadequacies in the quantum mechanical method. Calculated values are also presented for ¹⁴N NMR shieldings in the nitrogen oxyanions but these are in only qualitative agreement with the experimental values. Similarly, calculated values of magnetic susceptibility are in only qualitative agreement with experiment although trends along the BO ₃ ^3? -NO ₃ ^? series are properly reproduced.     

Stabilization of complex ions by the crystal field: CO 3 2− , NO 3 − , O 3 − , [(OH)4]4−, [(OH)3F]4−, [(OH)2F2]4−

According to Koopmans' theorem, only the electrons associated with molecular levels of negative energy are stable. Many ions which cannot exist in the isolated state because certain occupied levels are positive, become stable in crystals under the stabilization effect arising from the crystal field. As examples, we have studied CO ₃ ^2? in calcite, NO ₃ ^? in NaNO₃, and several natural limpurities: O ₃ ^? in fluorite, [(OH)₄]^4?, [(OH)₃F]^4? and [(OH)₂F₂]^4? in zircon and thorite, by means of the molecular self-consistent field, the crystal field being simulated by point charges. As expected, all the energies corresponding to the occupied levels are negative within the crystal field, contrary to what occurs in the isolated state. Informations concerning the structure and the size of the critical germ are obtained for CaCO₃ and NaNO₃.     

Thermodynamics of plagioclase II: Temperature evolution of the spontaneous strain at the I\bar 1 \leftrightarrow P\bar 1 phase transition in anorthite

The temperature dependence of the lattice parameters of pure anorthite with high Al/Si order reveals the predicted tricritical behaviour of the \(I\bar 1 \leftrightarrow P\bar 1\) phase transition at T _c ^* =510 K. The spontaneous strain couples to the order parameter Q° as x _i∝S _xQ ⁱ Q°² with S _xQ ¹ =4.166×10^?3, S _xQ ² =0.771×10^?3, S _xQ ³ =?7.223×10^?3 for the diagonal elements. The temperature dependence of Q° is $$Q^{\text{o}} = \left( {1 - \frac{T}{{510}}} \right)^\beta ,{\text{ }}\beta = \tfrac{{\text{1}}}{{\text{4}}}$$ A strong dependence of T _c ^* , S _xQ ⁱ and β is predicted for Al/Si disordered anorthite.     

The ionic conductivity in high-pressure polymorphs of calcite

Ionic conductivity of polycrystalline calcite containing varying amounts of PO ₄ ^3? ions was measured in the pressure range of 1–6 GPa and at room temperature. Electrical conductivity increased with pressure corresponding to the phase transition of calcite I to calcite II. The conductivity in calcite III decreased exponentially with pressure. Calculated activation volumes of the conductivity varied with PO ₄ ^3? content in the range of 0.94–5.34 cm³/mol. This variation corresponded to the lattice parameter change of calcite I due to PO ₄ ^3? incorporation and indicated the contribution of CO ₃ ^2? -vacancies associated with PO ₄ ^3? ions to the conductivity.     

On the nonstoichiometry and point defects of olivine

This paper presents the point-defect thermodynamics for fayalite and olivine solid solutions (Fe _x Mg_1?x )₂SiO₄. By means of thermogravimetry, the metal-to-oxygen ratio of these silicates has been determined as a function of oxygen potential, compositionx and temperature. Experiments were performed in the range of 1,000° C≦T≦1,280° C and 0.2≦x≦1.0. It is found that V _Me ^″ , Fe _Me ^· and the associate {Fe′ _Si ^′ Fe _Me ^· } are the majority defects. With this knowledge it is possible to calculate the nonstoichiometry at given temperature as a function of \(p_{O_2 } \) and \(a_{SiO_2 } \) . The cation vacancy concentration shows a \(p_{O_2 }^{1/5} \) -dependence (forx≧0.2) and increases at givenT and \(p_{O_2 } \) almost exponentially with compositionx. In the composition range studied here, the silicates show an oxygen excess, and FeO is more soluble in the olivine than SiO₂.     

Urban land-use effects on groundwater phosphate distribution in a shallow aquifer, Nanfei River basin, China

Groundwater, surface water, soil and river sediment samples, and information on land use in the Nanfei River basin (NRB) of China have been analyzed to study the geochemistry, distribution, and mobilization of phosphorus. The distribution of phosphate (PO ₄ ^3??/sup> ) and the relationships between PO ₄ ^3??/sup> and several constituents in groundwater were studied. Partial correlation analysis relating PO ₄ ^3??/sup> to types of land use was conducted using the data analyzing tool SPSS 15.0. The processes controlling the transport of PO ₄ ^3??/sup> are discussed. The conclusions from this study are: (1) urban land use has obvious impact on PO ₄ ^3??/sup> in groundwater, the average concentration of PO ₄ ^3??/sup> being 4.37?mg/L, greater than that resulting from farmland and mixed land use, which have average PO ₄ ^3??/sup> concentrations of 0.10 and 0.18?mg/L, respectively; (2) the partial correlation between PO ₄ ^3??/sup> and types of land use is significant with a coefficient of 0.760; (3) the PO ₄ ^3??/sup> concentrations in surface water are generally higher than those in groundwater, and the total phosphorus (TP) concentrations in river sediments are generally higher than those in soil samples; (4) groundwater is a carrier of PO ₄ ^3??/sup> and is likely responsible for the redistribution of PO ₄ ^3??/sup> in different regions of NRB.     

Optical absorption spectra of iron ions in vivianite

Absorption bands are determined in polarized optical spectra of vivianite Fe₃(PO₄)₂·8H₂O, recorded at room and low temperatures. These bands are caused by spin-allowed d-d transitions in structurally nonequivalent Fe _A ²⁺ (～11000 cm^-1 (γ-polarization) (and) ～12000 cm^-1 (β-polarization)) (and) Fe _B ²⁺ (～8400 cm^-1 (γ, α-polarization) and ～11200 cm^-1 (α-polarization)) ions. A charge transfer band (CTB) Fe _B ²⁺ +Fe _B ³⁺ →Fe _B ²⁺ +Fe _B ²⁺ (～15000 cm^-1) also determined, has polarizing features giving evidence of a change in the Fe _B ²⁺ -Fe _B ³⁺ bond direction, when compared with Fe _B ²⁺ -Fe _B ²⁺ . Bands of exchange-coupled Fe³⁺-Fe³⁺ pairs (～19400, ～20400, ～21300 and ～21700 cm^-1) which appear on oxidation of Fe²⁺ in paired Fe _B octahedra are also characterized.     

Electron paramagnetic resonance of PO 3 2− and SO 3 − radicals in anhydrite,celestite and barite: the hyperfine structure and dynamics

Electron paramagnetic resonance (EPR) measurements of natural anhydrite CaSO₄, celestite SrSO₄ and barite BaSO₄ have revealed the presence of PO ₃ ^2? and SO ₃ ^? radicals. Hyperfine structure from³³S has been detected and measured for the first time. Low-symmetry effects, which are manifested in noncoincidence of g and hyperfine axes, were observed for SO ₃ ^? . The dynamics of one of the two SO ₃ ^? types in anhydrite has been investigated. Variations of spin Hamiltonian parameters with temperature have been attributed to thermally induced jumps between the two magnetically inequivalent sites of this center.     

X-ray spectra of iron atoms in minerals

The results of X-ray fluorescence Ka _1,2 and Kβ₁,β′-spectra of iron in 54 samples, including 23 minerals, are presented. Spectrum characteristics are mainly dependent on the environment of iron in the sample, the most susceptible parameter being the chemical shift δβ₁. For the compounds investigated δβ₁ varies between ?1.58 eV and +1.56 eV when referring to metallic iron. Chemical shifts of compounds with predominantly covalent bonds exhibit more negative values, compounds with metallic bonds nearly vanishing values and compounds with predominantly ionic bonds more positive values. The FeKβ₁,β′-group of lines is actually a superposition of three lines: the long-wave line β′ and two overlapping lines β ₁ ⁵ and β ₁ ⁷ of which the superposition is conventionally denoted as β₁. The relative intensity of β ₁ ⁵ increases with ionicity of the bond, while that of β ₁ ⁷ decreases. The effective charge of iron has been determined for a group of iron-bearing minerals.     

Localized zones of denitrification in a floodplain aquifer in southern Wisconsin, USA

A floodplain aquifer within an agricultural watershed near Madison, Wisconsin (USA), was studied to determine whether denitrification was occurring below the surface organic layer. Groundwater levels and concentrations of O₂, Cl^?, NO ₃ ^? , SO ₄ ^2? , dissolved organic carbon (DOC), and major cations were monitored over a 1-year period along a 230-m transect between an agricultural field and a stream discharge point. Seventeen groundwater samples were analyzed for δ¹⁵N_NO3 and δ¹⁸O_NO3 composition. Samples in which NO ₃ ^? was too low for stable isotope analysis were analyzed for excess dissolved N₂. Groundwater NO ₃ ^? concentrations declined between the agricultural field and the discharge point. Chloride and δ¹⁵N_NO3/δ¹⁸O_NO3 data indicated that the drop in NO ₃ ^? was caused primarily by dilution of shallow NO ₃ ^? -rich water with deeper, NO ₃ ^? -depleted groundwater. Two localized zones of denitrification were identified in the upland-wetland transition by their δ¹⁵N_NO3 and δ¹⁸O_NO3 signatures, and two in the stream hyporheic zone by the presence of excess dissolved N₂. The combined stratigraphic, hydrologic, and geochemical data in these locations correspond to groundwater mixing zones where NO ₃ ^? is delivered to subsurface layers that support denitrification fueled by dissolved (e.g. DOC or dissolved Fe(II)) and/or solid-phase (e.g. particulate organic carbon, solid-associated Fe(II), or pyrite) electron donors.     

Zn and Pb solubility and speciation in aqueous chloride fluids at T-P parameters corresponding to granitoid magma degassing and crystallization

The solubility of all possible Zn and Pb species in aqueous chloride fluids was evaluated by means of thermodynamic simulations in systems ZnO(PbO)-aqueous solution of NaCl (KCl, NaCl + HCl) within broad ranges of temperature (600–900°C), pressure (0.7–5 kbar), and chloride concentrations, under parameters corresponding to the crystallization and degassing of granitoid magmas in the Earth’s crust. Our simulation results demonstrate that the addition of Cl to the fluid phase in the form of Na(K)Cl and HCl significantly increases the concentrations of Cl-bearing Zn and Pb complexes and the total concentration of the metals in the solutions in equilibrium with the solid oxides. In Zn-bearing fluids, the Zn(OH) ₂ ⁰ , ZnOH⁺, and Zn(OH) ₃ ^? —hydroxyl complexes and the ZnCl ₂ ⁰ , and ZnCl⁺ chlorocomplexes, which are predominant at low Cl concentrations (C_Cl < 0.05–0.1 m) give way to ZnCl ₄ ^2? with increasing C_Cl, which becomes the predominant Zn species of the fluid at C_Cl > 0.1–0.5 m throughout the whole temperature range in question and pressures higher than 1 kbar. For Pb-bearing fluids, the T-P-X region dominated by the Pb(OH) ₂ ⁰ , and Pb(OH) ₃ ^? hydroxyl complexes is remarkably wider than the analogous region for Zn, particularly at elevated temperatures (≥700°C) in alkaline solutions. An increase in C_Cl is associated with an increase in the concentration and changes in the speciation of Pb chlorocomplexes: PbCl ₂ ⁰ → PbCl ₃ ^? → PbCl ₄ ^2? . The concentrations of Zn and Pb chlorocomplexes increase with increasing pressure, decreasing temperature, and decrease pH with the addition of HCl to the system. It is demonstrated that the solubility of ZnO at any given T-P-X in alkaline solutions with low chloride concentrations are lower than the solubility of PbO. The Zn concentration increases more significantly than with the Pb concentration with increasing C_Cl and decreasing pH, so that the Zn concentration in acidic solutions is higher than the Pb concentration over broad ranges of temperature, pressure, and Cl concentration. Chloride complexes of Zn (ZnCl ₂ ⁰ , and ZnCl ₄ ^2? ) and Pb (PbCl ₂ ⁰ , and PbCl ₃ ^? are proved to be predominant within broad T-P-X-pH ranges corresponding to the parameters under which magmatic fluid are generated. Our simulation results confirm the hypothesis that chlorocomplexes play a leading role in Zn and Pb distribution between aqueous chloride fluids and granitic melts. These simulation results are consistent with experimental data on the Zn and Pb distribution coefficients (D(Zn)^f/m and D(Pb)^f/m, respectively) between aqueous chloride fluids and granitic melts that demonstrated that (1) D(Zn)^f/m and D(Pb)^f/m increase with increasing Na and K chloride concentrations in the aqueous fluid, (2) both D(Zn)^f/m and D(Pb)^f/m drastically increase when HCl is added to the fluid, and (3) (D(Zn)^f/m is higher than D(Pb)^f/m at any given T-P-X parameters. The experimentally established decrease in D(Zn)^f/m and D(Pb)^f/m with increasing pressure (at unchanging temperature and Cl concentration) is likely explained by an increase in the alkalinity of the aqueous chloride fluid in equilibrium with granite melt and, correspondingly, a decrease in the Zn and Pb solubility in this fluid.     

The lattice energy of forsterite. Charge distribution and formation enthalpy of the SiO 4 4− ion

In the lattice energy expression of forsterite, based on a Born-Mayer (electrostatic+repulsive+dispersive) potential, the oxygen charge z _o, the hardness parameter ρ and the repulsive radii r _Mg and r _Si appear as unknown parameters. These were determined by calculating the first and second partial derivatives of the energy with respect to the cell edges, and equalizing them to quantities related to the crystal elastic constants; the overdetermined system of equations was solved numerically, minimizing the root-mean-square deviation. To test the results obtained, the SiO ₄ ^4? ion was assumed to move in the unit-cell, and the least-energy configuration was sought and compared with the experimental one. By combining the two methods, the optimum set of parameters was: z _o=?1.34, ρ=0.27 Å, r _Mg=0.72 Å, r _Si=0.64 Å. The values ?8565.12 and ?8927.28 kJ mol^?1 were obtained, respectively, for the lattice energy E _Land for its ionic component E _L ⁰ ,which accounts for interactions between Mg²⁺ and SiO ₄ ^4? ions only. The charge distribution calculated on the SiO ₄ ^4? ion was discussed and compared with other results. Using appropriate thermochemical cycles, the formation enthalpy and the binding energy of SiO ₄ ^4? were estimated to be: ΔH _f(SiO ₄ ^4? )=2117.6 and E(SiO ₄ ^4? )=708.6 kJ mol^?1, respectively.     

Carbon Dioxide in igneous petrogenesis: I

A number of experimental CO₂ solubility data for silicate and aluminosilicate melts at a variety of P- T conditions are consistent with solution of CO₂ in the melt by polymer condensation reactions such as SiO _4(m ^4? +CO_2(v)+Si _n O _3n+1(m) ⁽²ⁿ⁺¹⁾ ?Si _n+1O _3n+4(m) ^(2n+4)? +CO _3(m ^)2? . For various metalsilicate systems the relative solubility of CO₂ should depend markedly on the relative Gibbs free change of reaction. Experimental solubility data for the systems Li₂O-SiO₂, Na₂O-SiO₂, K₂O-SiO₂, CaO-SiO₂, MgO-SiO₂ and other aluminosilicate melts are in complete accord with predictions based on Gibbs Free energies of model polycondesation reactions. A rigorous thermodynamic treatment of published P- T-wt.% CO₂ solubility data for a number of mineral and natural melts suggests that for the reaction CO_2(m) ? CO_2(v)

1. CO₂-melt mixing may be considered ideal (i.e., { \(a_{{\text{CO}}_{\text{2}} }^m = X_{{\text{CO}}_{\text{2}} }^m \) );
2. \(\bar V_{{\text{CO}}_{\text{2}} }^m \) , the partial molal volume of CO₂ in the melt, is approximately equal to 30 cm³ mole^?1 and independent of P and T;
3. Δ C _p ⁰ is approximately equal to zero in the T range 1,400° to 1,650 °C and
4. enthalpies and entropies of the dissolution reaction depend on the ratio of network modifiers to network builders in the melt. Analytic expressions which relate the CO₂ content of a melt to P, T, and \(f_{{\text{CO}}_{\text{2}} } \) for andesite, tholeiite and olivine melilite melts of the form

$$\ln X_{{\text{CO}}_{\text{2}} }^m = \ln f_{{\text{CO}}_{\text{2}} } - \frac{A}{T} - B - \frac{C}{T}(P - 1)$$ have been determined. Regression parameters are (A, B, C): andesite (3.419, 11.164, 0.408), tholeiite (14.040, 5.440,0.393), melilite (9.226, 7.860, 0.352). The solubility equations are believed to be accurate in the range 3<P<30 kbar and 1,100°<T<1,650 °C. A series of CO₂ isopleth diagrams for a wide range of T and P are drawn for andesitic, tholeiitic and alkalic melts.     

Submarine Groundwater Discharge-Derived Nutrient Loads to San Francisco Bay: Implications to Future Ecosystem Changes

Submarine groundwater discharge (SGD) was quantified at select sites in San Francisco Bay (SFB) from radium (²²³Ra and ²²⁴Ra) and radon (²²²Rn) activities measured in groundwater and surface water using simple mass balance box models. Based on these models, discharge rates in South and Central Bays were 0.3?C7.4?m³?day^?1?m^?1. Although SGD fluxes at the two regions (Central and South Bays) of SFB were of the same order of magnitude, the dissolved inorganic nitrogen (DIN) species associated with SGD were different. In the South Bay, ammonium (NH ₄ ⁺ ) concentrations in groundwater were three-fold higher than in open bay waters, and NH ₄ ⁺ was the primary DIN form discharged by SGD. At the Central Bay site, the primary DIN form in groundwater and associated discharge was nitrate (NO ₃ ^? ). The stable isotope signatures (??¹⁵N_NO3 and ??¹⁸O_NO3) of NO ₃ ^? in the South Bay groundwater and surface waters were both consistent with NO ₃ ^? derived from NH ₄ ⁺ that was isotopically enriched in ¹⁵N by NH ₄ ⁺ volatilization. Based on the calculated SGD fluxes and groundwater nutrient concentrations, nutrient fluxes associated with SGD can account for up to 16?% of DIN and 22?% of DIP in South and Central Bays. The form of DIN contributed to surface waters from SGD may impact the ratio of NO ₃ ^? to NH ₄ ⁺ available to phytoplankton with implications to bay productivity, phytoplankton species distribution, and nutrient uptake rates. This assessment of nutrient delivery via groundwater discharge in SFB may provide vital information for future bay ecological wellbeing and sensitivity to future environmental stressors.     

Le gisement de tungstène de Xihuashan (Sud-Jiangxi,Chine): Relations granites,altérations deutériques-hydrothermales,minéralisations

The Xihuashan tungsten deposit (South Jiangxi, China) is located on the border of a granitic stock composed of four intrusive units: γ _inf2a ^sup5 , γ _inf2b ^sup5 , γ _inf2c ^sup5 and γ _inf2e ^sup5 chronologically. The deposit is situated in γ _inf2a ^sup5 and γ _inf2b ^sup5 whose contact zone is marked by a stockscheider and by a sporadic fine-grained granite designated γ _inf2b′ ^sup5 . The feldspathic episyenitic veins or masses located mainly in γ _inf2b ^sup5 resulted from granite alteration. This alteration characterizes the fluid activity which followed previous mechanical action, remnant liquids draining under structural control. The quartz-bearing Xihuashan veins (Dayu mining district) are a typical wolframite-quartz vein deposit and have developed mainly in γ _inf2b ^sup5 . The density of the veins and the huge mineralizations in γ _inf2b ^sup5 can be explained by the carapace role played by γ _inf2a ^sup5 , γ _inf2b′ ^sup5 and the stockscheider. The deposit is formed by 615 economically valuable veins (medium grade: 1,08% in WO₃) characterized by four stages of mineralization; a reverse vertical zoning is generally observed. Thus, the Xihuashan tungsten deposit possesses a metallogenic value contributing to the comprehension of metallogenic and structural phenomena related to the evolution of granitic masses.     

Thermodynamic properties of Pd chloride complexes and the Pd2+(aq) ion in aqueous solutions

Based on the expert review of literature data on the thermodynamic properties of species in the Cl-Pd system, stepwise and overall stability constants are recommended for species of the composition [PdCl _n ]^{2 ? n} , and the standard electrode potential of the half-cell PdCl ₄ ^2? /Pd(c) is evaluated at E _298,15° = 0.646 ± 0.007 V, which corresponds to Δ _f G _298.15° = ?400.4 ± 1.4 kJ/mol for the ion PdCl ₄ ^2? (aq). Derived from calorimetric data, Δ _f H _298.15° PdCl ₄ ^2? (aq) = ?524.6 ± 1.6 kJ/mol and Δ _f H _298.15° Pd²⁺(aq) = 189.7 ± 2.6 kJ/mol. The assumed values of the overall stability constant of the PdCl ₄ ^2? ion and the standard electrode potential of the PdCl ₄ ^2? /Pd(c) half-cell correspond to Δ _f G _298.15° = 190.1 ± 1.4 kJ/mol and S _298.15° = ?94.2 ± 10 J/(mol K) for the Pd²⁺(aq) ion.