Hydrogeochemical assessment of groundwater in Moro area,Kwara state,Nigeria

Detailed study of chemical analysis results of several groundwater samples (UNICEF-Assisted Water project, Kwara state, Nigeria) were carried out in an attempt to assess the quality and usability of groundwaters in the Moro area. Chemical analysis results indicate higher concentrations of Ca²⁺, Mg²⁺, and HCO₃ ^– as compared to Na⁺, K⁺, Cl^–, and SO₄ ^2–. With exception of few locations where Fe is relatively higher, the concentrations of these ions together with other water quality parameters are all within permissible limits of the domestic and agricultural standards.On the basis of the analytical results, groundwaters in the study area are largely characterized as Ca-(Mg)-HCO₃ type reflecting (possibly) young facies with limited migratory history. The occurrence of Ca-(Mg)-Na-HCO₃ water type in certain areas is attributed to cation exchange processes. In addition, the observed scattered relationship between the TDS and the thickness of weathered horizons in the boreholes indicates the contribution of precipitation (recharge) to the ionic inputs in the groundwaters in addition to the weathering and dissolution processes.     

Cation exchange processes and human activities in unconfined aquifers

During the 1999–2002 water years, a hydrogeological research project was carried out on the unconfined aquifer of Trifilia in the Peloponnese. Seawater intrusion due to overpumping, and intensive use of fertilizers caused the groundwater quality degradation that is a typical case for the coastal aquifers in Greece. Isopiezometric maps along with ion distribution balances, ion distribution maps and factor analysis indicate the existence of three zones of groundwater quality. In the first zone of saline water, a cation exchange process between the Ca²⁺ of sediments and the Na⁺ of groundwater contribute to the formation of the water type Na⁺-Ca²⁺-Cl^–. In the second zone, which is considered as a transition zone, dominate the Ca²⁺-Na⁺-HCO₃^–-Cl^– water type. In the third zone of Ca²⁺-HCO₃^–-SO₄^2– water type, relationships among Ca²⁺, SO₄^2–, NO₃^– and NH₄ can be attributed to the dissociation of ammonium nitrate and sulfate fertilizers on one hand, and Ca²⁺ derivation from cation exchange processes between water, rocks and clay minerals, such as smectite and illite, on the other.     

Groundwater quality and its suitability for drinking and agricultural use in Chithar River Basin, Tamil Nadu, India

Hydrochemistry of groundwater in Chithar Basin, Tamil Nadu, India was used to assess the quality of groundwater for determining its suitability for drinking and agricultural purposes. Physical and chemical parameters of groundwater such as electrical conductivity, pH, total dissolved solids (TDS), Na⁺, K⁺, Ca²⁺, Mg²⁺, Cl^–, HCO₃^–, CO₃^2–, SO₄^2–, NO^–₃, F^–, B^– and SiO₂ were determined. Concentrations of the chemical constituents in groundwater vary spatially and temporarily. Interpretation of analytical data shows that mixed Ca–Mg–Cl, Ca–Cl and Na–Cl are the dominant hydrochemical facies in the study area. Alkali earths (Ca²⁺, Mg²⁺) and strong acids (Cl^–, SO₄^2–) are slightly dominating over alkalis (Na⁺, K⁺) and weak acids (HCO₃^–, CO₃^2–). The abundance of the major ions is as follows: Na⁺ Ca²⁺ Mg²⁺ > K⁺ = Cl^– > HCO₃^–> SO₄^2– > NO₃^– > CO₃^2– . Groundwater in the area is generally hard, fresh to brackish, high to very high saline and low alkaline in nature. High total hardness and TDS in a few places identify the unsuitability of groundwater for drinking and irrigation. Such areas require special care to provide adequate drainage and introduce alternative salt tolerance cropping. Fluoride and boron are within the permissible limits for human consumption and crops as per the international standards.     

Major ion chemistry of groundwaters in the Bahar area, Hamadan, western Iran

Hydrochemical investigations were carried out in Bahar area, Hamadan, western Iran, to assess the chemical composition of groundwater. The area falls in a semi-arid type of climate. In this area, groundwater has been exploited over the past century mainly for irrigation and water supply. A total of 135 representative groundwater samples were collected from different wells to monitor the water chemistry of various ions. Chemical analysis of the groundwater shows that the mean concentration of the cations is of the order Ca²⁺>Mg ²⁺>Na⁺>K⁺, while that for anions is SO₄^2–>HCO₃^–>Cl^–>NO₃^–. Statistical analyses indicate positive correlation between the following pairs of parameters Cl^– and Mg ²⁺ (r=0.71), Cl^– and Na⁺ (r=0.76), HCO₃^– and Na⁺ (r=0.56), SO₄^2– and Mg²⁺ (r=0.76), SO₄^2– and Na⁺ (r=0.69). Water presents a large spatial variability of the chemical facies (Ca-HCO₃, Ca-SO₄, Mg-HCO₃, Mg-SO₄, Na-HCO₃) which is in relation to their interaction with the geological formations of the basin (carbonates, dolomite and various silicates) and evaporation. The hydrochemical types Ca-HCO₃ and Ca-SO₄ dominate the largest part of the studied area. The dissolution of halite, calcite, dolomite, and gypsum explains part of the contained Na ⁺, Ca²⁺, Mg²⁺, Cl^–, SO₄^2– and HCO₃^–, but other processes, such as cation exchange and weathering of aluminosilicates also contribute to the water composition.     

Assessment of groundwater pollution due to tannery industries in and around Dindigul, Tamilnadu, India

The overexploitation of groundwater in some parts of the country induces water quality degradation. The untreated industrial effluents discharged on the surface causes severe groundwater pollution in the industrial belt of the country. This poses a problem of supply of hazard free drinking water in the rural parts of the country. There are about 80 tanneries operating in and around Dindigul town in upper Kodaganar river basin, Tamilnadu, India. The untreated effluents from the tanneries have considerably affected the quality of groundwater in this area. To assess the extent of groundwater deterioration, a detailed analysis of groundwater quality data has been carried out. The concentration of cations such as Calcium (Ca²⁺), Magnesium (Mg²⁺), Sodium (Na⁺) and Potassium (K⁺), and anions such as Bicarbonate (HCO₃^–), Sulphate (SO₄^2–), Chloride (Cl^–) and Nitrate (NO₃^–) in the groundwater have been studied. Apart from these constituents, pH, electrical conductivity (EC), total dissolved solid and total hardness (TH as CaCO₃) were also studied. The correlation of these constituents with the EC has been carried out. The highest correlation is observed between EC and chloride with a correlation coefficient of 0.99. Progressive reduction in correlation coefficients for Mg²⁺, (Na⁺ + K⁺), Ca²⁺ and SO₄^2– are observed as 0.91, 0.87, 0.86 and 0.56, respectively. It is found that the quality of groundwater in the area under investigation is deteriorated mainly due to extensive use of salt in the leather industries.     

Coupled substitutions in the tourmaline group

Statistical analysis of 136 natural tourmaline compositions from the literature reveals the presence and extent of coupled substitutions involving several cations and structural sites. In schorls and dravites these are a dehydroxylation type substitution (1) (OH)^–+R²⁺ = R³⁺+O^2– and an alkali-defect type substitution (2) R⁺+R²⁺ = R³⁺+, Al³⁺ being the predominant R³⁺ action. Substitution (1) which represents solid solution towards a proton-deficient end-member, R⁺ R ₃ ³⁺ R ₆ ³⁺ (BO₃)₃ Si₆O₁₈O₃(OH), accounts for three times as much of the observed compositional variability as does (2) which represents substitution toward a hypothetical alkali-free end-member, (R ₂ ²⁺ R³⁺) R ₆ ³⁺ (BO₃)₃Si₆O₁₈(OH)₄. The occurrence of both of these substituions produces intermediates between end-member schorl/ dravite, R⁺ R ₃ ²⁺ R ₆ ³⁺ (BO₃)₃Si₆O₁₈(OH)₄, and a new series within the tourmaline group, R _1–x ⁺ R ₃ ³⁺ R ₆ ³⁺ (BO₃)₃Si₆O₁₈O_3–x (OH)_1+x.In addition to dehydroxylation type, 2(OH)^–+Li⁺ = R³⁺+20^2–, and possibly alkali-defect type, 2R⁺+Li⁺ = R³⁺+2, substitutions, a third type Li⁺+O^2– = (OH)^–+, occurs in the elbaites giving rise to Li-poor, proton-rich species. All three substitutions serve to reduce the Li-content of natural elbaite which, as a result, does not attain the composition of the ideal end-member, Na(Li_1.5Al_1.5)Al₆(BO₃)₃Si₆O₁₈(OH)₄. Substitution from elbaite and schorl/dravite toward R _1–x ⁺ R ₃ ³⁺ R ₆ ³⁺ (BO₃)₃Si₆O₁₈O_3–x(OH)_1+x is very extensive and may be complete.Substitution toward R _1–x ⁺ R ₃ ³⁺ R ₆ ³⁺ (BO₃)₃Si₆O₁₈O_3–x(OH)_1+x results in improved local charge balance. The mean deviation from oxygen charge saturation is at a maximum in end-member schorl, dravite and elbaite. Substitutions (1) and (2) progressively decrease but substitution (1) does so more effectively, which may explain its predominance in nature. However, alkali-defective end-members appear to be unstable regardless of . Substitution (3) in the elbaites cannot be discussed on the basis of charge balance considerations at present due to the lack of structural information on proton-rich species.     

A geoelectrical-hydrogeochemical investigation of shallow groundwater occurrence in Ibadan, southwestern Nigeria

 An integrated geological, geoelectrical and hydrochemical investigation of shallow groundwater occurrence in the Ibadan area, southwestern Nigeria, is presented. The primary objective was to characterise the groundwater in a typical low-latitude environment underlain by Precambrian crystalline basement complex rocks. The dominant rocks comprise suites of gneisses and quartzites. Chemical analyses of the groundwater show that the mean concentration of the cations is in the order Na>Ca>Mg>K while that for the anions is Cl>HCO₃>NO₃>SO₄. Statistical analyses, using the product-moment coefficient of correlation, indicate positive correlations between the following pairs of parameters: TDS and conductivity (r=0.96); Na⁺+Mg²⁺ and Cl^– (r=0.95); Na⁺+K⁺ and Ca²⁺ (r=0.43); Na⁺+K⁺ and HCO₃ ^– (r=0.17); Ca²⁺ and Mg²⁺ (r=0.74); Ca²⁺ and HCO₃ ^– (r=0.33); Ca²⁺+Mg²⁺ and HCO₃ ^– (r=0.31) and pH and HCO₃ ^– (r=0.54). A very weak negative correlation was recorded between pH and Cl^–, with r=–0.003. Five groundwater groups have been identified, namely, (1) the Na-Cl, Na-Ca-Cl, Na-Ca-(Mg)-Cl; (2) the Ca-(Mg)-Na-HCO₃-Cl, Na-Ca-HCO₃-Cl, and Ca-HCO₃-Cl; (3) the Ca-(Mg)-Na-HCO₃, Ca-Na-HCO_3; (4) Ca-Na-Cl-(SO₄)-HCO₃ and (5) the Ca-(Mg)-Na-SO₄-HCO₃. The different groups reflect the diversity of bedrock types and consequently also of the products of weathering. Most of the water sampled is unfit for drinking on account of the high NO₃ ^– content. It can, however, be used for irrigation purposes as the sodium hazard is low while the salinity hazard ranges from low to medium. Resistivity soundings indicate the presence of a thick weathering profile, which could be up to 60 m. Such sites should be the target for any long-term and sustainable groundwater development in the area. Received: 15 April 1998 · Accepted: 4 July 1998     

Groundwater chemistry within a plateau neighboring Matsumoto city,Japan

The change in groundwater chemistry along the groundwater flow path in the Matsumoto tunnel vicinity was studied, and the origin of the groundwater and dissoluted substances was determined. The relationship between the concentration of HCO₃ ^–, Ca²⁺, and Na⁺, and CO₂ gas pressure in the groundwater indicated that the HCO₃ ^–, Ca²⁺, and Na⁺ were produced by the reaction of the CO₂ gas in the groundwater and feldspar in the rocks. The relationship between the concentration of NO₃ ^– and the Eh and pH values in the groundwater indicated that in an oxidative condition, ammonia-oxidizing and nitriteoxidizing bacteria used NH₄ ⁺ and produced NO₃ ^– and H⁺, and in a reductive condition, denitrifying bacteria used NO₃ ^– and produced N₂ gas and OH^–. The stable hydrogen and oxygen isotopic ratio in the groundwater and precipitation indicated that the groundwater originated from precipitation that had fallen on the area. The concentration of³H and the stable hydrogen and oxygen isotopic ratios in the groundwater suggested that it has been getting warmer climatically for more than 60 years. The stable carbon isotopic ratio indicated that the HCO₃ ^– in the groundwater, excluding deep well water, originated from CO₂ gas produced by organic matter in the soil. The deep well water, which had a higher concentration of HCO₃ ^– than the other groundwater sampled, was thought to have acquired HCO₃ ^– though contact with rocks. The³⁶Cl/Cl ratio indicated the recharge age of the deep well water sampled at a depth of 760 m at the foot of the plateau was recent.     

Hydrogeochemical investigation and qualitative assessment of surface water resources in West Bokaro coalfield,India

A hydrogeochemical study of surface water of the West Bokaro coalfield has been undertaken to assess its quality and suitability for drinking, domestic and irrigation purposes. For this purpose, fourteen samples collected from rivers and ponds of the coalfield were analysed for pH, conductivity, total dissolved solids (TDS), major cations (Ca²⁺, Mg²⁺, Na⁺ and K⁺), major anions (HCO₃^-, F^-, Cl^-, SO₄^2- and NO₃^-) and trace metals. The pH of the analysed water samples varied from 7.3 to 8.2, indicating slightly alkaline in nature. The electrical conductivity (EC) value varied from 93 μs cm^-1 to 906 μs cm^-1 while the TDS varied from 76 mg L^-1 to 658 mg L^-1. HCO₃^- and SO₄^2- are the dominant anion and Ca²⁺ and Na⁺ the cation in the surface water. The concentration of alkaline earth metals (Ca²⁺ + Mg²⁺) exceed the alkali metals (Na⁺ + K⁺) and HCO₃^- dominates over SO₄^2- + Cl^- concentrations in the majority of the surface water samples. Ca²⁺ -Mg²⁺ -HCO₃^- and Ca²⁺ -Mg²⁺ -Cl^- are the dominant hydrogeochemical facies in the surface water of the area. The water chemistry is mainly controlled by rock weathering with secondary contribution from anthropogenic sources. For quality assessment, analyzed water parameter values compared with Indian and WHO water quality standard. In majority of the samples, the analyzed parameters are well within the desirable limits and water is potable for drinking purposes. However, concentrations of TDS, TH, Ca²⁺, Mg²⁺ and Fe are exceeding the desirable limits in some water samples and needs treatment before its utilization. The calculated parameters such as sodium absorption ration, percent sodium, residual sodium carbonate, permeability index and magnesium hazard revealed good to permissible quality and suitable for irrigation purposes, however, higher salinity, permeability index and Mg-ratio restrict its suitability for irrigation at few sites.     

Water soluble components of PM10 Chongqing, China

The concentrations of water soluble ions (Na⁺, NH₄ ⁺, K⁺, Mg²⁺, Ca²⁺, NO₃ ^-, Cl^-, and SO ₄ ^2- ) in PM₁₀ samples collected on cellulose filters by a medium-volume cascade impactor were determined, which were obtained from three kinds of areas in Chongqing: industrial area (Jiulongpo district), commercial and residential area (Jiangbei district) and background area (Jinyun Mountain in the Beibei district). The results showed that except for the background site, the annual average values of PM₁₀ are 23% – 61% higher than the national air quality standard (GradeII) (0.1 mg/m³), even that the value of the control site is still 20% higher than American standard (0.05 mg/m³). This implied that serious pollution of fine particles occurred in Chongqing. Nine kinds of soluble ions in water of PM₁₀ were analyzed by ion chromatography (IC) and the annual average concentrations follow the order of [SO ₄ ^2- ] > [NO³ _-] > [Cl^-] > [F^-], and [Ca²⁺] > [NH₄ ⁺] > [K⁺] > [Na⁺] > [Mg²⁺]. Their values were different in these areas: the industrial area > the commercial and living area > the control area. As for NH_{4 +}, K⁺, Ca²⁺, NO₃ ^- and SO ₄ ^2- , their seasonal average concentrations show a similar variation trend: the values in spring and fall were higher than those in summer and winter. The seasonal average concentrations of [Cl^-], [F^-], [Na⁺] and [Mg²⁺] are much lower than those of other ions. However, the concentrations of [Na⁺] changed more greatly in different seasons than those of the other three ions. Correlation coefficients showed that the three areas have been polluted by coal smoke and dust to different extents, while some local resources of pollution should be taken into consideration as well.     

Chemistry and sulfur isotopic composition of precipitation at Bologna, Italy

Individual and monthly precipitation samples from the polluted atmosphere of Bologna (Emilia-Romagna province) were collected during March 1996 to May 1997 and analyzed for major ions in solution and S isotopes in dissolved SO₄.Weighted mean enrichment factors relative to seawater are found to be 1.0 for Na, 15.2 for K, 105 for Ca, 3.3 for Mg, 17.3 for SO₄ and 663 for HCO⁻₃. Very good positive correlations are observed for the Ca²⁺–Mg²⁺–HCO⁻₃–SO²⁻₄–NO⁻₃ system, indicating that dissolution of Ca (±Mg)-carbonate particles by H₂SO₄ and HNO₃ from combustion of oil and gas is a major process controlling the chemical composition of rain and snow. Na⁺ and Cl⁻ in monthly precipitation derive essentially from sea spray, but the contribution of Na⁺ from continental sources is appreciable in a number of individual rains. NH⁺₄ appears to be on average more abundant in spring and summer precipitation, its main sources being microbial activity in soils and application of fertilizers. K⁺ is probably of continental origin from soil dust.The S isotopic composition of SO₄ is systematically positive, with mean δ³⁴S values of +3.2±1.6‰ (n=40) in individual precipitation and +2.8±1.4‰ (n=12) in monthly precipitation. These isotopic compositions are interpreted in terms of a dominant contribution of S from anthropogenic emissions and subordinate contributions from biogenic and marine sources. Pollutant SO₄ is estimated to have a δ³⁴S value in the range +2.5 to +4.5‰, whereas a distinctive δ³⁴S of −4.5‰ or lower indicates SO₄ from oxidation of biogenic gases.The isotopic and chemical compositions of SO₄ do not depend on wind direction, thus testifying to a mostly local source for pollutant S in the Bologna atmosphere.     

Schorlomite: a discussion of the crystal chemistry, formula, and inter-species boundaries

Examination of schorlomite from ijolite at Magnet Cove (USA) and silicocarbonatite at Afrikanda (Russia), using electron-microprobe and hydrogen analyses, X-ray diffraction and Mössbauer spectroscopy, shows the complexity of substitution mechanisms operating in Ti-rich garnets. These substitutions involve incorporation of Na in the eightfold-coordinated X site, Fe²⁺ and Mg in the octahedrally coordinated Y site, and Fe³⁺, Al and Fe²⁺ in the tetrahedrally coordinated Z site. Substitutions Ti⁴⁺Fe³⁺Fe³⁺_–1Si_–1 and Ti⁴⁺Al³⁺Fe³⁺_–1Si_–1 are of major significance to the crystal chemistry of schorlomite, whereas Fe²⁺ enters the Z site in relatively minor quantities (<3% Fe). There is no evidence (either structural or indirect, such as discrepancies between the measured and calculated Fe²⁺ contents) for the presence of ^[6]Ti³⁺ or ^[4]Ti⁴⁺ in schorlomite. The simplified general formula of schorlomite can be written as Ca₃Ti⁴⁺₂[Si_3-x(Fe³⁺,Al,Fe²⁺)_xO₁₂], keeping in mind that the notion of end-member composition is inapplicable to this mineral. In the published analyses of schorlomite with low to moderate Zr contents, x ranges from 0.6 to 1.0, i.e. Ti⁴⁺ in the Y site is <2 and accompanied by appreciable amounts of lower-charged cations (in particular, Fe³⁺, Fe²⁺ and Mg). For classification purposes, the mole percentage of schorlomite can be determined as the amount of ^[6]Ti⁴⁺, balanced by substitutions in the Z site, relative to the total occupancy in the Y site: (^[6]Ti⁴⁺–^[6]Fe²⁺–^[6]Mg²⁺– ^[8]Na⁺)/2. In addition to the predominant schorlomite component, the crystals examined in this work contain significant (>15 mol.%) proportions of andradite (Ca₃Fe³⁺₂Si₃O₁₂), morimotoite (Ca₃Fe²⁺TiSi₃O₁₂), and Ca₃MgTiSi₃O₁₂. The importance of accurate quantitative determination and assignment of Fe, Ti and other cations to the crystallographic sites for petrogenetic studies is discussed.

A thermodynamic model of Fe–Cr spinels

A new thermodynamic model for multi-component spinel solid solutions has been developed which takes into account thermodynamic consequences of cation mixing in spinel sublattices. It has been applied to the evaluation of thermodynamic functions of cation mixing and thermodynamic properties of Fe₃O₄–FeCr₂O₄ spinels using intracrystalline cation distribution in magnetite, lattice parameters and activity-composition relations of magnetite–chromite solid solutions. According to the model, cation distribution in binary spinels, (Fe_1-x²⁺ Fe_x³⁺)[Fe_x²⁺Fe_2-2y-x³⁺Cr_2y]O₄, and their thermodynamic properties depend strongly on Fe²⁺–Cr³⁺ cation mixing. Mixing of Fe²⁺–Fe³⁺ and Fe³⁺–Cr³⁺ can be accepted as ideal. If Fe²⁺, Fe³⁺ and Cr are denoted as 1, 3 and 4 respectively, the equation of cation distribution is –RT ln(x²/((1–x)(2–2y–x)))= G₁₃^* + (1–2x)W₁₃+y(W₁₄–W₁₃–W₃₄) where G₁₃^* is the difference between the Gibbs energy of inverse and normal magnetite, W_ij is a Margules parameter of cation mixing and G₁₃^*, J/mol =–23,000+13.4 T, W₁₄=36 kJ/mol, W₁₃=W₃₄=0. The positive nonconfigurational Gibbs energy of mixing is the main reason for changing activity–composition relations with temperature. According to the model, the solvus in Fe₃O₄–FeCr₂O₄ spinel has a critical temperature close to 500°C, which is consistent with mineralogical data.     

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.     

Zirconolite,allanite and hoegbomite in a marble skarn from the Bergell contact aureole: implications for mobility of Ti,Zr and REE

Zirconolite, allanite and hoegbomite are present as accessory phases in a metasomatically altered spinel-calcite-marble from the contact with the Bergell intrusives (Switzerland/Italy). Textural relationships indicate a step-wise alteration of spinel to 1) hoegbomite or corundum + magnetite, 2) margarite and 3) chlorite. Replacement of spinel by hoegbomite can be described by the substitution 1.94(Mg²⁺, Fe²⁺, Zn²⁺, Mn²⁺, Ca²⁺)Ti⁴⁺ +0.12(OH^–) where Al³⁺ and Fe³⁺ are held constant. The average composition of the Bergell hoegbomites is given by the formula Fe _0.97 ²⁺ Mg_0.69Zn_0.04Ti_0.17Al_3.94Fe _0.06 ³⁺ O_7.98(OH)_0.02 and seems to be imposed by the composition of pre-existing spinel. During the first two steps of spinel alteration, calcite was replaced by anorthite+phlogopite, and the rare earth element(REE)-bearing minerals zirconolite, allanite and sphene were formed. Allanites have characteristic chondrite-normalized REE patterns with enrichment in the light REE. The zirconolite patterns show a marked increase in concentration from La to Ce, followed by an almost constant section. Sphene lacks detectable La, and its REE patterns vary from grain to grain. Contemporaneous formation of phlogopite, REE-bearing minerals and hoegbomite during replacement of the spinel-calcite-marble indicates that the metamorphic fluid introduced potassium along with REE and other high valence cations (Ti⁴⁺, Zr⁴⁺, U⁴⁺, Th^4A3804265, Nb^5A3804265, Y^3A3804265) possibly as polynuclear complexes. The abundance of fluorine-bearing phlogopite and fluor-apatite as well as their close association with REE-bearing minerals and hoegbomite suggests F^– and PO ₄ ^3– as likely ligands for complexing of the above mentioned elements.     

Hydrogeochemical investigation and groundwater quality assessment of Pratapgarh district,Uttar Pradesh

Hydogrochemical investigation of groundwater resources of Paragraph district has been carried out to assess the solute acquisition processes and water quality for domestic and irrigation uses. Fifty-five groundwater samples were collected and analyzed for pH, electrical conductivity, total dissolved solids, hardness, major anions (F^?, Cl^?, NO₃, HCO₃ ^?, SO₄ ^2?) and cations (Ca²⁺, Mg²⁺, Na⁺, K⁺). Study results reveal that groundwater of the area is alkaline in nature and HCO₃ ^?, Cl^?, Mg²⁺, Na⁺ and Ca²⁺ are the major contributing ions to the dissolved solids. The hydrogeochemical data suggest that weathering of rock forming minerals along with secondary contributions from agricultural and anthropogenic sources are mainly controlling the groundwater composition of Pratapgarh district. Alkaline earth metals (Ca²⁺+Mg²⁺) exceed alkalis (Na⁺+K⁺) and weak acid (HCO₃ ^?) dominate over strong acids (Cl^?+SO₄ ^2?) in majority of the groundwater samples. Ca-Mg-HCO₃ and Ca-Mg-Cl-HCO₃ are the dominant hydrogeochemical facies in the groundwater of the area. The computed saturation indices demonstrate oversaturated condition with respect to dolomite and calcite and undersaturated with gypsum and fluorite. A comparison of groundwater quality parameters in relation to specified limits for drinking water shows that concentrations of TDS, F^?, NO₃ ^? and total hardness exceed the desirable limits in many water samples. Quality assessment for irrigation uses reveal that the groundwater is good for irrigation. However, values of salinity, sodium adsorption ratio (SAR), residual sodium carbonate (RSC), %Na and Kelley index are exceeding the prescribed limit at some sites, demanding adequate drainage and water management plan for the area.     

Geochemical mass balances of major chemical constituents in the watershed of the Changhuajian River in China

Based on the geological background, R-mode factor statistics, and the analysis of the stability diagram for the corresponding system, five weathering reactions controlling the surface-water chemical composition in the watershed of the Changhuajiang River are deduced. In the mass balance model, the precipitation accounts for some solute input, since the rainwater is dilute without pollution. Most of the Ca²⁺ and HCO ₃ ^– ions are from the dissolution of calcite, K⁺, Na⁺, H₄SiO₄ and some of the Mg²⁺ and HCO ₃ ^– come from albite and biotite weathering to kaolinite. The dissolution of dolomite and gypsum controls the mass balances of Mg²⁺ and SO ₄ ^2– . The dissolution of calcite is the dominant chemical weathering reaction in the watershed because of its reactivity and high concentration. In the watershed in 1986, the chemical weathering rate was 0.073 (kg/m² a), and the mechanical denudation rate is 0.093 (kg/m² a). The chemical weathering mass output proportion of carbonate rocks to silicate rocks was about three to one.     

Chemistry of rainwaters in the south Pacific area of Russia

On the south-eastern edge of Russia, the chemical composition of rainwater is controlled by sea salts, terrestrial material, as well as volcanic (Kuril islands volcanic area) and anthropogenic emissions, mostly in the southern part of the area. The predominant major ions of the Primorye, Sakhalin and the Kuril Islands rainwaters were respectively HCO₃⁻–SO₄²⁻, Ca–Na, and of Cl–Na. Concentration of trace elements changes within 1–2 orders of magnitude but some difference in the distribution of the elements between continental and island rainwater is found. The concentration of the chemical elements in the particulate fraction varies from < 10% to 90% of the total concentration (dissolved + particulate) with the following distribution: Tl, Na, Ca, Sr, Zn, Cd (< 10%)–Be, Th, Bi, Rb, U, K, Sc (10–20%)–Cu, Mn, Mg, Mo, Se, Ba, Ni, As, Ag, Cs, Co, Y, Ga, V (20–50%)–Sb, Pb, Ge, Cr, Fe, Al (50–90%).The concentration of elements of the particulate fraction of the rainwater usually is significantly different from concentrations in the crust, including both higher and lower concentrations. The terrestrial contribution to dissolved elements was evaluated and follows the decreasing order: Fe > K, Mg, Ca > Ba, Sr > Na (65–1%). Close order was found for total (dissolved and solid) concentrations. Sea salt contribution to dissolved element concentration in the rainwater decrease in the following order: Cl, Mg > K, SO₄ > Ca > HCO₃⁻, Ba, Fe (78–0.1%). Calculation of anthropogenic and volcanic inputs for two ions (Cl⁻ and SO₄²⁻) shows that anthropogenic inputs for the Vladivostok and Yuzno-Sakhalinsk cities can be evaluated as 15–20% of Cl⁻ and up to 80–90% of SO₄²⁻. Volcanic components in the Kuril Islands, where anthropogenic inputs are absent, can reach up to 76% of SO₄²⁻ and 36% of Cl⁻.     

Reaction mechanisms,physical conditions,and mass transfer during hydrothermal alteration of mica and feldspar in granitic rocks from south-central Maine,USA

Samples of granitic rock from south-central Maine contain primary igneous minerals altered by hydrothermal fluids. The reaction mechanisms (by which the over-all mineralogical change during the alteration was accomplished) involve several different mineral-fluid reactions at different reaction sites in the rock. The reactions involve both molecular and charged species in solution. The different reaction sites correspond to alteration of different primary igneous minerals. Biotite is partially converted to chlorite+sphene; microcline to muscovite; plagioclase to various combinations of muscovite, epidote, and calcite. The different reaction sites are linked by exchange of ions: some reaction sites produce ions consumed at other sites and vice versa. Physical conditions during the hydrothermal event are estimated from mineralogical and thermochemical data: P = 3,500 (±300) bars; T =425 ° (± 25 °)C. The fluid was characterized by X _{CO 2} = 0–0.13; ln([K⁺]/[H⁺ ]) = 10.0; ln([Ca²⁺]/[H⁺]²)=9.1; ln([Na⁺]/[H⁺]) = 10.5; Fe/(Fe+Mg) = 0.95. Amounts of secondary minerals in altered rock, when compared to the inferred mineral reactions that formed them, indicate that small but significant amounts (0.01–0.3mol/ 1,000cm³ altered rock) of CO₂, H₂O, H⁺, and K⁺ were added to the granites by fluids during the alteration, as well as lesser amounts (< 0.01–0.03 mol/1,000cm³ altered rock) of Mg²⁺, Fe²⁺, Fe³⁺, Mn²⁺, Na⁺, and Ti⁴⁺. The sole element leached from the granitic rocks during alteration was Ca in amounts 0.1–0.3 mol/1,000 cm³ rock. By estimating the composition of the hydrothermal fluids before and after reaction with the granites and by measuring the amount of material added to or subtracted from the granites during the alteration, the amount and volume of hydrothermal fluid involved can be calculated. Two independent calculations require minimum volumes in the range 100–1,000 cm³ fluid/1,000cm³ altered rock to participate in the hydrothermal event.     

Origin of light volatile hydrocarbon gases in mud volcano fluids, Gulf of Cadiz — Evidence for multiple sources and transport mechanisms in active sedimentary wedges

Widespread mud volcanism across the thick (≤ 14 km) seismically active sedimentary prism of the Gulf of Cadiz is driven by tectonic activity along extensive strike–slip faults and thrusts associated with the accommodation of the Africa–Eurasia convergence and building of the Arc of Gibraltar, respectively. An investigation of eleven active sites located on the Moroccan Margin and in deeper waters across the wedge showed that light volatile hydrocarbon gases vented at the mud volcanoes (MVs) have distinct, mainly thermogenic, origins. Gases of higher and lower thermal maturities are mixed at Ginsburg and Mercator MVs on the Moroccan Margin, probably because high maturity gases that are trapped beneath evaporite deposits are transported upwards at the MVs and mixed with shallower, less mature, thermogenic gases during migration. At all other sites except for the westernmost Porto MV, δ¹³C–CH₄ and δ²H–CH₄ values of ~ − 50‰ and − 200‰, respectively, suggest a common origin for methane; however, the ratio of CH₄/(C₂H₆ + C₃H₈) varies from ~ 10 to > 7000 between sites. Mixing of shallow biogenic and deep thermogenic gases cannot account for the observed compositions which instead result mainly from extensive migration of thermogenic gases in the deeply-buried sediments, possibly associated with biodegradation of C₂₊ homologues and secondary methane production at Captain Arutyunov and Carlos Ribeiro MVs. At the deep-water Bonjardim, Olenin and Carlos Ribeiro MVs, generation of C₂₊-enriched gases is probably promoted by high heat flux anomalies which have been measured in the western area of the wedge. At Porto MV, gases are highly enriched in CH₄ having δ¹³C–CH₄ ~ − 50‰, as at most sites, but markedly lower δ²H–CH₄ values < − 250‰, suggesting that it is not generated by thermal cracking of n-alkanes but rather that it has a deep Archaeal origin. The presence of petroleum-type hydrocarbons is consistent with a thermogenic origin, and at sites where CH₄ is predominant support the suggestion that gases have experienced extensive transport during which they mobilized oil from sediments ~ 2–4 km deep. These fluids then migrate into shallower, thermally immature muds, driving their mobilization and extrusion at the seafloor. At Porto MV, the limited presence of petroleum in mud breccia sediments further supports the hypothesis of a predominantly deep microbial origin of CH₄.