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.     

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.     

Characterization, classification, and determination of drinkability of some Algerian thermal waters

In this study, the physicochemical parameters (Conductivity, pH, Cl^?, HCO ₃ ^? , PO ₄ ^3? , SO ₄ ^2? , NO ₃ ^? , NO ₂ ^? , F^?, TH, Ca²⁺, K⁺, Mg²⁺, Na⁺, and DS) were determined for 41 samples collected from fourteen places in Algeria. The temperature of the thermal water samples at collection sites varied from 26°C to 86°C. pH values varied from 6.5 to 8.5 (i.e., from slightly acidic to moderately alkaline); 90.24% of the samples exhibited relatively high salinity (DS?=?550–5,500 mg L^?1). Total hardness measurements indicated these waters to be moderately hard. Forty-six percent of the samples are Na–Cl in character. The ratios Na⁺/Ca²⁺, Na⁺/Mg²⁺, and (Na⁺ + K⁺)/(Ca²⁺ + Mg²⁺) were high in 90.24% of the samples. This indicates the ion exchange process is important, which indicates that most of the Algerian thermal waters had developed over a long period at a depth sufficient to react with the rock. Statistical analyses of the physicochemical data gave positive correlation values, thereby enabling good interpretation of the results and revealing the composition of ions present in the thermal waters, as well as some information about their origin. The therapeutic properties associated with thermal waters encourage people at spas to drink the water they bathe in. Therefore, we examined the drinkability of these thermal waters. World Health Organization (WHO 1993) standards were used to evaluate the thermal water quality for drinking. With respect to hardness, the samples were classified as moderately hard (58.54% of the samples), very hard (36.58% of the samples), and soft (4.88% of the samples). The drinkability study shows that only 16 samples of the investigated waters were drinkable and thus could be consumed without special precaution.     

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.     

Geochemical characterization of groundwater from shallow aquifer surrounding Fetzara Lake N. E. Algeria

Hydrogeochemical investigations were carried out around Fetzara Lake, Northeast Algeria, to assess the quality of groundwater for its suitability for drinking and irrigation purposes. The groundwater chemistry is mainly controlled by the water?Crock interactions, but also influenced by other processes such as evapotranspiration and ion exchange. Groundwater samples collected, during two periods (1993 and 2007) from wells in the area were analyzed for pH, EC, TDS, Ca²⁺, Mg²⁺, Na⁺, K⁺, CO ₃ ^2? , HCO ₃ ^? , Cl^?, SO ₄ ^2? , and NO ₃ ^? . The chemical relationships in Piper??s diagram and Gibbs??s diagram suggest that groundwaters mainly belong to noncarbonate alkali type and Cl^? group and are controlled by evaporation dominance, respectively, due to the sluggish drainage conditions, greater water?Crock interaction, and anthropogenic activities. A comparison of the groundwater quality in relation to drinking water quality standards proves that most of the water samples are not suitable for drinking. US Salinity Laboratory??s and Wilcox??s diagrams and %Na⁺ used for evaluating the water quality for irrigation suggest that the majority of the groundwater samples are not good for irrigation.     

Characterization of the Eva Verda basin aquifer (Saint Marcel, Aosta Valley, Italy) through geochemical and geostructural methods and analysis

The groundwater system of the Eva Verda basin (Saint Marcel Valley, southern side of the middle Aosta Valley, Italy) has many springs that can be used as sources for drinking water. This area is near the disused Servette mine, which can be a pollutant source (metals and sulfides) for the springs located downhill. Aquifer characterization was done using a multidisciplinary approach: geostructural, lithological, hydrogeological and geochemical. In particular, the geostructural analysis showed that the preferential water-flow direction is controlled by tectonics and that it has a trend along the slope toward the downhill springs. The mine drainage flow direction is in agreement with this trend and can pollute the springs. Chemical analysis revealed three water groups: (1) SO ₄ ^2- –Ca²⁺–Mg²⁺ rich water (mine drainage), (2) HCO ₃ ^- –SO ₄ ^2- –Ca²⁺ rich water and (3) HCO ₃ ^- –Ca²⁺ rich water (freshwater). The second group of water results from the different percentage mix between the first and the third waters. The low percentage of mine polluted water demonstrates that there is a high dilution and low pollution of waters that can be exploited for drinking.     

Spatial control of groundwater contamination,using principal component analysis

A study on the geochemistry of groundwater was carried out in a river basin of Andhra Pradesh to probe into the spatial controlling processes of groundwater contamination, using principal component analysis (PCA). The PCA transforms the chemical variables, pH, EC, Ca²⁺, Mg²⁺, Na⁺, K⁺, HCO \(_3^- \) , Cl^?, SO \(_4^{2-} \) , NO \(_3^-\) and F^?, into two orthogonal principal components (PC1 and PC2), accounting for 75% of the total variance of the data matrix. PC1 has high positive loadings of EC, Na⁺, Cl^?, SO \(_4^{2-} \) , Mg²⁺ and Ca²⁺, representing a salinity controlled process of geogenic (mineral dissolution, ion exchange, and evaporation), anthropogenic (agricultural activities and domestic wastewaters), and marine (marine clay) origin. The PC2 loadings are highly positive for HCO \(_3^- \) , F^?, pH and NO \(_3^- \) , attributing to the alkalinity and pollution controlled processes of geogenic and anthropogenic origins. The PC scores reflect the change of groundwater quality of geogenic origin from upstream to downstream area with an increase in concentration of chemical variables, which is due to anthropogenic and marine origins with varying topography, soil type, depth of water levels, and water usage. Thus, the groundwater quality shows a variation of chemical facies from Na⁺ > Ca²⁺ > Mg²⁺ > K⁺: HCO \(_3^- \) > Cl^? > SO \(_4^{2-}>\) NO \(_3^- \) > F^?at high topography to Na⁺ > Mg²⁺ > Ca²⁺ > K⁺: Cl^? > HCO \(_3^- \) > SO \(_4^{2-}>\) NO \(_3^- \) > F^? at low topography. With PCA, an effective tool for the spatial controlling processes of groundwater contamination, a subset of explored wells is indexed for continuous monitoring to optimize the expensive effort.     

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.     

Characterisation and quality assessment of groundwater with a special emphasis on irrigation utility: Thirumanimuttar sub-basin, Tamil Nadu, India

Thirumanimuttar sub-basin is of particular importance in the study of groundwater quality due to the release of effluents from industries, agricultural, sewage and urban runoff, brining considerable change in water quality. An investigation was carried out by collecting a total of 194 groundwater samples for two seasons to decipher hydrogeochemistry and groundwater quality for determining its suitability for agricultural purposes. The water is neutral to alkaline in nature with pH ranging from 6.78 to 9.22 with an average of 7.37. Higher electrical conductivity (EC) was noted in NW and mid-downstream parts of the study area. Higher NO ₃ ^? was observed during post-monsoon (POM) due to the action of leaching and anthropogenic process. The piper plot reveals the dominance of Na⁺?CCl^? and Na⁺?CHCO ₃ ^? , mixed Ca²⁺?CNa⁺?CHCO ₃ ^? , mixed Ca²⁺?CMg²⁺?CHCO ₃ ^? and Ca²⁺?CSO ₄ ^? types of hydrogeochemical facies. Higher total hardness in the groundwater is due to the effect of dyeing and bleaching industries discharging effluents affects the quality of water. Residual Sodium Carbonate value indicates 56% of the samples are not suitable for irrigation purposes in both seasons. Higher sodium percentage is noted during PRM indicating the dominance of ion exchange and weathering. Higher sodium adsorption ratio was observed during POM indicating the effect of leaching and dissolution of salts into the aquifer matrix. USSL plot indicates 15% of samples record high salinity to medium sodicity. The Permeability Index indicates water is moderate to good for irrigation purposes. In general, groundwater in the study area is influenced by both natural and anthropogenic activities.     

Hydrochemistry and pollution probability of selected sites along the Euphrates River, Western Iraq

The hydrochemistry of Euphrates River in the study area which extended from Hit to Al-Saqlawia was studied in order to determine the physical, chemical, and biological properties in addition to the radiation level. Thirty-one stations along the Euphrates River were chosen, 17 of them represented the Euphrates River itself, whereas the other stations are considered as point pollution sources which all empty their load directly in the Euphrates River with an average total discharge of 32 m³/s. Twenty-eight samples of the Euphrates water of both high- and low-flow periods were analyzed for cations (Ca²⁺, Mg²⁺, Na⁺, and K⁺), anions (SO ₄ ⁼ , Cl^?, CO ₃ ⁼ , HCO ₃ ^? , NO ₃ ^? , PO ₄ ^?3 ), H₂S boron, dissolved oxygen, biological oxygen demand, bacteriological tests, radiation levels in addition to physical parameters such as hydrogen number (pH), total dissolved solid, electrical conductivity, total suspended solid, and temperature. This study showed that the cations and anions during periods of high and low flows are within acceptable limit with exceptional Cl^?. Hydrochemical formula during the high flow was Na-Ca-Mg-Cl-SO₄, then it changed into Na-Ca-Mg-HCO3-SO₄-Cl during the low-flow period. The average output cations and anions at downstream (Saqlawiya area) was relatively higher than those of input at upstream (Hit area); this attributed to the natural and anthropogenic activities originated mainly from agricultural activity and population communities around the river. Radiation level for ²¹²Pb, ²¹⁴Pb, ⁴⁰k, ²²⁰Ac, and ²¹⁴Bi showed that the higher level of radiation is concentrated within sediment rather than in water, but the radiation in both is within acceptable limit.     

Spatial variations of groundwater vulnerability using cluster analysis

An investigation on quality of groundwater has been carried out in the river basin of Varaha located in Visakhapatnam District, Andhra Pradesh to find out the factors that are responsible for spatial variations of water vulnerability. The study area is underlain by the Precambrian rocks of Eastern Ghats over which the Recent Formations occur. Groundwater is a prime source for drinking and irrigation. The quality of groundwater is fresh and brackish with dominance of the latter. Groundwater samples are categorized into two major clusters A and B, using the dendrogram of cluster analyses. Out of these two major clusters, five sub-clusters I to V in the pre-monsoon season and six sub-clusters I to VI in the post-monsoon season are identified. The sub-clusters I to IV of pre-monsoon and I to V of post-monsoon seasons of the cluster A are characterized by less mineralized groundwater compared to those of V of pre-monsoon and VI of post-monsoon seasons of the cluster B, which represent highly mineralized groundwater. The low to high mineral content follows gradually from upstream to the downstream area, being higher in post-monsoon season in both the clusters A and B, depending upon the source, mineral dissolution, and precipitation, solubility and leaching of ions, ion exchange and adsorption processes. Spatial distributions of the sub-clusters give clues to understand the factors that cause variations of groundwater vulnerability at a specific site, vis-a-vis local and regional lithological and non-lithological influences. As a result, the quality of groundwater on a regional scale changes from Na⁺ > Mg²⁺ >Ca²⁺ > K⁺: HCO ₃ ^? > Cl^? > SO ₄ ^2? > NO ₃ ^? > F^? in the cluster A to Na⁺ > Mg²⁺ >Ca²⁺ > K⁺: Cl^? > HCO ₃ ^? > SO ₄ ^2? > NO ₃ ^? > F^? in the cluster B, following the topography. The classification of the area into the zones of relative groundwater vulnerability with respect to drinking water quality of the chemical composition of the sub-clusters helps the planners to identify the specific locations, where the inferior quality of groundwater can occur, for taking the remedial measures.     

Identification and evaluation of the hydrogeochemical processes of the lower part of Wadi Siham catchment area, Tihama plain, Yemen

One hundred forty-eight groundwater samples were collected from the lower part of Wadi Siham catchment area for hydrogeochemical investigations to understand the hydrogeochemical processes affecting groundwater chemistry and their relation with groundwater quality. Groundwater in the study area is abstracted from different aquifers. The study area is characterized by arid climate and extremely high relative humidity. The results indicate that groundwater in the study area is fresh to brackish in nature. The abundance of the major ions is as follows: Na⁺¹?>?Ca⁺²?>?Mg⁺²?≥?K⁺¹ and Cl^?1?>?HCO ₃ ^?1 ?>?SO ₄ ^?2 ?>?NO ₃ ^?1 . Various graphical and ionic ration plots, statistical analyses, and saturation indices calculations have been carried out using chemical data to deduce a hydrochemical evaluation of the study area. The prevailing hydrogeochemical processes operating in the study area are dissolution, mixing, evaporation, ion exchange, and weathering of silicate minerals in the eastern part (recharge areas). The reverse ion exchange and seawater intrusion control the groundwater chemistry along the Red Sea coast areas and few parts of the study area. Deterioration in groundwater quality from anthropogenic activities has resulted from saltwater intrusion along the coastal areas due to groundwater overpumping and extensive use of fertilizers and infiltration of sewage water. Salinity and nitrate contamination are the two major problems in the area, which is alarming considering the use of this water for drinking.     

A new pair of coexisting amphiboles : the grünerite and ferropargasite pair

A new coexisting amphibole pair was recently found in the Jianshan iron deposit, Loufan of Shanxi Province, China. Electron microprobe analysis shows that the coexisting pair is composed of grünerite K_0.001 (Na_0.027 Ca_0.073 Mn_0.031 Fe _1.801 ²⁺ )_1.932 (Fe _2.948 ²⁺ Mg_1.964 Ti_0.002 Al_0.087)₅Si_8.069 O_22.10(OH)₂ and ferropargasite (K_0.135 Na_0.461)_0.596 (Na_0.088 Ca_1.853 Mn_0.005 Fe _0.072 ²⁺ )₂(Mn_0.005Fe _2.789 ²⁺ Mg_0.875Ti_0.021Fe _0.499 ³⁺ Al_0.812)₅(Si_6.103Al_1.897)₈O_22.00(OH)₂. The two kinds of amphiboles occur in amphibole schist not only as separate phenocrysts, but also are combined to form “single-crystal” phenocrysts in the form of topotactic intergrowths with the common c- and b-axes. The boundary between topotactic grünerite and ferropargasite is optically and chemically sharp. In comparison with the coexisting ferromagnesian amphibole and calcic amphibole pair discovered by predecessors, the newly discovered pair has lower Mg/Fe ratios and wider miscibility gaps.     

Major ion chemistry and metal distribution in coal mine pit lake contaminated with industrial effluents: constraints of weathering and anthropogenic inputs

Ion chemistry of mine pit lake water reveals dominance of alkaline earths (Ca²⁺ and Mg²⁺) over total cation strength, while SO₄ ^2? and Cl^? constitute the majority of total anion load. Higher value of Ca²⁺?+?Mg²⁺/Na⁺?+?K⁺ (pre-monsoon 5.986, monsoon 8.866, post-monsoon 7.09) and Ca²⁺?+?Mg²⁺/HCO₃ ^??+?SO ₄ ² (pre-monsoon 7.14, monsoon 9.57, post-monsoon 8.29) is explained by weathering of Ca?CMg silicates and dissolution of Ca²⁺-bearing minerals present in parent rocks and overburden materials. Silicate weathering supposed to be the major geological contributor, in contrast to bicarbonate weathering does a little. Distribution coefficient for dissolved metals and sorbed to surface sediments is in the order of Cd?>?Pb?>?Fe?>?Zn?>?Cu?>?Cr?>?Mn. Speciation study of monitored metals in surface sediments shows that Fe and Mn are dominantly fractionated in exchangeable-acid reducible form, whereas rest of the metals (Cr, Pb, Cd, Zn, and Cu) mostly in residual form. Cd, Pb, and Zn show relatively higher recalcitrant factor that indicates their higher retention in lake sediments. Factor loading of monitored physico-chemical parameters resembles contribution/influences from geological weathering, anthropogenic inputs as well as natural temporal factors. Ionic load/strength of lake water accounted for geochemical process and natural factors, while pollutant load (viz BOD, COD and metals, etc.) is associated with anthropogenic inputs through industrial discharge.     

Identifying the hydrochemical processes of groundwater in Wadi Na’man, Western Saudi Arabia using factor analysis

The groundwater of Wadi Na??man, located in the western Saudi Arabia, is subject to intense exploitation to accommodate all the water demands of this arid area. The groundwater of its shallow aquifer undergoes significant decline in water level, increasing salinity due to long time of aridity and irregular rainfall. A multivariate statistical technique, factor analysis, was used to identify and understand hydrochemical association and processes leading to the variability of groundwater quality without losing any information of input pattern and avoid limitations that are associated with classical methods. R- and Q-modes of factor analysis were applied to 63 groundwater samples and 21 variables. This analysis revealed that three factors accounted for 55.9% of the total data variability. Factor 1 was dominated by Ca²⁺, Mg⁺, Na⁺, Cl^?, and SO ₄ ^2? , as well as trace elements such as phosphorus and boron, suggesting effects from possible water?Csoil/rock interaction and agricultural activities. Factor 2 represented high aluminum loading as a result of the weathering of aluminum silicate minerals. Factor 3 revealed negative loading of dissolved CO₃ and Zn, indicating long-term aridity. Plots of Factor 1 versus Factor 2 and Factor 3 demonstrated that the samples clustered into one group with good separation from outliers. In addition, assessment of the drinking quality suggested that salinity increases with SO ₄ ^2? ?CCl^??CCa²⁺.     

Role of geophysical and hydrogeological techniques in EIA studies to identify TSDF site for industrial waste management

This paper deals with the importance of integrated hydrogeological, geological and geophysical applications in identifying suitable site for treatment, storage and disposal facility (TDSF) for industrial waste management. The pollution control authorities (Civic body) have a mandate to provide proper TSDF for the industrial zones. One such zone of 2800 acres, established by State Industries Promotion Corporation of Tamil Nadu (SIPCOT) at Perundurai in southern India, is selected to identify suitable TSDF site. The zone is envisaged to cater 22500 MTA (metric tones per annum) of industrial waste generated by 565 units. Hydrogeological and geological setup forms an important criterion in the process of environmental impact assessment (EIA) to establish proposed activity. Hydrogeological, geophysical and socio-economic/ecological studies were carried out to identify suitable TSDF site. Vertical electrical sounding (VES), multi-electrode resistivity imaging (MERI), ground penetrating radar (GPR) scanning, and infiltration tests were performed within the proposed TSDF site of 50 acres land. An inventory of 54 key wells includes depth to water level (varies from 9.7 to 15 m, below ground level) and water chemistry (pH, TDS, Ca²⁺, Mg²⁺, Na⁺, K⁺, Cl^?, HCO ₃ ^? , SO ₄ ^2? , NO ₃ ^? and F^?) helped in identifying physical environment around (5 km radius) proposed TSDF site. Geophysical and hydrogeological investigations verified with drillings (at 5 locations) within the proposed TSDF site resulted, shallow hard rock at 4.5 m depth, the absence of groundwater, and low infiltration rate (4.3 cm/hour) of soil in the western side (45 acres) of proposed 50 acres land reveals suitability of TSDF site.     

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.     

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.     

Theoretical studies of the electronic structure of copper in tetrahedral and triangular coordination with sulfur

Molecular orbital calculations are presented for the copper-sulfur polyhedral clusters CuS ₄ ^7? , CuS ₄ ^6? , CuS ₃ ^5? and CuS ₃ ^4? , which occur in many minerals. Calculated and experimental optical and X-ray energies are found to be in good agreement. The crystal field orbitals of Cu⁺ in tetrahedrally coordinated sulfides are found to be less tightly bound than the S3p nonbonding orbitals by about 2–3 eV whereas the e and t ₂ crystal field orbitals are split by about 1 eV. The crystal field splitting of Cu²⁺ in tetrahedral coordination is about 0.7–0.8 eV while the separation of the S3p nonbonding orbitals and the partially filled t ₂ crystal field orbital is about 2 eV. In triangular coordination both the Cu⁺ and Cu²⁺ crystal field orbitals are more stable than in tetrahedral coordination, more widely split and more strongly mixed with the S3p orbitals. CuS is shown to be unstable as the mixed oxidation state compound Cu^2+III (Cu^+IV)₂S^2?(S ₂ ^2? ); rather each Cu is predicted to have a fractional oxidation state and partially-empty crystal field orbitals.     

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.