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.     

Chemistry and sulfur isotope investigation of industrial wastewater contamination into groundwater aquifers, Piteå County, N. Sweden

The possible contamination of a groundwater system with industrial wastewater originating from a paper mill factory has been investigated in Piteå, N. Sweden. Six samples were collected from the wastewater in the waste dump and twelve samples from the adjacent groundwater were analyzed for chemistry and sulfur isotopes. The industrial wastewater is a saline water consisting mainly of Na–HCO₃–SO₄, having a high pH and showing δ³⁴S values between 7‰ and 9‰ affected by bacterial sulfate reduction. The groundwaters are relatively dilute, dominated by Na⁺, Ca²⁺ and HCO₃⁻, but with varying concentrations as exemplified by sulfate with concentrations varying between 3 and 69 mg L^− 1 while the δ³⁴S values range from − 0.5‰ to 14.3‰. The data suggest that the main S sources in the waters are the bedrock sulfides and/or atmospheric deposition, which, sometimes, are overlapped by bacterial sulfate reduction. Contamination from the waste dump does not occur.     

Groundwater quality assessment in parts of Eastern Niger Delta, Nigeria

Hydrogeochemical analyses were carried out on groundwater samples collected from 20 producing wells in different parts of the Eastern Niger Delta. Results show that the concentrations of the major cations (Na⁺, K⁺, Ca²⁺, Mg²⁺) and anions (Cl^–, SO ₄ ^2– , HCO ₃ ^– ) are below the World Health Organization (WHO) standards set for domestic purposes. The occurrence of slightly saline water in certain areas is attributed to local hydrogeological processes occurring in the area. On the basis of the analytical results, two hydrogeochemical facies are delineated. These are calcium-magnesium-chloride-sulfate-bicarbonate (Ca-Mg-Cl-SO₄-HCO₃) and calcium-sodium-chloride-sulfatebicarbonate (Ca-Na-Cl-SO₄-HCO₃) to the west and east of the study area, respectively.     

Coexisting cummingtonite and calcic amphibole in amphibolites from the Schneeberg complex,Tyrol, Austria

Summary The formation of cummingtonite in two Ca and Al-poor and Mg-rich amphibolites from the Austroalpine Schneeberg complex occurred at a maximum temperature of about 550°C (5 kb). This is a result of the amphibolite facies Alpine overprint in this part of the Eastern Alps.Textural and chemical relations suggest (Mg_–1Si_–1Al₂)-continuous reactions in the bivariant CMASH-assemblageCam-Cum-Chl ^* followed by the discontinuous reactionCam+Chl+Qu=Cum+Plg+H₂O to be responsible for the formation of cummingtonite in these samples.The Mg–Fe distribution coefficient with values of 0.6–0.7 is similar to cummingtonite-Ca-amphibole pairs from amphibolites with oligoclase+quartz reported in the literature. The Mg/(Mg+Fe) ratio of the calcic amphiboles is lower (0.539–0.555) than the coexisting cummingtonites (0.648–0.662).

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Koexistierende Cummingtonite und Hornblenden in Amphiboliten des Schneeberger Zuges, Tirol, Österreich

Zusammenfassung In zwei Ca- und Al-armen Amphiboliten des nördlichen Schneebergerzuges (Rotmoostal) bildete sich Cummingtonit bei Maximaltemperaturen von 550°C (5 kb) bei der Altalpidschen Metamorphose.Texturelle und chemische Beziehungen lassen vermuten, daß sich Cummingtonite sowohl nach kontinuierlichen Reaktionen (in bezug auf den Tschermak-Vektor Mg_–1Si_–1Al₂) gebildet hat, als auch aus Hornblende und Chlorit nach der diskontinuierlichen ACF-ReaktionCam+Chl+Qu=Cum+Plg+H₂O hervorgegangen ist.Der Mg–Fe-Verteilungskoeffizient zwischen Hornblende und Cummingtonit entspricht den aus der Literatur bekannten Werten. Er beträgt zwischen 0.6–0.7 für die beginnende Amphibolitfazies. Die Mg/(Mg+Fe)-Verhältnisse sind höher in Cummingtonit (0.648–0.662) als in der koexistierenden Hornblende (0.539–0.555).

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With 4 Figures     

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     

Origins of high nitrate in groundwater in Tanzania

Dodoma is located in a semi-arid climate (mean annual rainfall 550 mm) in an area of crystalline basement rock. The groundwater contains high nitrate with NO₃⁻ concentrations averaging 150 mg l⁻¹ and total mineralization between 1000–3000 mg l⁻¹. Factor analysis has been used for the identification of factors that bring about the chemical character of groundwater. Three rotated factors, explaining 77.2% of the total data variance, were extracted. The first factor accounts for 51.0% of the variance and shows high positive correlation with Na⁺, K⁺, Mg²⁺, Ca²⁺, Cl⁻, SO₄²⁻, HCO₃⁻ and SEC and is attributed to the leaching of surface and soil salts together with mineral dissolution. The second factor accounts for 14.1% of the variance and is positively correlated with NO₃⁻ and negatively correlated with pH; this is explained by the nitrification process taking place on the sewage effluents. The third factor is highly positively correlated with ¹⁸O and ²H, accounting for 12.1% of the variance and is a consequence of evaporation processes. Nitrate concentrations greater than 100 mg l⁻¹ are commonly found in both deep and shallow groundwaters. It is concluded that the high nitrate concentrations have originated from the sewage effluents that are advecting and dispersing through macropores under bypass flow mechanisms.     

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.     

Hydrochemistry and isotope compositions of groundwater from the Shihongtan sandstone-hosted uranium deposit, Xinjiang, NW China

Groundwaters and surface water in the Shihongtan sandstone-hosted U ore district, Xinjiang, NW China, were sampled and analyzed for their major-, and trace element concentrations and oxygen, hydrogen, boron and strontium isotope compositions in order to assess the possible origins of the waters and water–rock interactions that occurred in the deep aquifer system. The waters in the study district have been grouped into three hydrochemical facies: Facies 1, potable spring-water, is a pH neutral (7.0), Na–Ca–HCO₃ type water with low total dissolved solids (TDS; 0.2 g/l, fresh) and has δ¹⁸O of − 8.3‰, δD of − 48.2‰,δ¹¹B of 1.5‰, and ⁸⁷Sr/⁸⁶Sr of 0.70627. Facies 2 groundwaters are mildly acidic to mildly alkaline (pH of 6.5–8.0, mean 7.3), Na–Ca–Mg–Cl–SO₄ type waters with moderate TDS (8.2 g/l–17.2 g/l, mean 9.3 g/l, brackish) and haveδ¹⁸O values in the − 5.8‰ to − 9.3‰ range (mean − 8.1‰), δD values in the − 20.8‰ to − 85.5‰ range (mean − 47.0‰),δ¹¹B values in the + 9.5‰ to + 39.1‰ range (mean + 17.1‰), and ⁸⁷Sr/⁸⁶Sr values in the 0.70595 to 0.70975 range (mean 0.70826). Facies 3, Aiting Lake water, is a mildly alkaline (pH = 7.4), Na–Ca–Mg–Cl–SO₄ type water with the highest TDS (249.1 g/l, brine) and has δ¹⁸O of − 2.8‰, δD of − 45.8‰,δ¹¹B of 21.2‰, and ⁸⁷Sr/⁸⁶Sr of 0.70840. The waters from the study district show a systematic increase in major, trace element and TDS concentrations and δ¹¹B values along the pathway of groundwater migration which can only be interpreted in terms of water–rock interaction at depth and strong surface evaporation. The hydrochemical and isotopic data presented here confirm that the groundwaters in the Shihongtan ore district are the combined result of migration, water–rock interaction and mixing of meteoric water with connate waters contained in sediments.     

Geochemistry of the mineral waters and gases of the Mukhen deposit,Far East

This work reports new hydrochemical data on the two types of cold high p CO₂ groundwaters from the Mukhen deposit (Khabarovsk district). The first type is classed with HCO₃-Ca-Mg waters with a relatively low TDS (up to 1.7 g/l) and high concentrations of Fe²⁺, Mn²⁺, Ba²⁺, and SiO₂. The second type is of HCO₃-Na composition with high TDS (up to 14 g/l) and elevated Li⁺, B, Sr²⁺, Br^?, and I^?. New oxygen (δ¹⁸O) and hydrogen (δD) isotopic data on the waters and carbon (δ¹³C) isotopic data on the gas phase, together with a detailed geological and hydrogeological analysis of the study area, allowed us to decipher the origin of both the mineral waters. Based on the tritium content (³H) in the ground and surface waters of the area, the duration of the mineral water circulation was estimated. It was established that the both types of groundwaters were formed during interaction of meteoric water with bedrock under active influence of CO₂, however HCO₃-Na groundwaters have longer residence time than HCO₃-Ca-Mg groundwaters.     

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.     

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.     

National scale evaluation of groundwater chemistry in Korea coastal aquifers: evidences of seawater intrusion

Pollution of groundwater by seawater intrusion poses a threat to sustainable agriculture in the coastal areas of Korea. Therefore, seawater intrusion monitoring stations were installed in eastern, western, and southern coastal areas and have been operated since 1998. In this study, groundwater chemistry data obtained from the seawater intrusion monitoring stations during the period from 2007 to 2009 were analyzed and evaluated. Groundwater was classified into fresh (<1,500 μS/cm), brackish (1,500–3,000 μS/cm), and saline (>3,000 μS/cm) according to EC levels. Among groundwater samples (n = 233), 56, 7, and 37% were classified as the fresh, brackish, and saline, respectively. The major dissolved components of the brackish and saline groundwaters were enriched compared with those of the fresh groundwater. The enrichment of Na⁺ and Cl⁻ was especially noticeable due to seawater intrusion. Thus, the brackish and saline groundwaters were classified as Ca–Cl and Na–Cl types, while the fresh groundwater was classified as Na–HCO₃ and Ca–HCO₃ types. The groundwater included in the Na–Cl types indicated the effects of seawater mixing. Ca²⁺, Mg²⁺, Na⁺, K⁺, SO₄ ²⁻, and Br⁻ showed good correlations with Cl⁻ of over r = 0.624. Of these components, the strong correlations of Mg²⁺, SO₄ ²⁻, and Br⁻ with Cl⁻ (r ≥ 0.823) indicated a distinct mixing between fresh groundwater and seawater. The Ca/Cl and HCO₃/Cl ratios of the groundwaters gradually decreased and approached those of seawater. The Mg/Cl, Na/Cl, K/Cl, SO₄/Cl, and Br/Cl ratios of the groundwaters gradually decreased, and were similar to or lower than those of seawater, indicating that Mg²⁺, Na⁺, K⁺, SO₄ ²⁻, and Br⁻, as well as Cl⁻ in the saline groundwater can be enriched by seawater mixing, while Ca²⁺ and HCO₃ ⁻ are mainly released by weathering processes. The influence of seawater intrusion was evaluated using threshold values of Cl⁻ and Br⁻, which were estimated as 80.5 and 0.54 mg/L, respectively. According to these criteria, 41–50% of the groundwaters were affected by seawater mixing.     

Biogeochemistry of trace metals (Mn, Sr, Rb, Ba, Cu, Zn, Pb and Cd) in a river-wetland-lake system (Balaton Region, Hungary)

Mn, Sr, Ba, Rb, Cu, Zn, Pb and Cd concentrations have been measured seasonally in the water and deposited sediments of the system comprising: Zala river (main input) — Lakes Kis-Balaton 1 and 2 (small artificial lakes created in a former bay of Lake Balaton) — Keszthely bay (hypertrophic part of Lake Balaton). The concentrations of the trace elements together with pH, alkalinity, dissolved cations (Ca²⁺, Mg²⁺, Na⁺, and K⁺), dissolved inorganic ligands (Cl^–, SO₄ ^2–), particulate Al, Ca, inorganic and organic carbon are used to assess the contamination of the study area and biogeochemical processes controlling trace element concentrations. Thermodynamic speciation calculations have also been utilized to enhance our understanding of the system. In the sediments Rb, Ba, Cu and Zn concentrations were mainly controlled by the abundance of the aluminosilicate fraction. Strontium was mainly associated with the calcium carbonate fraction. The aluminosilicate fraction constitutes a major sink for Mn and Cd but the concentration of these elements are also strongly related to calcite precipitation. The main processes that control the dissolved distribution of trace elements in the Balaton system were: solid phase formation (carbonate) for Mn; coprecipitation with calcite for Sr, Ba, Rb and possibly Mn and Cd; adsorption/desorption processes (pH dependent) for Zn and Pb; solubilization of Mn and precipitation of Cd and Cu in reed covered wetland areas where anoxic conditions were probably existing during the warm season. A preliminary budget of atmospheric and river input to Lake Balaton has also been outlined. Although Lake Balaton, is subjected to anthropogenic inputs mainly from agricultural and domestic activities, their impact on trace element concentrations in the Balaton system is very limited due to the efficiency of removal processes (i.e. adsorption and co-precipitation) and to high sedimentation rates and strong sediment re-suspension. Anthropogenic inputs are only detected for Pb.     

Water–Rock Interactions: An Investigation of the Relationships Between Mineralogy and Groundwater Composition and Flow in a Subtropical Basalt Aquifer

A holistic study of the composition of the basalt groundwaters of the Atherton Tablelands region in Queensland, Australia was undertaken to elucidate possible mechanisms for the evolution of these very low salinity, silica- and bicarbonate-rich groundwaters. It is proposed that aluminosilicate mineral weathering is the major contributing process to the overall composition of the basalt groundwaters. The groundwaters approach equilibrium with respect to the primary minerals with increasing pH and are mostly in equilibrium with the major secondary minerals (kaolinite and smectite), and other secondary phases such as goethite, hematite, and gibbsite, which are common accessory minerals in the Atherton basalts. The mineralogy of the basalt rocks, which has been examined using X-ray diffraction and whole rock geochemistry methods, supports the proposed model for the hydrogeochemical evolution of these groundwaters: precipitation + CO₂ (atmospheric + soil) + pyroxene + feldspars + olivine yields H₄SiO₄, HCO₃ ⁻, Mg²⁺, Na⁺, Ca²⁺ + kaolinite and smectite clays + amorphous or crystalline silica + accessory minerals (hematite, goethite, gibbsite, carbonates, zeolites, and pyrite). The variations in the mineralogical content of these basalts also provide insights into the controls on groundwater storage and movement in this aquifer system. The fresh and weathered vesicular basalts are considered to be important in terms of zones of groundwater occurrence, while the fractures in the massive basalt are important pathways for groundwater movement.     

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.

Geochemical evolution of groundwater in carbonate aquifers in Taiyuan, northern China

Thirty-nine samples of both cold and thermal karst groundwater from Taiyuan, northern China were collected and analyzed with the aim of developing a better understanding of the geochemical processes that control the groundwater quality evolution in the region’s carbonate aquifers. The region’s karst groundwater system was divided into three geologically distinct sub-systems, namely, the Xishan Mountain karst groundwater subsystem (XMK), the Dongshan Mountain karst groundwater subsystem (DMK) and the Beishan Mountain karst groundwater subsystem (BMK). Hydrochemical properties of the karst groundwaters evolve from the recharge zones towards the cold water discharge zones and further towards the thermal water discharge zones. In the XMK and the DMK, the hydrochemical type of the groundwater evolves from HCO₃-Ca·Mg in the recharge - flow-through zone, to HCO₃·SO₄-Ca·Mg/SO₄·HCO₃-Ca·Mg in the cold water discharge zone, and further to SO₄-Ca·Mg in the thermal water discharge zone. By contrast, the water type changes from HCO₃-Ca·Mg to HCO₃·SO₄-Ca·Mg in the BMK, with almost invariable TDS and temperatures all along from the recharge to the discharge zone. The concentrations of Sr, Si, Fe, F⁻ and of some trace elements (Al, B, Li, Mn, Mo, Co, Ni) increase as groundwater temperature increases. Different hydrogeochemical processes occur in the three karst groundwater sub-systems. In the XMK and the DMK, the geochemical evolution of the groundwater is jointly controlled by carbonate dissolution/precipitation, gypsum dissolution and dedolomitization, while only calcite and dolomite dissolution/precipitation occurs in the BMK without dedolomitization. The hydrogeochemical data of the karst groundwaters were used to construct individual geochemical reaction models for each of the three different karst groundwater sub-systems. The modeling results confirm that dedolomization is the major process controlling hydrochemical changes in the XMK and the DMK. In the thermal groundwaters, the dissolution rates of fluorite, siderite and strontianite were found to exceed those of the cold karst groundwater systems, which can explain the higher concentrations of F⁻, Fe and Sr²⁺ that are found in these waters.     

Field setting,mineralogy, chemistry,and genesis of arc picrites,New Georgia,Solomon Islands

The field setting, petrography, mineralogy, and geochemistry of a suite of picrite basalts and related magnesian olivine tholeiites (New Georgia arc picrites) from the New Georgia Volcanics, Kolo caldera in the active ensimatic Solomon Islands arc are presented. These lavas, with an areal extent in the order of 100² km and almost 1 km thick in places, are located close to the intersection of the Woodlark spreading zone with the Pacific plate margin. They contain abundant olivine (Fo_94-75) and diopside (Cr₂O₃ 1.1-0.4%, Al₂O₃ 1–3%), and spinels characterised by a large range in Cr/(Cr+Al) (0.85–0.46) and Mg/(Mg+ Fe⁺⁺) (0.65–0.1). The spinels are Fe⁺⁺⁺ rich, with Fe⁺⁺⁺/ (Fe⁺⁺⁺+Cr+Al) varying from 0.06 to 1.0. A discrete group of spinels with the highest Cr/(Cr+Al) (0.83–0.86) and lowest Fe⁺⁺⁺ contents are included in the most Mg-rich olivine (Fo_91–94) and both may be xenocrystal in origin.The lavas, which range between 10–28% MgO, define linear trends on oxide (element) — MgO diagrams and these trends are interpreted as olivine (0.9) clinopyroxene (0.1) control lines. For the reconstructed parent magma composition of these arc picrites, ratios involving CaO, Al₂O₃, TiO₂, Zr, V and Sc are very close to chondritic. REE patterns are slightly LREE — enriched ((La/Sm)^N 1.3–1.43) and HREE are flat. All lavas show marked enrichments in K, Rb, Sr, Ba, and LREE relative to MORB with similar MgO contents, but the TiO₂ content of the proposed parent magma is close to those of postulated primary MORB liquids. It is proposed that the arc parent magma was produced by partial melting of sub-oceanic upper mantle induced by the introduction of LILE — enriched hydrous fluids derived by dehydration and/or partial melting of subducted ocean crust and possibly minor sediments.     

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 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.     

Adsorption of rare earth elements onto Carrizo sand: Experimental investigations and modeling with surface complexation

Rare earth element (REE) adsorption onto sand from a well characterized aquifer, the Carrizo Sand aquifer of Texas, has been investigated in the laboratory using a batch method. The aim was to improve our understanding of REE adsorption behavior across the REE series and to develop a surface complexation model for the REEs, which can be applied to real aquifer-groundwater systems. Our batch experiments show that REE adsorption onto Carrizo sand increases with increasing atomic number across the REE series. For each REE, adsorption increases with increasing pH, such that when pH >6.0, >98% of each REE is adsorbed onto Carrizo sand for all experimental solutions, including when actual groundwaters from the Carrizo Sand aquifer are used in the experiments. Rare earth element adsorption was not sensitive to ionic strength and total initial REE concentrations in our batch experiments. It is possible that the differences in experimental ionic strength conditions (i.e., 0.002-0.01 M NaCl) chosen were insufficient to affect REE adsorption behavior. However, cation competition (e.g., Ca, Mg, and Zn) did affect REE adsorption onto Carrizo sand, especially for light rare earth elements (LREEs) at low pH. Rare earth element adsorption onto Carrizo sand can be successfully modeled using a generalized two-layer surface complexation model. Our model calculations suggest that REE complexation with strong surface sites of Carrizo sand exceeds the stability of the aqueous complexes LnOH²⁺, LnSO₄⁺, and LnCO₃⁺, but not that of Ln(CO₃)₂^- or LnPO₄^o in Carrizo groundwaters. Thus, at low pH (<7.3), where major inorganic ligands did not effectively compete with surface sites for dissolved REEs, free metal ion (Ln³⁺) adsorption was sufficient to describe REE adsorption behavior. However, at higher pH (>7.3) where solution complexation of the dissolved REEs was strong, REEs were adsorbed not only as free metal ion (Ln³⁺) but also as aqueous complexes (e.g., as Ln(CO₃)₂^- in Carrizo groundwaters). Because heavy rare earth elements (HREEs) were preferentially adsorbed onto Carrizo sand compared to LREEs, original HREE-enriched fractionation patterns in Carrizo groundwaters from the recharge area flattened along the groundwater flow path in the Carrizo Sand aquifer due to adsorption of free- and solution-complexed REEs.