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.     

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.     

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.     

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.     

The solubility of MoO3 in aqueous solutions of HClO4 at T = 300°C and P = 100 bar by experimental data

The solubility of crystalline MoO₃ in aqueous solutions of HClO₄ at T = 300°C and P = 100 bar was determined in experiments. It was shown that the acidity of the solution is the determining factor of the solubility of molybdenum trioxide under hydrothermal parameters. The formation constant was calculated for the HMoO ₄ ^? neutral complex (pK ₀ = 3.50 ± 0.20).     

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.     

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.     

Molecular orbitals of Si2O 7 6− , Si3O 10 8− , etc., and mixed (B,Al,P,Si) m applied to clusters and X-ray spectroscopy data of silicates

The Si, Al L_{II, III} and OK_α emission and quantum yield spectra were obtained for 24 silicates. It was found that in minerals of a homogeneous anion composition the Si L_{II, III} line has double-humped structure, and when in addition to SiO ₄ ^4? ions of other composition (BeO ₄ ^6? , AlO ₄ ^5? etc.) are present it has triple-humped structure. The process of crystal-glass transition was studied by X-ray spectroscopy. The result is that in spite of the original form of the Si L_{II, III} line of the mineral this line changes its structure in glass and exhibits a typical double-humped structure. The CNDO/2 approach was used to calculate the electronic structure of basic structural groups of silicates from SiO ₄ ^4? to Si₅O ₁₆ ^12? by replacing one or two of the Si atoms by Be, B, Al and P. A qualitative interpretation of the X-ray spectra is presented.     

Thermodynamics of minerals of variable composition: Andradite-grossularite and pistacite-clinozoisite solid solutions

Exchange-mineral equilibria with Al and Fe³⁺ aqueous chloride solutions (aq.), Andr + AlCl _aq ³ = FeCl _aq ³ + Gros, (1) Psc + AlCl _aq ³ = FeCl _aq ³ + Czo, (2) were studied under the following experimental conditions: 500°;C and 580°;C and 1 and 2 kbar, respectively, with an overall concentration of metals in the aqueous solutions of about 0.5 M and pH 3. The mixing functions of the components in garnet and epidote were calculated from the experimental data. Thermodynamic treatment of experimental evidence for reaction (1) led to the conclusion that, within the accuracy of experiment, garnet in the andradite-grossularite series was an ideal solid solution. However, epidote solid solution markedly departed from the ideal, as was shown by concentration and pressure-temperature (PT) dependencies of Gibbs's molar excess energies and by mixing-volume concentration dependence.     

Assessment of hydrogeochemical processes in a coastal region: Application of multivariate statistical model

Hydrogeochemical studies have been carried out in a coastal region, using multivariate statistical model, for better understanding the controlling processes that influence the aquifer chemistry. Two principal components (PC1 and PC2) are extracted from the data set of chemical variables (pH, TDS, Ca²⁺, Mg²⁺, Na⁺, K⁺, HCO ₃ ^? , Cl^?, SO ₄ ^2? , NO ₃ ^? and F^?), which account for 79% of the total variation in the quality of groundwater. The PC1 (salinity controlled process) includes the concentrations of TDS, Mg²⁺, Na⁺, K⁺, Cl^?, SO ₄ ^2? and NO ₃ ^? , while the PC2 (alkalinity controlled process) comprises the concentrations of pH, HCO ₃ ^? and F^?. The spatial distribution of PC scores identifies the locations of high salinity and alkalinity processes. The first process corresponds to the influences of geogenic, anthropogenic and marine sources, and the second one to the influence of water-soil-rock interaction. Thus, the present study shows the usefulness of multivariate statistical model as an effective means of interpretation of spatial controlling processes of groundwater chemistry.     

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.     

Gold Solubility in SiO2—HCl—H2O System at 200℃：a Preliminary Assessment of the Implications of Silicification with Regard to Gold Mineralization

The complexation between gold and silica was experimentally, confirmed and calibrated at 200 °C: $$\begin{gathered} Au^ + + H_3 SiO_4^ - \rightleftharpoons AuH_3 SiO_4^0 \hfill \\ \log K_{(200^\circ C)} = 19.26 \pm 0.4 \hfill \\ \end{gathered} $$ Thermodynamic calculations show that AuH₃SiO ₄ ⁰ would be far more abundant than AuCl ₂ ^? under physicochemical conditions of geological interest, suggesting that silica is much more important than chloride as ligands for gold transport. In systems containing both sulfur and silica, AuH₃SiO ₄ ⁰ would be increasingly more important than Au (HS) ₂ ^? as the proportion of SiO₂ in the system increases. The dissolution of gold in aqueous SiO₂ solutions can be described by the reaction: $$\begin{gathered} Au + 1/4O_2 + H_4 SiO_4^0 \rightleftharpoons AuH_3 SiO_4^0 + 1/2H_2 O \hfill \\ log K_{(200^\circ C)} = 6.23 \hfill \\ \end{gathered} $$ which indicates that SiO₂ precipitation is an effective mechanism governing gold deposition, and thus explains the close association of silicification and gold mineralization.     

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.     

Characterization and origin of two Fe3+ EPR spectra in kaolinite

The electron paramagnetic resonance (EPR) spectra of Fe³⁺ in a well cristallized kaolinite from Decazeville in France are well resolved. It is shown that in this sample there are mainly two slightly different spectra, well separated at low temperature and characterized at -150° C by the constants B ₂ ⁰ = 0.112 cm^?1, B ₂ ² = 0.0688 cm^?1 for one and B ₂ ⁰ = 0.116 cm^?1, B ₂ ² = 0.0766 cm^?1 for the second. These two spectra arise from Fe³⁺ substituted for Al³⁺ at the two octahedral positions in equal amounts. The temperature dependence of EPR spectra was studied and was explained by a modification of the octahedral sites.     

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.     

Hydrochemical characteristics of groundwater in the plains of Phalgu River in Gaya, Bihar, India

Assessment of groundwater quality is essential to ensure sustainable use of it for drinking, agricultural, and industrial purposes. The chemical quality of groundwater of Gaya region has been studied in detail in this work to delineate the potable groundwater zones. A total of 30 groundwater samples and 2 surface water samples were collected in and around Gaya district of Bihar. The major cations follow the trend: Ca²⁺?>?Mg²⁺?>?Na⁺?>?K⁺. The domination of calcium ions in the groundwater is due to weathering of rocks. The K⁺ ranged between 0.2 and 47.95 ppm, suggesting its abundance the below desired limit; but some samples were found to be above permissible limit. K⁺ weathering of potash silicate and the use of potash fertilizer could be the source. The major anions abundance followed the order HCO ₃ ^? ?>?Cl^??>?SO ₄ ^2? ?>?NO ₃ ^? ?>?PO ₄ ^3? . Dissolution of carbonates and reaction of silicates with carbonic acid accounts for the addition of HCO ₃ ^? to the groundwater and oxidation of sulphite may be the source of SO ₄ ^2? . Principal component analysis was utilized to reflect those chemical data with the greatest correlation and seven major principal components (PCs) representing >80 % of cumulative variance were able to interpret the most information contained in the data. PC1, PC2 and PC3 reflect the hydrogeochemical processes like mineral dissolution, weathering and anthropogenic sources. PC4, PC5, PC6 and PC7 show monotonic, random and independent relationships.     

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.     

Using chemical analysis and modeling to enhance the understanding of soil solution of some calcareous soils

The chemistry of soil solutions can be altered by human activities, due to the intense agricultural and husbandry, leading to leaching of nutrients and subsequently elevating ground water levels. Multivariate statistical and inverse geochemical modeling techniques were used to determine the main factors controlling soil solution chemistry of calcareous soils. In this research, a total of 21 calcareous soils was characterized and assessed for soil solution using soil column. The major cations in the studied soil solutions were in the decreasing order as Ca²⁺ > Mg²⁺ > Na⁺ > K⁺. The anions were also arranged in decreasing order as HCO $ _{3}^{ - } $  > Cl $ ^{ - } $  > SO $ _{4}^{2 - } $  > NO $ _{3}^{ - } $ . Concentrations of NO $ _{3}^{ - } $ , P, and K⁺ in soil solutions were in the range of 6.8–307.5 mg l^?1 (mean 63.2 mg l^?1), 5.0–10.4 mg l^?1 (mean 5.9 mg l^?1), and 2.8–54.6 mg l^?1 (mean 11.3 mg l^?1), respectively. Results suggest that the concentration of P in the soil solutions could be primarily controlled by the solubility of dicalcium phosphate dihydrate and dicalcium phosphate. Interactions between soil properties and observed solubility of nutrients were described, and put into empirical multivariate formulations. Obtained equations contained electrical conductivity (EC) as a key factor in determining nutrients solubility. Inverse geochemical modeling of soil solution using PHREEQC indicates the dissolution of calcite, anhydrite, halite, CO₂ (g), N₂ (g), and hydroxyapatite, and precipitation of sulfur. Cation exchange between Ca²⁺, Mg²⁺, K⁺ and Na⁺ occurred with Mg²⁺ and K⁺ into the solution, and Ca²⁺ and Na⁺ out of the solution. Determination of soil solution will improve soil management in the area, and preventing groundwater deterioration.     

Interdiffusion of NaSi—CaAl in peristerite

The ‘average’ interdiffusion coefficient ( \(\bar D\) ) for NaSi—CaAl exchange in plagioclase for the interval from An₀ to An₂₆ was estimated from experimentally determined homogenization times for peristerite exsolution lamellae. The average spacing between adjacent (unlike) lamellae is 554±77 Å. Dry heating in air at 1,100°C for 98 days produced no change in the exsolution microstructure; thus \(\bar D\) (dry)<10^?17 cm²/s. This limit is consistent with the recently reported ‘average’ \(\bar D\) (dry) values for the Huttenlocher interval (An_70–90) at this temperature. At 1.5 GPa with about 0.2 weight percent water added the ‘average’ diffusion coefficient from 1,100°C to 900°C is given by: \(\bar D\) (wet)=18 _?15 ⁺¹⁰⁸ (cm²/s) exp (?97±5 (kcal/mol)/RT), where R is the gas constant, and T is °K. This \(\bar D\) (wet) at 1,100°C is more than three orders of magnitude greater than \(\bar D\) (dry) for Na- and Ca-rich plagioclases.     

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? .