Hydrochemical and isotopic characteristics of groundwater in the Ndop plain,northwest Cameroon: resilience to seasonal climatic changes

Shallow groundwater (>30 mbgl) is an essential source of drinking water to rural communities in the Ndop plain, northwest Cameroon. As a contribution to water management, the effect of seasonal variation on the groundwater chemistry, hydrochemical controls, drinking quality and recharge were investigated during the peaks of the dry (January) and rainy (September) seasons. Field measurements of physical parameters were preceded by sampling 58 groundwater samples during both seasons for major ions and stable isotope analyses. The groundwater, which was barely acidic (mean pH of 6) and less mineralised (TDS < 272 mg/l), showed no significant seasonal variation in temperature, pH and TDS during the two seasons. The order of cation abundance (meq/l) was Na⁺ > Ca²⁺ > Mg²⁺ > K⁺ and Na⁺ > Mg²⁺ > Ca²⁺ > K⁺ in the dry and rainy seasons, respectively, but that of anions ( \( {\text{HCO}}_{3}^{ - } \)  >  \( {\text{NO}}_{3}^{ - } \)  > Cl^? >  \( {\text{SO}}_{4}^{2 - } \)  > F^?) was similar in both seasons. This suggests a negligible effect of seasonal variations on groundwater chemistry. The groundwater, which was CaMgHCO₃ and NaHCO₃, is chemically evolved rainfall (CaMgSO₄Cl) in the area. Silicate mineral dissolution and cation-exchange were the main controls on groundwater chemistry while there was little anthropogenic influence. The major ions and TDS concentrations classified the water as suitable for human consumption as per WHO guidelines. The narrow cluster of δ¹⁸O and δD of same groundwater from both seasons between the δ¹⁸O and δD values of May–June precipitation along the Ndop Meteoric Water Line indicates meteoric origin, rapid recharge (after precipitation) and timing of recharge between May and June rainfall. Diffuse groundwater recharge mainly occurs at low altitudes (<1,400 m asl) within the plain. Besides major ions and TDS, the similar δ¹⁸O and δD of groundwater from both seasons indicate a consistent groundwater recharge and flow pattern throughout the year and resilience to present day short-term seasonal climatic variations. However, controlled groundwater abstraction is recommended given the increasing demand.     

Weathering Processes in the Min Jiang: Major Elements, {}^{87}{\text{Sr/}}{}^{86}{\text{Sr}},\;\delta {}^{34}{\text{S}}_{{\text{SO}}_{\text{4}} } ,\;{\text{and}}\;\delta {}^{18}{\text{O}}_{{\text{SO}}_{\text{4}} }

We investigated the dissolved major elements, $ {}^{87}{\text{Sr/}}{}^{86}{\text{Sr}},\;\delta {}^{34}{\text{S}}_{{\text{SO}}_{\text{4}} } ,\;{\text{and}}\;\delta {}^{18}{\text{O}}_{{\text{SO}}_{\text{4}} } $ composition of the Min Jiang, a headwater tributary of the Chang Jiang (Yangtze River). A forward calculation method was applied to quantify the relative contribution to the dissolved load from rain, evaporite, carbonate, and silicate reservoirs. Input from carbonate weathering dominated the major element composition (58–93%) and that from silicate weathering ranged from 2 to 18% in unperturbed Min Jiang watersheds. Most samples were supersaturated with respect to calcite, and the CO₂ partial pressures were similar to or up to ～5 times higher than atmospheric levels. The Sr concentrations in our samples were low (1.3–2.5 μM) with isotopic composition ranging from 0.7108 to 0.7127, suggesting some contribution from felsic silicates. The Si/(Na^* + K) ratios ranged from 0.5 to 2.5, which indicate low to moderate silicate weathering intensity. The $ \delta {}^{34}{\text{S}}_{{\text{SO}}_{\text{4}} } \;{\text{and}}\;\delta {}^{18}{\text{O}}_{{\text{SO}}_{\text{4}} } $ for five select samples showed that the source of dissolved sulfate was combustion of locally consumed coal. The silicate weathering rates were 23–181 × 10³ mol/km²/year, and the CO₂ consumption rates were 31–246 × 10³ mol/km²/year, which are moderate on a global basis. Upon testing various climatic and geomorphic factors for correlation with the CO₂ consumption rate, the best correlation coefficients found were with water temperature (r ² = 0.284, p = 0.009), water discharge (r ² = 0.253, p = 0.014), and relief (r ² = 0.230, p = 0.019).     

Integrated geophysical, geochemical and hydrogeological investigation of shallow groundwater resources in parts of the Ikom-Mamfe Embayment and the adjoining areas in Cross River State, Nigeria

Information generated from geophysical, geochemical and hydrogeological data has been used in assessing the groundwater resource potential, quality and usability and in mapping flow directions within the shallow subsurface of the Mamfe Embayment, Cross River State, Nigeria. The electrical resistivity technique in which the Schlumberger’s vertical electrical sounding field procedure has been adopted was the geophysical method employed; lithology logs from drilling records, discharge rates, static water level information were the hydrogeological information utilized, while the geochemical techniques involve analyses of water samples. Apparent resistances were measured using different resistivity meters including OYO McOhm (model 2115), ABEM terrameter (SAS300B and SAS1000 models) and IGIS (SSP-ATS-MRP model) with maximum current electrode separation reaching 1 km in some communities. Geological information was used as control in the modelling and interpretation of all geophysical data. The physico-chemical parameters of the water samples from the different water sources in the area were determined using different analytical techniques and in some cases, by in situ direct measurement of some parameters. Measured values of electrical conductivity, static water level, available aquifer discharge information and calculated SAR and %Na were integrated into the geophysical and hydrogeological results. The shallow subsurface of the area is segmented into four hydrogeological provinces [crystalline basement province (CBP), Cross River Plain Province (CRPP), Nkporo-Afikpo Shales Province (NASP) and alluvial/buried river province (ABRP) with localized groundwater flow patterns]. Results indicated that the alluvial (discharge rate of 3.83 L/s), fractured sandstone (discharge rate of 2.43 L/s) and basement (discharge rate of 1.80 L/s) aquifers are more yielding than the aquifers in areas covered with deformed shales (discharge rate of 0.62 L/s) and siltstone aquifers (discharge rate of 0.97 L/s). The aquifer horizons are inhomogeneous and anisotropic with topography and lithology exerting significant influence on groundwater flow direction. However, there appears to be some high yielding aquifers at depths greater than 100 m in the CRPP areas although researches on their distribution are still ongoing. Precipitation is the major source of recharge and the water is enriched with Na⁺, K⁺, Ca²⁺, Mg²⁺, ${\text{HCO}}_{ 3}^{ - }$ , Cl^?, ${\text{SO}}_{ 4}^{2 - }$ and ${\text{NO}}_{ 3}^{ - }$ throughout the year. Graphical analyses of hydrochemical data using Piper and Stiff diagrams show that Ca–(Mg)–CO₃–HCO₃ is the dominant water facies. Results from EC, SAR and %Na show that the water is fresh and belongs to the good-to-excellent class and is, therefore, suitable for domestic, agricultural and industrial use.     

Hydrochemical characteristics of surface and groundwater and suitability for drinking and agricultural use in the Upper Tigris River Basin,Diyarbakır–Batman,Turkey

Investigations were undertaken into the quality of surface water and groundwater bodies within the Upper Tigris Basin in Turkey to determine their suitability for potable and agricultural use. In the study area, the majority of the groundwater and surface water samples belong to the calcium–magnesium–bicarbonate type (Ca–Mg–HCO₃) or magnesium–calcium–bicarbonate type (Mg–Ca–HCO₃). Chemical analysis of all water samples shows that the mean cation concentrations (in mg/L) were in the order Ca²⁺ > Mg²⁺ > Na⁺ > K⁺ and that of anions are in the order \( \text{HCO}_{3}^{ - } \) > \( \text{SO}_{4}^{2 - } \) > Cl^? > \( \text{CO}_{3}^{ - } \) for all groundwater and surface water samples. The Mg²⁺/Ca²⁺ ratio ranges from 0.21 to 1.30 with most of the values greater than 0.5, indicating that weathering of dolomites is dominant in groundwater. The analysis reveals that all of the samples are neutral to slightly alkaline (pH 7.0–8.7). Groundwater and surface water suitability for drinking usage was evaluated according to the World Health Organization and Turkish Standards (TSE-266) and suggests that most of the samples are suitable for drinking. Various determinants such as sodium absorption ratio, percent sodium (Na %), residual sodium carbonate and soluble sodium percentage revealed that most of the samples are suitable for irrigation. According to MH values, all of the well water samples were suitable for irrigation purposes, but 80 and 81.82% of Zillek springs and surface water samples were unsuitable. As per the PI values, the water samples from the study area are classified as Class I and Class II and are considered to be suitable for irrigation.     

Appraisal of groundwater quality in a crystalline aquifer: a chemometric approach

The purpose of this study is to assess the groundwater quality and identify the processes that control the groundwater chemistry in a crystalline aquifer. A total of 72 groundwater samples were collected during pre- and post-monsoon seasons in the year 2014 in a semi-arid region of Gooty Mandal, Anantapur district, Andhra Pradesh, India. The study utilized chemometric analysis like basic statistics, Pearson’s correlation coefficient (r), principal component analysis (PCA), Gibbs ratio, and index of base exchange to understand the mechanism of controlling the groundwater chemistry in the study area. The results reveal that groundwater in the study area is neutral to slightly alkaline in nature. The order of dominance of cations is Na⁺ > Ca²⁺ > Mg²⁺ > K⁺ while for anions, it is \( {\mathrm{HCO}}_3^{-}>{\mathrm{Cl}}^{-} \)>\( {\mathrm{NO}}_3^{-} \)>\( {\mathrm{SO}}_4^{2-} \)>\( {\mathrm{CO}}_3^{2-}>{\mathrm{F}}^{-} \) in both seasons. Based on the Piper classification, most of the groundwater samples are identified as of sodium bicarbonate (\( {\mathrm{Na}}^{+}-{\mathrm{HCO}}_3^{-}\Big) \) type. According to the results of the principal component analysis (PCA), three factors and two factors were identified pre and post monsoon, respectively. The present study indicates that the groundwater chemistry is mostly controlled by geogenic processes (weathering, dissolution, and ion exchange) and some extent of anthropogenic activities.     

Crystal chemistry of Fe3+-bearing (Mg,Fe)SiO3 perovskite: a single-crystal X-ray diffraction study

Magnesium silicate perovskite is the predominant phase in the Earth’s lower mantle, and it is well known that incorporation of iron has a strong effect on its crystal structure and physical properties. To constrain the crystal chemistry of (Mg, Fe)SiO₃ perovskite more accurately, we synthesized single crystals of Mg_0.946(17)Fe_0.056(12)Si_0.997(16)O₃ perovskite at 26 GPa and 2,073 K using a multianvil press and investigated its crystal structure, oxidation state and iron-site occupancy using single-crystal X-ray diffraction and energy-domain Synchrotron Mössbauer Source spectroscopy. Single-crystal refinements indicate that all iron (Fe²⁺ and Fe³⁺) substitutes on the A-site only, where \( {\text{Fe}}^{ 3+ } /\Upsigma {\text{Fe}}\sim 20\,\% \) based on Mössbauer spectroscopy. Charge balance likely occurs through a small number of cation vacancies on either the A- or the B-site. The octahedral tilt angle (Φ) calculated for our sample from the refined atomic coordinates is 20.3°, which is 2° higher than the value calculated from the unit-cell parameters (a = 4.7877 Å, b = 4.9480 Å, c = 6.915 Å) which assumes undistorted octahedra. A compilation of all available single-crystal data (atomic coordinates) for (Mg, Fe)(Si, Al)O₃ perovskite from the literature shows a smooth increase of Φ with composition that is independent of the nature of cation substitution (e.g., \( {\text{Mg}}^{ 2+ } - {\text{Fe}}^{ 2+ } \) or \( {\text{Mg}}^{ 2+ } {\text{Si}}^{ 4+ } - {\text{Fe}}^{ 3+ } {\text{Al}}^{ 3+ } \) substitution mechanism), contrary to previous observations based on unit-cell parameter calculations.     

An experimental study of Ti and Zr partitioning among zircon, rutile, and granitic melt

In order to evaluate the effect of trace and minor elements (e.g., P, Y, and the REEs) on the high-temperature solubility of Ti in zircon (zrc), we conducted 31 experiments on a series of synthetic and natural granitic compositions [enriched in TiO₂ and ZrO₂; Al/(Na + K) molar ~1.2] at a pressure of 10 kbar and temperatures of ~1,400 to 1,200 °C. Thirty of the experiments produced zircon-saturated glasses, of which 22 are also saturated in rutile (rt). In seven experiments, quenched glasses coexist with quartz (qtz). SiO₂ contents of the quenched liquids range from 68.5 to 82.3 wt% (volatile free), and water concentrations are 0.4–7.0 wt%. TiO₂ contents of the rutile-saturated quenched melts are positively correlated with run temperature. Glass ZrO₂ concentrations (0.2–1.2 wt%; volatile free) also show a broad positive correlation with run temperature and, at a given T, are strongly correlated with the parameter (Na + K + 2Ca)/(Si·Al) (all in cation fractions). Mole fraction of ZrO₂ in rutile $ \left( {\mathop X\nolimits_{{{\text{ZrO}}_{ 2} }}^{\text{rt}} } \right) $ in the quartz-saturated runs coupled with other 10-kbar qtz-saturated experimental data from the literature (total temperature range of ~1,400 to 675 °C) yields the following temperature-dependent expression: $ {\text{ln}}\left( {\mathop X\nolimits_{{{\text{ZrO}}_{ 2} }}^{\text{rt}} } \right) + {\text{ln}}\left( {a_{{{\text{SiO}}_{2} }} } \right) = 2.638(149) - 9969(190)/T({\text{K}}) $ , where silica activity $ a_{{{\text{SiO}}_{2} }} $ in either the coexisting silica polymorph or a silica-undersaturated melt is referenced to α-quartz at the P and T of each experiment and the best-fit coefficients and their uncertainties (values in parentheses) reflect uncertainties in T and $ \mathop X\nolimits_{{{\text{ZrO}}_{2} }}^{\text{rt}} $ . NanoSIMS measurements of Ti in zircon overgrowths in the experiments yield values of ~100 to 800 ppm; Ti concentrations in zircon are positively correlated with temperature. Coupled with values for $ a_{{{\text{SiO}}_{2} }} $ and $ a_{{{\text{TiO}}_{2} }} $ for each experiment, zircon Ti concentrations (ppm) can be related to temperature over the range of ~1,400 to 1,200 °C by the expression: $ \ln \left( {\text{Ti ppm}} \right)^{\text{zrc}} + \ln \left( {a_{{{\text{SiO}}_{2} }} } \right) - \ln \left( {a_{{{\text{TiO}}_{2} }} } \right) = 13.84\left( {71} \right) - 12590\left( {1124} \right)/T\left( {\text{K}} \right) $ . After accounting for differences in $ a_{{{\text{SiO}}_{2} }} $ and $ a_{{{\text{TiO}}_{2} }} $ , Ti contents of zircon from experiments run with bulk compositions based on the natural granite overlap with the concentrations measured on zircon from experiments using the synthetic bulk compositions. Coupled with data from the literature, this suggests that at T ≥ 1,100 °C, natural levels of minor and trace elements in “granitic” melts do not appear to influence the solubility of Ti in zircon. Whether this is true at magmatic temperatures of crustal hydrous silica-rich liquids (e.g., 800–700 °C) remains to be demonstrated. Finally, measured $ D_{\text{Ti}}^{{{\text{zrc}}/{\text{melt}}}} $ values (calculated on a weight basis) from the experiments presented here are 0.007–0.01, relatively independent of temperature, and broadly consistent with values determined from natural zircon and silica-rich glass pairs.     

Assessment of spatial distribution of contaminants and their levels in soil and water resources of Calabar,Nigeria using geophysical and geological data

The contamination levels of soils and water resources in Calabar, Nigeria have been investigated using resistivity (vertical electrical sounding and electrical resistivity tomography), geochemical analyses of soil and water resources and textural analysis. Sixty randomly sited VES sites were investigated in two seasons while ERT investigations were performed along four profiles. The geochemical investigations were spread across seasons in order to track seasonal changes in physico-chemical parameters: hydrogen ion concentration (pH), electrical conductivity, total dissolved solids, chloride ion (Cl^?), nitrate ion (\( {\text{NO}}_{ 3}^{ - } \)), bicarbonate (\( {\text{HCO}}_{ 3}^{ - } \)), sulphate ion (\( {\text{SO}}_{ 4}^{2 - } \)), calcium ion (Ca²⁺), sodium ion (Na⁺), potassium ion (K⁺) and magnesium ion (Mg²⁺). Additionally, concentrations of ammonium, aluminium and nitrite ions in soils were determined. Results show that ionic concentrations in the sand-dominated soils and water are within permissible limits and baseline standards. The resistivities follow known trends in the area. However, at the central waste disposal site, a localised thin (< 5 m), low resistivity (< 15 Ωm) anomaly suspected to be due to contamination by leachates was observed. Comparatively, the contaminated area is also characterised by marginal increase in ionic concentrations. Strong attenuation capacities of overlying and adjoining clay/lateritic sediments and optimal design of the waste dump site probably reduced the spread of contaminants. The contaminated zone need to be closely monitored so that it does not extend to the aquifers. Hence, all strategies presently being used in managing wastes in Calabar should be sustained.     

Groundwater quality assessment from a hard rock terrain, Salem district of Tamilnadu, India

A total of 162 groundwater samples for three representative seasons were collected from Salem district of Tamilnadu, India to decipher hydrogeochemistry and groundwater quality for determining its suitability for drinking and agricultural proposes. The water is neutral to alkaline in nature with pH ranging from 6.6 to 8.6 with an average of 8.0. Higher electrical conductivity was observed during post-monsoon season. The abundance of major ions in the groundwater was in the order of $ {\text{Na} > \text{Ca} > \text{Mg} > \text{K} = \text{Cl} > \text{HC}}{{\text{O}}_3}\; > \;{\text{S}}{{\text{O}}_4}\; > \;{\text{N}}{{\text{O}}_3} $ . Piper plot reveals the dominance of geochemical facies as mixed Ca–Mg–Cl, Na–Cl, Ca–HCO₃, Ca–Na–HCO₃, and Ca–Cl type. NO₃, Cl, SO₄, and F exceed the permissible limit during summer and post-monsoon seasons. Sodium adsorption ratio was higher during post-monsoon and southwest monsoon season indicating high and low salinity, satisfactory for plants having moderate salt tolerance on soils. Permeability index of water irrespective of season falls in class I and class II indicating water is moderate to good for irrigation purposes. As per the classification of water for irrigation purpose, water is fit for domestic and agricultural purposes with minor exceptions irrespective of seasons.     

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

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

Majoritic garnet grains within shock-induced melt veins in amphibolites from the Ries impact crater suggest ultrahigh crystallization pressures between 18 and 9 GPa

Shock-induced melt veins in amphibolites from the Nördlinger Ries often have chemical compositions that are similar to bulk rock (i.e., basaltic), but there are other veins that are confined to chlorite-rich cracks that formed before the impact and these are poor in Ca and Na. Majoritic garnets within the shock veins show a broad chemical variation between three endmembers: (1) \({}^{\text{VIII}}{{\text{M}^{2+}}_3} {}^{\text{VI}}{\text{Al}}_{2} ({}^{\text{IV}}{\text{SiO}}_{4} )_{3}\) (normal garnet, Grt), (2) \({}^{\text{VIII}}{{\text{M}^{2+}}_3} {}^{\text{VI}}[{\text{M}}^{2 + } ({\text{Si,Ti}})]({}^{\text{IV}}{\text{SiO}}_{4} )_{3}\)  (majorite, Maj), and (3) \({}^{\text{VIII}}({{\text {Na} {\text M}^{2+}}_2}) {}^{\text{VI}}[ ({\text{Si,Ti}}){\text {Al}}]({}^{\text{IV}}{\text{SiO}}_{4} )_{3}\) (Na-majorite₅₀Grt₅₀), whereby M²⁺ = Mg²⁺, Fe²⁺, Mn²⁺, Ca²⁺. In particular, we observed a broad variation in ^VI(Si,Ti) which ranges from 0.12 to 0.58 cations per formula unit (cpfu). All these majoritic garnets crystallized during shock pressure release at different ultrahigh pressures. Those with high ^VI(Si,Ti) (0.36–0.58 cpfu) formed at high pressures and temperatures from amphibole-rich melts, while majoritic garnets with lower ^VI(Si,Ti) of 0.12–0.27 cpfu formed at lower pressures and temperatures from chlorite-rich melts. Furthermore, majoritic garnets with intermediate values of ^VI(Si,Ti) (0.24–0.39) crystallized from melts with intermediate contents of Ca and Na. To the best of our knowledge the ‘MORB-type’ Ca–Na-rich majoritic garnets with maximum contents of 2.99 wt% Na₂O and calculated crystallisation pressures of 16–18 GPa are the most extreme representatives ever found in terrestrial shocked materials. At the Ries, the duration of the initial contact and compression stage at the central location of impact is estimated to only ~ 0.1 s. We used a ~ 200-µm-thick shock-induced vein in a moderately shocked amphibolite to model its pressure–temperature–time (P–T–t) path. The graphic model manifests a peak temperature of ~ 2600 °C for the vein, continuum pressure lasting for ~ 0.02 s, a quench duration of ~ 0.02 s and a shock pulse of ~ 0.038 s. The small difference between the continuum pressure and the pressure of majoritic garnet crystallization underlines the usefulness of applying crystallisation pressures of majoritic garnets from metabasites for calculation of dynamic shock pressures of host rocks. Majoritic garnets of chlorite provenance, however, are not suitable for the determination of continuum pressure since they crystallized relatively late during shock release. An extraordinary glass- and majorite-bearing amphibole fragment in a shock-vein of one amphibolite documents the whole unloading path.     

The Hydrolysis of Al(III) in NaCl solutions: A Model for M(II), M(III), and M(IV) Ions

Understanding the identity and stability of the hydrolysis products of metals is required in order to predict their behavior in natural aquatic systems. Despite this need, the hydrolysis constants of many metals are only known over a limited range of temperature and ionic strengths. In this paper, we show that the hydrolysis constants of 31 metals [i.e. Mn(II), Cr(III), U(IV), Pu(IV)] are nearly linearly related to the values for Al(III) over a wide range of temperatures and ionic strengths. These linear correlations allow one to make reasonable estimates for the hydrolysis constants of +2, +3, and +4 metals from 0 to 300°C in dilute solutions and 0 to 100°C to 5 m in NaCl solutions. These correlations in pure water are related to the differences between the free energies of the free ion and complexes being almost equal $$ \Updelta {\text{G}}^\circ \left( {{\text{Al}}^{3 + } } \right) - \Updelta {\text{G}}^\circ \left( {{\text{Al}}\left( {\text{OH}} \right)_{j}^{{\left( {3 - j} \right)}} } \right) \cong \Updelta {\text{G}}^\circ \left( {{\text{M}}^{n + } } \right) - \Updelta {\text{G}}^\circ \left( {{\text{M}}\left( {\text{OH}} \right)_{j}^{{\left( {n - j} \right)}} } \right) $$ The correlation at higher temperatures is a result of a similar relationship between the enthalpies of the free ions and complexes $$ \Updelta {\text{H}}^\circ \left( {{\text{Al}}^{3 + } } \right) - \Updelta {\text{H}}^\circ \left( {{\text{Al}}\left( {\text{OH}} \right)_{j}^{3 - j} } \right) \cong \Updelta {\text{H}}^\circ \left( {{\text{M}}^{n + } } \right) - \Updelta {\text{H}}^\circ \left( {{\text{M}}\left( {\text{OH}} \right)_{j}^{n - j} } \right) $$ The correlations at higher ionic strengths are the result of the ratio of the activity coefficients for Al(III) being almost equal to that of the metal. $$ \gamma \left( {{\text{M}}^{n + } } \right)/\gamma \left( {{\text{M}}\left( {\text{OH}} \right)_{j}^{n - j} } \right) \cong \gamma \left( {{\text{Al}}^{3 + } } \right)/\gamma \left( {{\text{Al}}\left( {\text{OH}} \right)_{j}^{3 - j} } \right) $$ The results of this study should be useful in examining the speciation of metals as a function of pH in natural waters (e.g. hydrothermal fresh waters and NaCl brines).     

Multiple-pumped-well aquifer test to determine the anisotropic properties of a karst limestone aquifer in Pasco County, Florida, USA

Groundwater-level data from an aquifer test utilizing four pumped wells conducted in the South Pasco wellfield in Pasco County, Florida, USA, were analyzed to determine the anisotropic transmissivity tensor, storativity, and leakance in the vicinity of the wellfield. A weighted least-squares procedure was used to analyze drawdowns measured at eight observation wells, and it was determined that the major axis of transmissivity extends approximately from north to south and the minor axis extends approximately from west to east with an angle of anisotropy equal to N4.54°W. The transmissivity along the major axis ${\left( {T_{{\xi \xi }} } \right)}$ is 14,019 m² day^–1, and the transmissivity along the minor axis ${\left( {T_{{\eta \eta }} } \right)}$ is 4,303 m² day^–1. The equivalent transmissivity $T_{e} = {\left( {T_{{\xi \xi }} T_{{\eta \eta }} } \right)}^{{1 \mathord{\left/ {\vphantom {1 2}} \right. \kern-0em} 2}} = 7,767{{\text{m}}^{2} } \mathord{\left/ {\vphantom {{{\text{m}}^{2} } {{\text{day}}^{{ - {\text{1}}}} }}} \right. \kern-0em} {{\text{day}}^{{ - {\text{1}}}} }$ , and the ratio of anisotropy is 3.26. The storativity of the aquifer is 7.52?×?10^?4, and the leakance of the overlying confining unit is 1.37?×?10^?4 day^?1. The anisotropic properties determined for the South Pasco wellfield in this investigation confirm the results of previous aquifer tests conducted in the wellfield and help to quantify the NW–SE to NE–SW trends for regional fracture patterns and inferred solution-enhanced flow zones in west-central Florida.     

The ferric-ferrous ratio of natural silicate liquids equilibrated in air

Results of chemical analyses of glasses produced in 46 melting experiments in air at 1,350° C and 1,450° C on rocks ranging in composition from nephelinite to rhyolite have been combined with other published data to obtain an empirical equation relating in \((X_{{\text{Fe}}_{\text{2}} {\text{O}}_{\text{3}} }^{{\text{liq}}} /X_{{\text{FeO}}}^{{\text{liq}}} )\) to T, \(\ln f_{{\text{O}}_{\text{2}} } \) and bulk composition. The whole set of experimental data range over 1,200–1,450° C and oxygen fugacities of 10^?9.00 to 10^?0.69 bars, respectively. The standard errors of temperature and \(\log _{10} f_{{\text{O}}_{\text{2}} } \) predictions from this equation are 52° C and 0.5 units, respectively, for 186 experiments.     

Dehydration kinetics of antigorite using in situ high-temperature infrared microspectroscopy

The dehydration kinetics of serpentine was investigated using in situ high-temperature infrared microspectroscopy. The analyzed antigorite samples at room temperature show relatively sharp bands at around 3,655–3,660 cm^?1 (band 1), 3,570–3,595 cm^?1 (band 2), and 3,450–3,510 cm^?1 (band 3). Band 1 corresponds to the Mg–OH bond, and bands 2 and 3 correspond to OH associated with the substitution of Al for Si. Isothermal kinetic heating experiments at temperatures ranging from 625 to 700 °C showed a systematic decrease of the OH band absorbance with heating duration. The one-dimensional diffusion was found to provide the best fit to the experimental data, and diffusion coefficients were determined with activation energies of 219 ± 37 kJ mol^?1 for the total water band area, 245 ± 46 kJ mol^?1 for band 1, 243 ± 57 kJ mol^?1 for band 2, and 256 ± 53 kJ mol^?1 for band 3. The results indicate that the dehydration process is controlled by one-dimensional diffusion through the tetrahedral geometry of serpentine. Fluid production rates during antigorite dehydration were calculated from kinetic data and range from 3 × 10^?4 to 3 × 10^?5  $ {\text{m}}_{\text{fluid}}^{ 3} \,{\text{m}}_{\text{rock}}^{ - 3} \,{\text{s}}^{ - 1} $ . The rates are high enough to provoke hydraulic rupture, since the relaxation rates of rocks are much lower than these values. The results suggest that the rapid dehydration of antigorite can trigger an intermediate-depth earthquake associated with a subducting slab.     

Hydrothermal alteration and zeolitization of the Fohberg phonolite,Kaiserstuhl Volcanic Complex,Germany

The subvolcanic Fohberg phonolite (Kaiserstuhl Volcanic Complex, Germany) is an economic zeolite deposit, formed by hydrothermal alteration of primary magmatic minerals. It is mined due to the high (>40 wt%) zeolite content, which accounts for the remarkable zeolitic physicochemical properties of the ground rock. New mineralogical and geochemical studies are carried out (a) to evaluate the manifestation of hydrothermal alteration, and (b) to constrain the physical and chemical properties of the fluids, which promoted hydrothermal replacement. The alkaline intrusion is characterized by the primary mineralogy: feldspathoid minerals, K-feldspar, aegirine–augite, wollastonite, and andradite. The rare-earth elements-phase götzenite is formed during the late-stage magmatic crystallization. Fluid-induced re-equilibration of feldspathoid minerals and wollastonite caused breakdown to a set of secondary phases. Feldspathoid minerals are totally replaced by various zeolite species, calcite, and barite. Wollastonite breakdown results in the formation of various zeolites, calcite, pectolite, sepiolite, and quartz. Zeolites are formed during subsolidus hydrothermal alteration (<150 °C) under alkaline conditions. A sequence of Ca–Na-dominated zeolite species (gonnardite, thomsonite, mesolite) is followed by natrolite. The sequence reflects an increase in \(\log [(a_{{{\text{Na}}^{ + } }} )/(a_{{{\text{H}}^{ + } }} )]\) and decrease in \(\log [(a_{{{\text{Ca}}^{2 + } }} )/(a_{{{\text{H}}^{ + } }}^{2} )]\) of the precipitating fluid. Low radiogenic ⁸⁷Sr/⁸⁶Sr values indicate a local origin of the elements necessary for secondary mineral formation from primary igneous phases. In addition, fractures cut the intrusive body, which contain zeolites, followed by calcite and a variety of other silicates, carbonates, and sulfates as younger generations. Stable isotope analysis of late-fracture calcite indicates very late circulation of meteoric fluids and mobilization of organic matter from surrounding sedimentary units.     

Impact of land use change on groundwater quality in a typical karst watershed of southwest China: a case study of the Xiaojiang watershed,Yunnan Province

The impact of land-use change on the quality of groundwater in the Xiaotjiang watershed, China was assessed for the period 1982–2004. Groundwater samples were collected from 30 monitoring points across the watershed, and were representative of the various changes, determined by remote sensing and geographical information systems. The results indicate that 610 km² (60% of the total watershed area) were subject to land-use change during the period. The most important changes were the conversion of 135 km² of forested land to cultivated land, and 211 km² of unused land to cultivated land. The main impact was ascribed to diffuse pollution from fertilizers applied to newly cultivated land, and from building development. Overall the groundwater pH value was significantly increased, as were the concentrations of ions , , , , and Cl⁻ in groundwater whilst the concentrations of Ca²⁺ and declined. More precisely, in the regions where forested land and unused land were converted into cultivated land, the pH value and the concentrations of Mg²⁺, , , , , Cl⁻ increased whilst the concentrations of Ca²⁺ and declined. However in the region where cultivated land was converted into construction land, the pH value and the concentrations of Ca²⁺, Mg²⁺, , , , , , Cl⁻ increased.

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Résumé  L’impact des changements de l’utilisation du territoire sur la qualité de l’eau souterraine dans le bassin versant de Xiaojiang, en Chine, a été évalué de 1982 à 2004. Des échantillons d’eau souterraine ont été récoltés à partir de 30 points d’observation éparpillés sur le bassin, représentant les divers changements déterminés par télédétection et système d’information géographique. Les résultats indiquent que 610 km² (soit 60% de la surface du bassin) ont été sujets à des modifications de l’utilisation du territoire sur cette période. Les changements les plus importants furent la conversion de 135 km² de forêt et 211 km² de terres inutilisées en terres cultivées. Le principal impact est attribué à la pollution diffuse des engrais utilisés en agriculture et pour les batiments. De manière générale le pH de l’eau souterraine a augmenté significativement, ainsi que les concentrations des ions , , , , et Cl⁻, tandis que les concentration en Ca²⁺ et ont diminué. Plus précisément dans les régions transformées en terres cultivées, la valeur du pH et les concentrations en Mg²⁺, , , , , Cl⁻ ont augmenté tandis que les concentrations en Ca²⁺ et ont diminué. Toutefois dans les régions cultivées converties en zones de construction, le pH et les concentrations en Ca²⁺, Mg²⁺, , , , , , Cl⁻ ont augmenté.

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Resumen  El impacto del cambio en uso de la tierra en la calidad del agua en la cuenca Xiaojiang, China fue evaluado para el periodo 1982–2004. Muestras de agua subterránea fueron tomadas de 30 puntos de monitoreo a través de la cuenca, y fueron representativas de los múltiples cambios, determinados por sensores remotos y sistemas de información geográfica. Los resultados indican que 610 km² (60% del área total de la cuenca) estaban sujetos a cambios de uso de la tierra durante el periodo estudiado. Los cambios más importantes fueron la conversión de 135 km² de bosques a tierra cultivada, y 211 km² de tierra sin uso (ociosa) a tierra cultivada. El impacto principal fue causado por contaminación difusa de fertilizantes aplicados a la tierra recientemente cultivada, y a desarrollo de construcciones. En general el pH en agua subterránea creció significantemente, al igual que las concentraciones de los iones , , , , y Cl⁻ en agua subterránea mientras que las concentraciones de Ca²⁺ y decrecieron. Mas precisamente, en las regiones donde bosque y tierra ociosa fueron convertidas en tierra cultivada, el valor de pH y las concentraciones de Mg²⁺, , , , , Cl⁻ crecieron mientras las concentraciones de Ca²⁺ y decrecieron. Sin embargo en la región donde tierra cultivada fue convertida en construcciones, el valor de pH y las concentraciones de Ca²⁺, Mg²⁺, , , , , , Cl⁻ crecieron.

     

Adsorption kinetics of chromium(III) removal from aqueous solutions using natural red earth

Laboratory-scale-simulated experiments were carried out using Cr(III) solutions to identify the Cr(III) retention behavior of natural red earth (NRE), a natural soil available in the northwestern coastal belt of Sri Lanka. The effects of solution pH, initial Cr(III) concentration and the contact time were examined. The NRE showed almost 100 % Cr(III) adsorption within the first 90 min. [initial [Cr(III)] = 0.0092–0.192 mM; initial pH 4.0–9.0]. At pH 2 (298 K), when particle size ranged from 125 to 180 μm the Cr(III) adsorption data were modeled according to Langmuir convention assuming site homogeneity. The pH-dependent Cr(III) adsorption data were quantified by diffused layer model assuming following reaction stoichiometries: $$ \begin{aligned} 2\, {>}{\text{AlOH}}_{{({\text{s}})}} + {\text{ Cr }}\left( {\text{OH}} \right)_{{ 2\,({\text{aq}})}}^{ + } \, \to \, \left( { {>}{\text{AlO}}} \right)_{ 2} {\text{Cr}}_{{({\text{s}})}}^{ + } + {\text{ 2H}}_{ 2} {\text{O}} \quad {\text{log K 15}}. 5 6\\ 2\, {>}{\text{FeOH}}_{{({\text{s}})}} + {\text{ Cr}}\left( {\text{OH}} \right)_{{ 2\,({\text{aq}})}}^{ + } \, \to \, \left( { {>}{\text{FeO}}} \right)_{ 2} {\text{Cr}}_{{({\text{s}})}}^{ + } + {\text{ 2H}}_{ 2} {\text{O}}\quad {\text{log K 5}}.0 8.\\ \end{aligned} $$ The present data showed that NRE can effectively be used to mitigate Cr(III) from aqueous solutions and this method is found to be simple, effective, economical and environmentally benign.     

Spatial control of groundwater contamination,using principal component analysis

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

Later stages of evolution of an epithermal system: Au–Ag mineralizations at Apigania Bay, Tinos Island, Cyclades, Hellas, Greece

Precious metals accompany all types of epithermal deposits. In general, the largest of these deposits occur in intrusive or extrusive rocks of alkaline or calc-alkaline affinity. The Apigania Bay vein system and Au–Ag mineralization is hosted in Mesozoic marbles and schists, and is composed primarily of five nearly parallel, high-angle quartz veins that extend for at least 200 m. Gold–silver mineralization, in association with more than thirty ore and vein minerals, is developed in three stages and occurs at the contact of marbles and schists. Zones of epidote–chlorite–calcite and sericite–albite alteration are associated with precious metal-bearing milky and clear quartz veins. Fluid inclusion studies suggest that hydrothermal mineralization was deposited under hydrostatic pressures of ~100 bars, at temperature of 120–235°C, from low to moderate, calcium-bearing, saline fluids of 0.2 to 6.8 equiv. wt.% NaCl. Calculated isotope compositions (δ¹⁸O?=??4.7‰ to 1.7‰ and δD?=??120‰ to ?80‰) for waters in equilibrium with milky and clear quartz are consistent with mixing with dilute, low temperature meteoric ore fluids. Calculated δ ¹³C_CO2 (0.6‰ to 1.1‰) and δ ³⁴S_H2S (?7.3 to ?0.3‰) compositions of the ore fluids indicate exchange, in an open system, with a metasedimentary source. Gold and silver deposition was associated with degassing of hydrogen due to intense uplift of the mineralizing area. The physicochemical conditions of mineralization stages I to III range between 200°C and 150°C, $f_{{\text{S}}_2 } = 10^{ - 18.1} $ to 10^?16.8, $f_{{\text{O}}_2 } = 10^{ - 44.0} $ to 10^?41.5, pH?=?6.9 to7.6, $f_{{\text{H}}_{\text{2}} {\text{S}}} = 10^{ - 3.4} $ to 10^?2.6 and $a_{{\text{H}}_{\text{2}} {\text{S}}} = 10^{ - 2.7} $ to 10^?2.6. Apigania Bay could be possibly considered the latest evolutional phase of Tinos hydrothermal system.