Alkali ion migration in albite and K-feldspar

As part of a study of ion migration mechanisms in feldspars, the dynamical behaviour of the alkali metal cations ions in albite and K-feldspar has been investigated using a combination of dielectric spectroscopy and atomistic computer simulation techniques. The low-frequency dielectric properties of these minerals have been studied from room temperature to 1100 K. At each temperature, the dielectric constant, conductivity and dielectric loss were determined over a range of frequencies from 100 Hz to 10 MHz. At high temperatures a distinct Debye-type relaxation in the dielectric loss spectra was observed for both albite and K-feldspar; the activation energy for these processes was determined to be 1.33 eV in both albite and K–feldspar. Atomistic simulation techniques were used to elucidate the mechanism and energetics of the cation migration processes. Mechanisms involving the conventional hopping of Na⁺ and K⁺ ions between cation sites in the (010) plane were found to give calculated energy barriers in good agreement with the experimentally determined activation energies. These results assist in understanding the nature of the processes responsible for the observed dielectric behaviour.     

Octahedral cation ordering in olivine at high temperature. II: an in situ neutron powder diffraction study on synthetic MgFeSiO4 (Fa50)

 The partitioning of Fe and Mg between the M1 and M2 octahedral sites of olivine has been investigated by in situ time-of-flight neutron powder diffraction. The degree of M-cation order was determined from direct measurements of site occupancies in a synthetic sample of Fo50Fa50 heated to 1250 °C at the Fe-FeO oxygen buffer. Fe shows slight preference for M1 at temperatures below about 600 °C, progressively disordering on heating to this temperature. Above 630 °C, the temperature at which site preferences cross over (T _cr), Fe preferentially occupies M2, becoming progressively more ordered into M2 on increasing temperature. The cation-ordering behaviour is discussed in relation to the temperature dependence of the M1 and M2 site geometries, and it is suggested that vibrational entropy, crystal field effects and changes in bond characteristics play a part in the cross-over of partitioning behaviour. The temperature dependence of site ordering is modelled using a Landau expansion of the free energy of ordering of the type ΔG = −hQ + gTQ +  (T − T _c)Q ² +  Q ⁴, with a/h = 0.00406 K⁻¹, b/h = 2.3, T _c = 572 K and g/h = 0.00106 K⁻¹. These results suggest that the high-temperature ordering behaviour across the forsterite-fayalite join will have a bearing on the activity-composition relations of this important rock-forming mineral, and indicate that Fe-Mg olivine solid solutions become less ideal as temperature increases. Received: 12 August 1999 / Accepted: 25 April 2000     

Effects of dry density and exchangeable cations on the diffusion process of sodium ions in compacted montmorillonite

As a part of the safety assessment of the geological disposal of high-level radioactive waste, the effects of dry density and exchangeable cations on the diffusion process of Na⁺ ions in compacted bentonite were studied from the viewpoint of the activation energy for diffusion. The apparent self-diffusion coefficients of Na⁺ ions in compacted Na-montmorillonite and in a Na- and Ca-montmorillonite mixture were determined by one-dimensional, non-steady diffusion experiments at different temperatures and dry densities. A unique change in activation energy as a function of dry density was found for the Na⁺ ions in compacted Na-montmorillonite. The activation energy suddenly decreased from 18.1 to 14.1 kJ mol^− 1 as the dry density increased from 0.9 to 1.0 Mg m^− 3, whereas it increased to 24.7 kJ mol^− 1 as the dry density increased to 1.8 Mg m^− 3. Examination of the effect of exchangeable cations on the activation energies determined that the activation energies were almost constant, approximately 25 kJ mol^− 1, for the montmorillonite specimens at a dry density of 1.8 Mg m^− 3. However, three different activation energy values were obtained at a dry density of 1.0 Mg m^− 3. These findings cannot be explained by the conventional diffusion model (the pore water diffusion model), which suggests that the predominant diffusion process alternates among pore water diffusion, interlayer diffusion, and external surface diffusion.     

Assessing variability of water quality in a groundwater-fed perennial lake of Kashmir Himalayas using linear geostatistics

This paper presents a study on Manasbal lake, which is one of the high altitude lakes in the Kashmir Valley, India. Eighteen water samples were analysed for major ions and trace elements to assess the variability of water quality of the lake for various purposes. Geostatistics, the theory of regionalized variables, was then used to enhance the dataset and estimate some missing spatial values. Results indicated that the concentration of major ions in the water samples in winter was higher than in summer. The scatter diagrams suggested the dominance of alkaline earths over the alkali elements. Three types of water were identified in the lake that are referred to as Ca–HCO₃, Mg–HCO₃ and hybrid types. The lake water was found to be controlled by rock–water interaction with carbonate lithology as a dominant source of the solutes. The major (Ca^2 +, Mg^2 +, Na⁺, K⁺, NO₃ and HCO₃^-{\rm{HCO}}_{3}^{-}, CO₃ and Cl) and trace elements of the lake water were within the World Health Organization standards, therefore the lake water was considered chemically safe for drinking purposes. Although NO₃ concentration (ranging from 1.72 to 2 mg/L), is within the permissible limit and not very alarming, the gradually increasing trend is not acceptable. It is however, important to guard its spatio-temporal variability as the water is used for domestic as well as agricultural purposes. This study is significant as hydrogeological information on such high altitude lakes in India is scanty.     

K-Na exchange in phlogopite on the scale of a single layer

Hydrothermal atomic force microscopy (HAFM) was used to investigate K⁺-Na⁺ ion exchange in phlogopite in-situ. The exchange of K⁺ for Na⁺ caused the interlayer distance to swell by approximately 5 Å. A distinct reaction front could be resolved between the K⁺-areas and the swollen (hydrated) Na⁺-areas, indicating a single reaction step mechanism. Although the fronts revealed kinematic variability due to inhomogeneities, the data indicate a diffusion mechanism within the interlayers. Diffusion coefficients ranged between 2 × 10⁻⁸ and 35 × 10⁻⁸ cm²/s, depending on the depth of the interlayer, the solution composition, and temperature. An activation energy of 15 kJ/mol was calculated from the temperature dependence of the diffusion coefficients. In addition to the regular 5 Å swelling, bulge-shaped irregular swelling of up to 200 nm could be observed. This irregular swelling might be an initial stage of delamination.Reducing the Na⁺-concentration in the solution at a constant K⁺-concentration was found to reduce the exchange rate. The exchange ceases completely when the equilibrium ratio r(K⁺/Na⁺) of the solution is reached. The measured r(K⁺/Na⁺) of 0.013 indicates a lower K⁺-selectivity for interlayers that are closer to the surface. This lower selectivity is most likely related to a lower strain energy associated with the expansion of interlayers close to the surface.Reversing the exchange reaction caused the interlayers to shrink to their original height. The kinematics of the front of the reverse reaction were significantly enhanced. In parts, swollen Na⁺-areas were engulfed and trapped by the shrunken K⁺-areas. No morphological indications of remnant alterations other than these trapped islands and the irregular swelling were observed.     

Fluid chemistry and processes at the Porgera gold deposit, Papua New Guinea

The Porgera gold deposit in Papua New Guinea is a world-class example of an alkalic-type epithermal gold system (stage II), which overprints a precursor stage of magmatic-hydrothermal gold mineralization (stage I). Gas and ion chromatographic analyses of fluid inclusions contained in vein minerals from both mineralization stages have been carried out in order to constrain the compositions of the fluids involved in, and the processes attending, ore deposition. These data indicate the presence of three end-member liquids, the most dilute of which was present throughout the mineralization history and is interpreted to represent evolved groundwater of meteoric origin. Its composition is estimated to have been approximately 500 mM Na⁺, 10 mM K⁺, 5 mM Li⁺, 250 mM Cl⁻, 0.15 mM Br⁻, and 0.01 mM I⁻, plus significant concentrations of dissolved gases. More saline liquids were also present during the two main stages of ore formation, and although their compositions differ, both are interpreted to have been derived at least in part from magmatic fluids, and to have been the media by which gold was introduced into the system. Stage I minerals contain fluid inclusions which decrease in salinity towards this dilute end-member composition through the vein paragenesis, reflecting progressive dilution at depth of the magmatic fluid source by groundwaters. Ore deposition is thought to have been caused largely by simple cooling and/or wallrock reactions, although limited in situ fluid mixing may also have occurred. The most saline fluids, present in early quartz and pyrite, contain at least 810 mM Na⁺, 530 mM Ca²⁺, 130 mM K⁺, 12 mM Li⁺, 87 mM SO₄ ²⁻, 960 mM Cl⁻, 1.1 mM Br⁻, and 0.05 mM I⁻, plus significant but variable concentrations of dissolved gases. Fluid inclusions from stage II hydraulic breccia veins reveal the presence of two distinct liquids with contrasting salinities, which were present at different times during vein formation. A higher salinity liquid appears to have predominated during mineralization, whereas lower salinity groundwaters filled the structures during intervening periods. The ore-forming fluid may have been forcibly injected into the veins from depth during fracturing and depressurization events, displacing the resident groundwaters in the process. The original composition of this fluid is estimated to have been at least 1770 mM Na⁺, 59 mM K⁺, 180 mM Li⁺, 210 mM SO₄ ²⁻, 680 mM Cl⁻, 1.4 mM Br⁻, and 0.09 mM I⁻, plus 1.5 mol% CO₂, 0.19 mol% CH₄, and 0.04 mol% N₂. Gas chromatographic analyses of fluid inclusions from stage II samples show a decrease in total gas content between early unmineralized veins and post-mineralization vuggy quartz (suitable samples could not be obtained from the ore stage itself). Post-mineralization samples plot along an experimental gas-saturation curve in the CO₂-CH₄-H₂O-NaCl system, obtained at conditions similar to those attending stage II ore deposition at Porgera (200–300 bar, ˜165 °C). These results are interpreted to indicate a period of depressurization-induced phase separation during hydraulic fracturing, which resulted in rich ore deposition. Volatile gases such as CH₄ and N₂, in addition to CO₂ in solution, are shown to have a significant negative effect on total gas solubility. This effect may be of critical importance in lowering the temperature and increasing the depth (pressure) at which phase separation can occur in epithermal systems. Received: 28 November 1995 / Accepted: 17 July 1996     

Geochemical alterations in surface waters of Govind Ballabh Pant Sagar,Northern Coalfield,India

Major ions showed high concentrations, ionic strength and chemical activity in the surface waters of Govind Ballabh Pant Sagar reservoir. Various geochemical ratios showed the dominance of silicate over carbonate weathering and major ions such as Na⁺ + K⁺ account for about 52 % of the cation budget. The high Na⁺ and K⁺ showed sedimentation of rock/coal particles consisting of highly weathered silicate minerals contributed by the discharge of mine water, fly ash mixing during transportation, etc. Further, Ca²⁺ + Mg²⁺/Na⁺ + K⁺ ratio was <1 (0.92) indicating the occurrence of silicate weathering in the reservoir catchment. The comparative assessment showed that the proportion of Ca²⁺ + Mg²⁺/Na⁺ + K⁺ tends to be lower along the coal mining belts compared to non-coal mining regions in the world. The Ca²⁺/SO₄ ^2? ratio <1 revealed not only H₂CO₃ but H₂SO₄ also acting as a source of protons for rock weathering. The cause underlying these differences can be related directly to geological substrate and anthropogenic activities.     

Correlative and comparative characterization of main ion concentrations in laterite groundwater in semi-arid northern Burkina Faso

About 24 samples from hand-dug wells and boreholes were used to characterize concentrations of the main inorganic ions in a laterite environment under semi-arid climatic conditions in Tikaré, northern Burkina Faso. It was found that the most represented groundwater anion in groundwater was HCO₃ ⁻ with average levels of 49.1 mg/L in the dry season and 33.5 mg/L in the rainy season. The most represented cation was Ca²⁺ with mean concentrations of 13.7 and 9.5 mg/L, respectively. The main processes, which influence the concentrations of these ions, are evaporation (dry season), local enrichment of recharge water in some elements, ion exchange and fixation by clay minerals (in case of K⁺). The best correlations were found between Ca²⁺ and Mg²⁺ (r = 0.95), Cl⁻ and Na⁺ (r = 0.95), HCO₃ ⁻ and Mg²⁺ (r = 0.89), HCO₃ ⁻ and Ca²⁺ (r = 0.89), and between HCO₃ ⁻ and Na⁺ (r = 0.80). In general, the quality of the groundwater from the different wells sampled for this study was good enough to serve as drinking water. However, there were situations where the quality of water was polluted because of anthropogenic contaminants (mainly NO₃ ⁻, K⁺, Cl⁻) from septic tanks and manure pits located in the vicinity of some sampled wells. In addition, application of fertilizers also represents a potential anthropogenic contamination source with regard to SO₄ ²⁻, Ca²⁺, K⁺, Na⁺, and Mg²⁺. Considering the high concentrations of SO₄ ²⁻, Mg²⁺, Na⁺ and Ca²⁺ found in one borehole, the deeper, fractured aquifers were also likely to be enriched in these elements. In contrast, the shallow aquifers are likely to be contaminated with Cl⁻, NO₃ ⁻ and K⁺. Cl⁻ and K⁺ seem to be locally present in recharge water as shown by their relative higher mean concentrations in the rainy season samples.     

Petrologic and geochemical investigation of carbonates in peridotite xenoliths from northeastern Tanzania

Primary carbonates in peridotite xenoliths from the East African Rift in northeastern Tanzania occur as intergranular patches with accessory minerals (olivine and spinel), as patches with accessory magmatic minerals (nepheline), and as round monomineralic inclusions in primary olivine grains. All are characterized by calcitic compositions (Ca/Ca + Mg + Fe from 0.83 to 0.99), extremely low SiO₂ + Al₂O₃ + Na₂O + K₂O, low trace element abundance [total rare-earth element (REE) abundance <25 ppm], uniform extinction, and lack of reaction textures with the host xenolith. Calculated Fe–Mg exchange coefficients between carbonate and primary olivine indicate disequilibrium in most samples. Combined with the lack of significant reaction textures, this suggests that the carbonates were introduced shortly before or during eruption of the host magma. A global compilation of electron microprobe analyses of mantle-derived carbonates (in xenoliths, xenocrysts, and megacrysts) reveals compositional clusters near end member calcite, end member magnesite, and stoichiometric dolomite. Eutectic liquid compositions are less common, suggesting that many carbonate inclusions reported worldwide may be crystalline precipitates. Likewise, the calcites in this study are not interpreted to represent quenched carbonatitic melts, but are interpreted instead to be crystalline cumulates from such melts. These inferences are consistent with recent experiments, which show that carbonatitic melts cannot become more calcitic than CaCO₃∼80 wt%. Low trace element abundance may be a diagnostic feature of cumulate carbonate, and in combination with petrography and major element composition, serve to distinguish it from quenched carbonated liquid. Received: 30 July 1999 / Accepted: 5 February 2000     

Experimental Na/K exchange between alkali feldspar and an NaCl–KCl salt melt: chemically induced fracturing and element partitioning

The exchange of Na⁺ and K⁺ between alkali feldspar and a NaCl–KCl salt melt has been investigated experimentally. Run conditions were at ambient pressure and 850 °C as well as 1,000 °C. Cation exchange occurred by interdiffusion of Na⁺ and K⁺ on the feldspar sub-lattice, while the Si–Al framework remained unaffected. Due to the compositional dependence of the lattice parameters compositional heterogeneities resulting from Na⁺/K⁺ interdiffusion induced coherency stress and associated fracturing. Depending on the sense of chemical shift, different crack patterns developed. For the geometrically most regular case that developed when potassic alkali feldspar was shifted toward more sodium-rich compositions, a prominent set of cracks corresponding to tension cracks opened perpendicular to the direction of maximum tensile stress and did not follow any of the feldspar cleavage planes. The critical stress needed to initiate fracturing in a general direction of the feldspar lattice was estimated at ≤0.35 GPa. Fracturing provided fast pathways for penetration of salt melt or vapor into grain interiors enhancing overall cation exchange. The Na/K partitioning between feldspar and the salt melt attained equilibrium values in the exchanged portions of the grains allowing for extraction of the alkali feldspar mixing properties.     

Determination of cation distribution in (Co,Ni,Zn)2SiO4 olivine by synchrotron X-ray diffraction

 The cation distribution of Co, Ni, and Zn between the M1 and M2 sites of a synthetic olivine was determined with a single-crystal diffraction method. The crystal data are (Co_0.377Ni_0.396Zn_0.227)₂SiO₄, M _r  = 212.692, orthorhombic, Pbnm, a = 475.64(3), b = 1022.83(8), and c = 596.96(6) pm, V = 0.2904(1) nm³, Z = 4, D _x  = 4.864 g cm⁻³, and F(0 0 0) = 408.62. Lattice, positional, and thermal parameters were determined with MoKα radiation; R = 0.025 for 1487 symmetry-independent reflections with F > 4σ(F). The site occupancies of Co, Ni, and Zn were determined with synchrotron radiation employing the anomalous dispersion effect of Co and Ni. The synchrotron radiation data include two sets of intensity data collected at 161.57 and 149.81 pm, which are about 1 pm longer than Co and Ni absorption edges, respectively. The R value was 0.022 for Co K edge data with 174 independent reflections, and 0.034 for Ni K edge data with 169 reflections. The occupancies are 0.334Co + 0.539Ni + 0.127Zn in the M1 sites, and 0.420Co + 0.253Ni + 0.327Zn in the M2 sites. The compilation of the cation distributions in olivines shows that the distributions depend on ionic radii and electronegativities of constituent cations, and that the partition coefficient can be estimated from the equation: ln [(A/B)_M1/(A/B)_M2] = −0.272 (IR _A -IR _B ) + 3.65 (EN _A −EN _B ), where IR (pm) and EN are ionic radius and electronegativity, respectively. Received: 8 April 1999 / Revised, accepted: 7 September 1999     

The threshold value of epikarst runoff in forest karst mountain area

Hydrochemical investigations were carried out in Damagh area, Hamadan, western Iran, to assess chemical composition of groundwater. Forty representative groundwater samples were collected from different wells to monitor the water chemistry of various ions. Chemical analysis of the groundwater showed that the mean concentration of the cations is in the order Na⁺ > Ca²⁺ > Mg²⁺ > K⁺, while that for anions was HCO₃⁻ > Cl⁻ > SO₄^{2 −} > NO₃⁻. All of the investigated groundwaters present two different chemical facies (Ca–HCO₃ and Na–HCO₃) which is in relation with their interaction with the geological formations of the basin, cation exchange between groundwater and clay minerals and anthropogenic activities. The principal component analysis (PCA) performed on groundwater identified three principal components controlling their variability in groundwater. Electrical conductivity, Mg²⁺, Na⁺, SO₄²⁻, and Cl⁻ content were associated in the same component (PC1) (salinity), determined principally by anthropogenic activities. The pH, CO₃^{2 −}, HCO₃⁻, and Ca²⁺ (PC2) content were related to the geogenic factor. Finally, the NO₃⁻, Cl⁻ and K⁺ (PC3) were controlled by anthropogenic activity as a consequence of inorganic fertilizers.     

Geochemical assessment of groundwater around Macherla-Karempudi area,Guntur district,Andhra Pradesh

Groundwater in Palnad sub-basin is alkaline in nature and Na⁺-Cl⁻-HCO₃⁻ type around Macherla-Karempudi area in Guntur district, Andhra Pradesh. Total dissolved solids (TDS) show strong positive correlation with Cl⁻, Na⁺, Ca²⁺ and Mg²⁺, and positive correlation with SO₄²⁻, K⁺ and HCO₃⁻. Calcareous Narji Formation is the dominant aquifer lithology, and water-rock interaction controls the groundwater chemistry of the area. Chloro-alkaline indices (CAI) are positive at Miriyala, Adigopula, Mutukuru, Macherla and Durgi suggesting replacement of Na⁺ and K⁺ ions from water by Mg⁺⁺ and Ca⁺⁺ ions from country rock through base exchange reactions. Negative CAI values are recorded at Terala, Rayavaram and Nehrunagar, which indicate exchange of Na⁺ and K⁺ from the rock as cation-anion exchange reaction (chloro-alkaline disequilibrium). TDS range from 91 to 7100 ppm (Avg. 835 ppm) and exceed the prescribed limit of drinking water around Mutukuru, Durgi, Rayavaram, Khambampadu and Ammanizamalmadaka areas. Scanty rainfall and insufficient groundwater recharge are the prime factors responsible for high salinity in the area. Fluoride content ranges from <1 to 3.8 ppm and contaminated areas were identified around Macherla (1 sq km; 3.8ppm), Mandadi (1 sq km, 2.1ppm) and Adigopula (2 sq km, <1 to 3.7 ppm). The % Na⁺ content varies from 17 to 85 with the mean value of 57, and eighty (80) samples showed higher %Na⁺ in comparison to the prescribed limit of 60 for irrigation water. Sodium Adsorption Ratio (SAR) and % Na⁺ in relation to total salt concentration indicate that groundwater (51%) mostly falls under doubtful to poor quality for irrigation purpose. Groundwater of Adigopula village is fluoride contaminated and remedial measures are suggested to improve the water quality.     

A high-temperature and high-pressure Raman spectroscopic study of CaGeO3 garnet

 High-pressure and high-temperature Raman spectra of CaGeO₃ tetragonal garnet have been collected to 11.5 GPa and 1225 K, respectively, in order to investigate possible intrinsic anharmonic behaviour in this phase. The Raman peak positions were observed to vary linearly with pressure and temperature within the ranges studied, with the higher-energy peaks showing larger P- and T-induced shifts than the low energy modes. The observed T-induced shifts are similar to those reported for grossular and andradite, while the observed P-induced shifts are generally larger than those of aluminosilicate and MgSiO₃ majorite garnets (Gillet et al. 1992; Rauch et al. 1996) due to the larger bulk modulus of CaGeO₃ garnet. The observed mode shifts of CaGeO₃ garnet were used to determine the isothermal and isobaric mode Grüneisen parameters for this phase. These parameters are similar in value to those reported previously for grossular and andradite (Gillet et al. 1992). The calculated intrinsic anharmonic parameters, a _i , for CaGeO₃ garnet were determined to be nonzero, indicating significant anharmonic behaviour for this phase. These values, which range from −3.8 × 10⁻⁵ K⁻¹ to −1.3 × 10⁻⁵ K⁻¹, are also similar to those reported for andradite and grossular, but smaller than those determined for pyrope (Gillet et al. 1992). Hence, we expect MgSiO₃ majorite to show greater anharmonicity than the germanate analogue studied by us. The anharmonic parameters determined for CaGeO₃ tetragonal garnet may now be introduced into quasiharmonic vibrational heat capacity models to account for the observed anharmonic behaviour. Received: 21 April 1999 / Revised, accepted: 11 September 1999     

Origin and geochemical reaction paths of sabkha brines: Sabkha Jayb Uwayyid, eastern Saudi Arabia

Sabkhas are ubiquitous geomorphic features in eastern Saudi Arabia. Seven brine samples were taken from Sabkha Jayb Uwayyid in eastern Saudi Arabia. Brine chemistry, saturation state with respect to carbonate and evaporate minerals, and evaporation-driven geochemical reaction paths were investigated to delineate the origin of brines and the evolution of both brine chemistry and sabkha mineralogy. The average total dissolved solids in the sabkha brines is 243 g/l. The order of cation dominance is Na⁺   >>  Mg²⁺ >>  Ca²⁺>K⁺, while anion dominance is Cl⁻ >> SO₄ ²⁻ >> HCO₃ ⁻. Based on the chemical divide principle and observed ion ratios, it was concluded that sabkha brines have evolved from deep groundwater rather than from direct rainfall, runoff from the surroundings, or inflow of shallow groundwater. Aqueous speciation simulations show that: (1) all seven brines are supersaturated with respect to calcite, dolomite, and magnesite and undersaturated with respect to halite; (2) three brines are undersaturated with respect to both gypsum and anhydrite, while three brines are supersaturated with respect to both minerals; (3) anhydrite is a more stable solid phase than gypsum in four brines. Evaporation factors required to bring the brines to the halite phase boundary ranged from 1.016 to 4.53. All reaction paths to the halite phase boundary follow the neutral path as CO₂ is degassed and dolomite precipitates from the brines. On average, a sabkha brine containing 1 kg of H₂O precipitates 7.6 g of minerals along the reaction path to the halite phase boundary, of which 52% is anhydrite, 35.3% is gypsum, and 12.7% is dolomite. Bicarbonate is the limiting factor of dolomite precipitation, and sulfate is the limiting factor of gypsum and anhydrite precipitation from sabkha brines.     

Partition coefficients of Nb and Ta between rutile and anhydrous haplogranite melts

Partition coefficients (D) for Nb and Ta between rutile and haplogranite melts in the K₂O-Al₂O₃-SiO₂ system have been measured as functions of the K₂O/Al₂O₃ ratio, the concentrations of Nb₂O₅ and Ta₂O₅, the temperature, in air and at 1 atmosphere pressure. The Ds increase in value as the K^* [K₂O/(K₂O + Al₂O₃)] molar ratio continuously decreases from highly peralkaline [K^* ∼ 0.9] to highly peraluminous [K^* ∼ 0.35] melts. The D values increase more dramatically with a unit decrease in K^* in peraluminous melts than in peralkaline melts. This compositional dependence of Ds can be explained by the high activity of NbAlO₄ species in peraluminous melts and the high activity of KONb species (or low activity of NbAlO₄ species) in peralkaline melts. A coupled substitution, Al⁺³ + Nb⁺⁵ (or Ta⁺⁵) = 2Ti⁺⁴, accounts for the Ds of Nb (Ta) being much greater in peraluminous melts than in peralkaline melts because this substitution allows Nb (Ta) to enter into the rutile structure more easily. The Ds of Ta between rutile and melt are greater than those of Nb at comparable concentrations because the molecular electronic polarizability of Ta is weaker than that of Nb. The Nb⁺⁵ with a large polarizing power forms a stronger covalent bond with oxygen than Ta⁺⁵ with a small polarizing power. The formation of the strong bond, Nb-O, distorts the rutile structure more severely than the weak bond, Ta-O; therefore, it is easier for Ta to partition into rutile than for Nb. These results imply that the utilization of the Nb/Ta ratio in liquid as a petrogenetic indicator in granitic melts must be done with caution if rutile (or other TiO₂-rich phases) is a liquidus phase. The crystallization of rutile will increase the Nb/Ta ratio of the residual liquid because the Ds of Ta between rutile and melts are greater than those of Nb. Received: 28 December 1998 / Accepted 27 September 1999     

An empirical model for the calculation of spinel-melt equilibria in mafic igneous systems at atmospheric pressure: 2. Fe-Ti oxides

In order to develop models simulating the crystallization of Fe-Ti oxides in natural lavas, we have processed published experimental data on magnetite-melt and ilmenite-melt equilibria. These data include 62 Mt-melt and 75 Ilm-melt pairs at temperatures 1040–1150 °C, oxygen fugacities from IW to NNO+2, and bulk compositions ranging from ferrobasalts to andesites and dacites. Five major cations (Fe³⁺, Fe²⁺, Ti⁴⁺, Mg²⁺ and Al³⁺) were considered for the purpose of describing Fe-Ti oxide saturation as a function of melt composition, temperature and oxygen fugacity at 1 atmosphere pressure. The empirically calibrated mineral-melt expression based on multiple linear regressions is: ln D _i  = a/T + blog f _O2 + c + d ₁ X _Na + d ₂ X _K + d ₃ X _P, where D _i represents molar distribution coefficients of the given cations between Mt/Ilm and melt; X _Na, X _K, and X _P are the molar fractions of Na, K, and P in the melt. The empirically calibrated Mt-melt and Ilm-melt equilibria equations allowed us to develop two models for calculating crystallization temperatures of the Fe-Ti oxides in the melts with an accuracy of 10–15 °C, and compositions with an accuracy of 0.5–2 mol%. These models have been integrated into the COMAGMAT-3.5 program, improving our ability to study numerically the effects of temperature and oxygen fugacity on the stability and phase equilibria of Fe-Ti oxides. Application of this approach to the tholeiitic series of Chazhma Sill from Eastern Kamchatka (Russia) indicates oxygen fugacity conditions near NNO + 0.5. Numerical simulation of fractional crystallization of an iron-enriched basaltic andesite parent at these oxidizing conditions accurately reproduces the FeO-SiO₂ relations observed in the Chazhma suite. Received: 3 March 1998 / Accepted: 7 August 1998     

The partitioning of copper between silicate melts and two-phase aqueous fluids: An experimental investigation at 1 kbar, 800° C and 0.5 kbar, 850° C

 Experiments were performed in the three phase system high-silica rhyolite melt+low-salinity aqueous vapor+hydrosaline brine, to investigate the partitioning equilibria for copper in magmatic-hydrothermal systems at 800° C and 1 kbar, and 850° C and 0.5 kbar. D^aqm/mlt _Cu and apparent equilibrium constants, K^aqm/mlt _Cu,Na, between the aqueous mixture (aqm=quenched vapor+brine) and the silicate melt (mlt) are calculated. D^aqm/mlt _Cu increases with increasing aqueous chloride concentration and is a function of pressure. K^aqm/mlt _Cu,Na=215(±73) at 1 kbar and 800° C and K^aqm/mlt _Cu,Na=11(±6) at 0.5 kbar and 850°C. Decreasing pressure from 1 to 0.5 kbar lowers K^aqm/mlt _Cu,Na by a factor of approximately 20. Data revealed no difference in K^aqm/mlt _Cu,Na or D^aqm/mlt _Cu as a function of the melt aluminium saturation index. Within the 2-phase field the K^aqm/mlt _Cu,Na show no variation with total aqueous chloride, indicating that copper-sodium exchange between the vapor, brine and silicate melt is independent of the mass proportion of vapor and brine. Model copper-sodium apparent equilibrium constants for the hydrosaline brine and the silicate melt revealed a negative dependence on pressure. Model apparent equilibrium constants for copper-sodium exchange between the brine and vapor were close to unity at 1 kbar and 800° C. Received: 27 June 1994/Accepted: 30 March 1995     

Hydrogeochemical analysis and evaluation of groundwater quality in the Gadilam river basin,Tamil Nadu,India

Water samples were collected from different formations of Gadilam river basin and analyzed to assess the major ion chemistry and suitability of water for domestic and drinking purposes. Chemical parameters of groundwater such as pH, electrical conductivity (EC), total dissolved solids (TDS), Sodium (Na⁺), Potassium (K⁺), Calcium (Ca⁺), Magnesium (Mg⁺), Bicarbonate (HCO₃  ^-_{3}^{\ \,-}), Sulphate (SO₄  ^-_{4}^{\ \,-}), Phosphate (PO₄  ^-_{4}^{\ \,-}) and Silica (H₄SiO₄) were determined. The geochemical study of the aquatic systems of the Gadilam river basin show that the groundwater is near-acidic to alkaline and mostly oxidizing in nature. Higher concentration of Sodium and Chloride indicates leaching of secondary salts and anthropogenic impact by industry and salt water intrusion. Spatial distribution of EC indicates anthropogenic impact in the downstream side of the basin. The concentration levels of trace metals such as Iron (Fe), Lead (Pb), Nickel (Ni), Bromide (Br), Iodide (I) and Aluminium (Al) have been compared with the world standard. Interpretation of data shows that some trace metals such as Al, Ni and Pb exceed the acceptable limit of world standard. Geophysical study was carried out to identify the weathered zone in the hard rock and contaminated zone by anthropogenic impact in the downstream of river Gadilam. A few of the groundwater samples in the study area were found to be unsuitable for domestic and drinking purposes.     

Experimental study of the K2ZrSi3O9 (wadeite)–K2TiSi3O9 and K2(Zr,Ti)Si3O9–phlogopite systems at 2–3 GPa

Experiments ranging from 2 to 3 GPa and 800 to 1300 °C and at 0.15 GPa and 770 °C were performed to investigate the stability and mutual solubility of the K₂ZrSi₃O₉ (wadeite) and K₂TiSi₃O₉ cyclosilicates under upper mantle conditions. The K₂ZrSi₃O₉–K₂TiSi₃O₉ join exhibits complete miscibility in the P–T interval investigated. With increasing degree of melting the solid solution becomes progressively enriched in Zr, indicating that K₂ZrSi₃O₉ is the more refractory end member. At 2 GPa, in the more complex K₂ZrSi₃O₉–K₂TiSi₃O₉–K₂Mg₆Al₂Si₆O₂₀(OH)₄ system, the presence of phlogopite clearly limits the extent of solid solution of the cyclosilicate to more Zr-rich compositions [Zr/(Zr + Ti) > 0.85], comparable to wadeite found in nature, with TiO₂ partitioning strongly into the coexisting mica and/or liquid. However, at 1200 °C, with increasing pressure from 2 to 3 GPa, the partitioning behaviour of TiO₂ changes in favour of the cyclosilicate, with Zr/(Zr + Ti) of the K₂(Zr,Ti)Si₃O₉ phase decreasing from ∼0.9 to ∼0.6. The variation in the Ti content of the coexisting phlogopite is related to its degree of melting to forsterite and liquid, following the major substitution ^VITi+^VI□=2^VIMg. Received: 26 January 1999 / Accepted: 10 January 2000